Thermal Processes in The Metallurgical Industry

Thermal processes in the metallurgical industry
Suggested Revisions by Environment Canada including comments arising from discussions in Geneva at EGB II 1 in 2005 and comments submitted by February 2006 to the Stockholm Secretariat. 28.April.2006
Guidelines on BAT and Guidance on BEP
Environment Canada Revision, April 28, 2006
Table of contents
TABLE OF CONTENTS.................................................................................................................................3 V.D Thermal processes in the metallurgical industry:............................................................................5 SUMMARIES BY SOURCE CATEGORIES PART III OF ANNEX C ....................................................................6 VI.B. Thermal processes in the metallurgical industry not mentioned in Annex C, Part II: ..................6 SECTION V 8
GUIDANCE/GUIDELINES BY SOURCE CATEGORY: SOURCE CATEGORIES IN PART II OF ANNEX C..................................................................................8 V.D. THERMAL PROCESSES IN THE METALLURGICAL INDUSTRY...................................................................8 (i) Secondary copper production...............................................................................................................8 (ii) Sinter plants in the iron and steel industry........................................................................................21 (iii) Secondary aluminium production.....................................................................................................34 (iv) Secondary zinc production................................................................................................................47 SECTION VI. GUIDANCE/GUIDELINES BY SOURCE CATEGORY SOURCE CATEGORIES IN PART III OF ANNEX C..............................................................................57 VI.B THERMAL PROCESSES IN THE METALLURGICAL INDUSTRY NOT MENTIONED IN ANNEX C, PART II. .58 (i) Secondary lead production.................................................................................................................58 (ii) Primary aluminium production.........................................................................................................67 (iii) Magnesium production.....................................................................................................................77 (iv) Secondary steel production...............................................................................................................89 (v) Primary base metals smelting..........................................................................................................106
Section IV. Compilation of summaries of Sections V and VI V.D Thermal processes in the metallurgical industry:
(i) Secondary copper production
Secondary copper smelting involves copper production from copper scrap, sludge, computer and electronic scrap, and drosses from refineries. Processes involved in copper production are feed pretreatment, smelting, alloying and casting. Organic materials in feed such as oils, plastics and coatings, and temperatures between 250 C and 500 C, may give rise to chemicals listed in Annex C of the Stockholm Convention. Best available techniques include presorting, cleaning feed materials, maintaining temperatures above 850 C, utilizing afterburners with rapid quenching, activated carbon adsorption and fabric filter dedusting. Achievable performance levels for secondary copper smelters: < 0.51 ng I-TEQ/Nm3.1
(ii) Sinter plants in the iron and steel industry

Sinter plants in the iron and steel industry are a pretreatment step in the production of iron whereby fine particles of iron ores and, in some plants, secondary iron oxide wastes (collected dusts, mill scale) are agglomerated by combustion. Sintering involves the heating of fine iron ore with flux and coke fines or coal to produce a semi-molten mass that solidifies into porous pieces of sinter with the size and strength characteristics necessary for feeding into the blast furnace. PCDD and PCDF appear to be formed in the iron sintering process via de novo synthesis. PCDF generally dominate in the waste gas from sinter plants. The PCDD/PCDF formation mechanism appears to start in the upper regions of the sinter bed shortly after ignition, and then the dioxins, furans and other compounds condense on cooler burden beneath as the sinter layer advances along the sinter strand towards the burn-through point. Primary measures identified to prevent or minimize the formation of PCDD/PCDF during iron sintering include the stable and consistent operation of the sinter plant, continuous parameter monitoring, recirculation of waste gases, minimization of feed materials contaminated with persistent organic pollutants or contaminants leading to formation of such pollutants, and feed material preparation. Secondary measures identified to control or reduce releases of PCDD/PCDF from iron sintering include adsorption/absorption (for example, activated carbon injection) and high-efficiency dedusting, as well as fine wet scrubbing of waste gases combined with effective treatment of the scrubber waste waters and disposal of waste-water sludge in a secure landfill. The achievable performance level for an iron sintering plant operating according to best available techniques: < 0.2 ng TEQ/Nm3.
(iii) Secondary aluminium production

Secondary aluminium smelting involves the production of aluminium from used aluminium products processed to recover metals by pretreatment, smelting and refining. Fuels, fluxes and alloys are used, while magnesium removal is practised by the addition of chlorine, aluminium chloride or chlorinated organics. Chemicals listed in Annex C of the
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1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines. The operating oxygen concentration conditions of exhaust gases are used for metallurgical sources. Guidelines on BAT and Guidance on BEP Environment Canada Revision, April 28, 2006
Stockholm Convention probably result from organics in the feed, chlorine compounds and temperatures between 250 C and 500 C. Best available techniques include high-temperature advanced furnaces, oil- and chlorine-free feeds (if alternatives are available), afterburners with rapid quench, activated carbon adsorption and dedusting fabric filters. The achievable performance level for secondary aluminium smelters: < 0. 51 ng I-TEQ/Nm3.
(iv) Secondary zinc production

Secondary zinc smelting involves the production of zinc from materials such as dusts from copper alloy production and electric arc steel making, and residues from steel scrap shredding and galvanizing processes. Production processes include feed sorting, pretreatment cleaning, crushing, sweating furnaces to 364 C, melting furnaces, refining, distillation and alloying. Oils and plastics in feed, and temperatures between 250 C and 500 C, may give rise to chemicals listed in Annex C of the Stockholm Convention. Best available techniques include feed cleaning, maintaining temperatures above 850 C, fume and gas collection, afterburners with quenching, activated carbon adsorption and fabric filter dedusting. The achievable performance level for secondary zinc smelters: < 0.51 ng I-TEQ/Nm3.
Summaries by source categories Part III of Annex C

VI.B. Thermal processes in the metallurgical industry not mentioned in Annex C, Part II:
(i) Secondary lead production
Secondary lead smelting involves the production of lead and lead alloys, primarily from scrap automobile batteries, and also from other used lead sources (pipe, solder, drosses, lead sheathing). Production processes include scrap pretreatment, smelting and refining. Oils and plastics in feed, and temperatures between 250 and 500 C, may give rise to chemicals listed in Annex C of the Stockholm Convention. Best available techniques include the use of plastic-free and oil-free feed material, high furnace temperatures above 850 C, effective gas collection, afterburners and rapid quench, activated carbon adsorption, and dedusting fabric filters. The achievable performance levels for secondary lead smelters: < 0.1 ng I-TEQ/Nm 3.
(ii) Primary aluminium production

Primary aluminium is produced directly from the mined ore, bauxite. The bauxite is refined into alumina through the Bayer process. The alumina is reduced into metallic aluminium by electrolysis through the Hall-Hroult process (either using self-baking anodes Sderberg anodes or using prebaked anodes). Primary aluminium production is generally thought not to be a significant source of chemicals listed in Annex C of the Stockholm Convention. However, contamination with PCDD and PCDF is possible through the graphite-based electrodes used in the electrolytic smelting process. Possible techniques to reduce the production and release of chemicals listed in Annex C from the primary aluminium sector include improved anode production and control, and using advanced smelting processes. The achievable performance level in this sector should be < 0.1 ng TEQ/Nm 3.
(iii) Magnesium production
SECTION V. Guidelines/guidance by source category: Part II of Annex C
Magnesium is produced either from raw magnesium chloride with molten salt electrolysis, or magnesium oxide reduction with ferrosilicon or aluminium at high temperatures, as well as through secondary magnesium recovery (for example, from asbestos tailings). The addition of chlorine or chlorides, the presence of carbon anodes and high process temperatures in magnesium production can lead to the formation of chemicals listed in Annex C of the Stockholm Convention and their emission in air and water. Alternative techniques may include the elimination of the carbon source by using non-graphite anodes, and the application of activated carbon. However, achievable performance depends on the type of process and controls utilized.
(iv) Secondary steel production

Secondary steel is produced through direct smelting of ferrous scrap using electric arc furnaces. The furnace melts and refines a metallic charge of scrap steel to produce carbon, alloy and stainless steels at non-integrated steel mills. Ferrous feed materials may include scrap, such as shredded vehicles and metal turnings, or direct reduced iron. Chemicals listed in Annex C of the Stockholm Convention, such as PCDD and PCDF, appear to be most probably formed in the electric arc furnace steel-making process via de novo synthesis by the combustion of non-chlorinated organic matter such as polystyrene, coal and particulate carbon in the presence of chlorine donors. Many of these substances are contained in trace concentrations in the steel scrap or are process raw materials such as injected carbon. Primary measures include adequate off-gas handling and appropriate off-gas conditioning to prevent conditions leading to de novo synthesis formation of PCDD/PCDF. This may include postcombustion afterburners, followed by rapid quench of off-gases. Secondary measures include adsorbent injection (for example, activated carbon) and high-level dedusting with fabric filters. The achievable performance level using best available techniques for secondary steel production is < 0.1 ng I-TEQ/Nm3.
(v) Primary base metals smelting

Primary base metals smelting involves the extraction and refining of nickel, lead, copper, zinc and cobalt. Generally, primary base metals smelting facilities process ore concentrates. Most primary smelters have the technical capability to supplement primary concentrate feed with secondary materials (for example, recyclables). Production techniques may include pyrometallurgical or hydrometallurgical processes. Chemicals listed in Annex C of the Stockholm Convention are thought to originate through high-temperature thermal metallurgical processes; hydrometallurgical processes are therefore not considered in this section on best available techniques for primary base metals smelting. Available information on emissions of PCDD and PCDF from a variety of source sectors (for example, incinerators, steel electric arc furnaces, iron sintering plants) suggests that process technologies and techniques, and associated off-gas conditioning, can influence the formation and subsequent release of PCDD/PCDF. Consideration should be given to hydrometallurgical processes, where technically feasible, as alternatives to pyrometallurgical processes when considering proposals for the construction and commissioning of new base metals smelting facilities or processes. Primary measures include the use of hydrometallurgical processes, quality control of feed materials and scrap to minimize contaminants leading to PCDD/PCDF formation, effective process control to avoid conditions leading to PCDD/PCDF formation, and use of flash smelting technology. Identified secondary measures include high-efficiency gas cleaning and conversion of sulphur dioxide to sulphuric acid, effective fume and gas collection and high-efficiency dust removal. The achievable performance level using best available techniques for base metals smelters is < 0.1 ng I-TEQ/Nm3.
Section V Guidance/guidelines by source category: Source categories in Part II of Annex C

V.D. Thermal processes in the metallurgical industry
(i) Secondary copper production
Summary
Secondary copper smelting involves copper production from copper scrap, sludge, computer and electronic scrap, and drosses from refineries. Processes involved in copper production are feed pretreatment, smelting, alloying and casting. Organic materials in feed such as oils, plastics and coatings, and temperatures between 250 and 500 C, may give rise to chemicals listed in Annex C of the Stockholm Convention. Best available techniques include: presorting, cleaning feed materials, maintaining temperatures above 850 C, utilizing afterburners with rapid quenching, activated carbon adsorption and fabric filter dedusting. Achievable performance levels for secondary copper smelters: < 0.51 ng I-TEQ/Nm3.
1.
Process description
Secondary copper smelting involves pyrometallurgical processes dependent on the copper content of the feed material, size distribution and other constituents. Feed sources are copper scrap, sludge, computer scrap, drosses from refineries and semi-finished products. These materials may contain organic materials like coatings or oil, and installations take this into account by using de-oiling and decoating methods or by correct design of the furnace and abatement system (European Commission 2001, p. 201202). Copper can be infinitely recycled without loss of its intrinsic properties. The quoted material that follows is from Secondary Copper Smelting, Refining and Alloying , a report of the Environmental Protection Agency of the United States of America (EPA 1995). Secondary copper recovery is divided into 4 separate operations: scrap pre-treatment, smelting, alloying, and casting. Pre-treatment includes the cleaning and consolidation of scrap in preparation for smelting. Smelting consists of heating and treating the scrap for separation and purification of specific metals. Alloying involves the addition of 1 or more other metals to copper to obtain desirable qualities characteristic of the combination of metals. Scrap pre-treatment may be achieved through manual, mechanical, pyrometallurgical, or hydrometallurgical methods. Manual and mechanical methods include sorting, stripping, shredding, and magnetic separation. Pyrometallurgical pre-treatment may include sweating (the separation of different metals by slowly staging furnace air temperatures to liquefy each metal separately), burning insulation from copper wire, and drying in rotary kilns to volatilize oil and other organic compounds. Hydrometallurgical pre-treatment methods include flotation and leaching to recover copper from slag. Leaching with sulphuric acid is used to recover copper from slime, a byproduct of electrolytic refining.
Guidelines on BAT and Guidance on BEP Environment Canada Revision, April 28, 2006
Smelting of low-grade copper scrap begins with melting in either a blast or a rotary furnace, resulting in slag and impure copper. If a blast furnace is used, this copper is charged to a converter, where the purity is increased to about 80 to 90 percent, and then to a reverberatory furnace, where copper of about 99 percent purity is achieved. In these firerefining furnaces, flux is added to the copper and air is blown upward through the mixture to oxidize impurities. These impurities are then removed as slag. Then, by reducing the furnace atmosphere, cuprous oxide (CuO) is converted to copper. Fire-refined copper is cast into anodes, which are used during electrolysis. The anodes are submerged in a sulphuric acid solution containing copper sulphate. As copper is dissolved from the anodes, it deposits on the cathode. Then the cathode copper, which is as much as 99.99 percent pure, is extracted and recast. The blast furnace and converter may be omitted from the process if average copper content of the scrap being used is greater than about 90 percent. In alloying, copper-containing scrap is charged to a melting furnace along with 1 or more other metals such as tin, zinc, silver, lead, aluminium, or nickel. Fluxes are added to remove impurities and to protect the melt against oxidation by air. Air or pure oxygen may be blown through the melt to adjust the composition by oxidizing excess zinc. The alloying process is, to some extent, mutually exclusive of the smelting and refining processes described above that lead to relatively pure copper. The final recovery process step is the casting of alloyed or refined metal products. The molten metal is poured into moulds from ladles or small pots serving as surge hoppers and flow regulators. The resulting products include shot, wire bar, anodes, cathodes, ingots, or other cast shapes. Figure 1 expressespresents the process in diagrammatic form.
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Figure 1. Secondary copper smelting

Input
Lower grade residues, fluxes, coke, oxygen Black copper
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Potential output
Smelting reduction
Slag
Air emissions CO Dust, metal oxide fume recycled Dioxins, volatile organic compounds Land emissions Furnace linings Land releasesemissions, filter dust (recycled), furnace linings
Flux, scrap, air, oxygen

Converter copper
Converter
Slag
Clean scrap, reductant, air
Anode furnace
Air emissions:, SO2, metals, dust
Anodes
Anode scrap
Electrolytic refining
Ni, etc.
Final slag
Slime
Cathodes
Construction
Particulate matter
Input
Lower grade residues, fluxes, coke, oxygen Black copper
Potential output Smelting reduction

Slag Air emissions CO Dust, metal oxide fume recycled Dioxins, volatile organic compounds Land emissions Furnace linings Land releasesemissions, filter dust (recycled), furnace linings Slag Air emissions:, SO2, metals, dust
Flux, scrap, air, oxygen

Converter copper
Converter
Clean scrap, reductant, air
Anode furnace
Anodes
Anode scrap
Electrolytic refining
Ni, etc.
Final slag
Slime
Cathodes
Construction
Particulate matter
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Source: European Commission 2001, p. 217
Artisinal and small enterprise metal recovery activities may be significant, particularly in developing countries and countries with economies in transition. These activities may contribute significantly to pollution and have negative health impacts. For example, artisinal zinc smelting is an important atmospheric mercury emission source. The technique used to smelt both zinc and mercury is simple; the ores are heated in a furnace for a few hours, and zinc metal and liquid mercury are produced. In many cases there are no pollution control devices employed at all during the melting process. Other metals that are known to be produced by artisinal and small enterprise metal recovery activities include antimony, iron, lead, manganese, tin, tungsten, gold, silver, copper, and aluminum.
These are not considered best available techniques or best environmental practices. However, as a minimum, appropriate ventilation and material handling should be carried out.
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2.
Sources of chemicals listed in Annex C of the Stockholm Convention
The formation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) is probably due to the presence of chlorine from plastics and trace oils in the feed material. As copper is the most efficient metal to catalyse PCDD/PCDF formation, copper smelting is a concern.
2.1.
General information on emissions from secondary copper smelters
Airborne emissions consist of nitrogen oxides (NO x), carbon monoxide (CO), dust and metal compounds, organic carbon compounds and PCDD/PCDF. Off-gases usually contain little or no sulphur dioxide (SO2), provided sulphidic material is avoided. Scrap treatment and smelting generate the largest quantity of atmospheric emissions. Dust and metal compounds are emitted from most stages of the process and are more prone to fugitive emissions during charging and tapping cycles. Particulate matter is removed from collected and cooled combustion gases by electrostatic precipitators or fabric filters. Fume collection hoods are used during the conversion and refining stages due to the batch process, which prevents a sealed atmosphere. NO x is minimized in low-NOx burners, while CO is burnt in hydrocarbon afterburners. Burner control systems are monitored to minimize CO generation during smelting (European Commission 2001, p. 218229).
2.2.
Emissions of PCDD/PCDF to air
PCDD/PCDF are formed during base metal smelting through incomplete combustion or by de novo synthesis when organic and chlorine compounds such as oils and plastics are present in the feed material. Secondary feed often consists of contaminated scrap. The process is described in European Commission 2001, p. 133: PCDD/PCDF or their precursors may be present in some raw materials and there is a possibility of de-novo synthesis in furnaces or abatement systems. PCDD/PCDF are easily adsorbed onto solid matter and may be collected by all environmental media as dust, scrubber solids and filter dust. The presence of oils and other organic materials on scrap or other sources of carbon (partially burnt fuels and reductants, such as coke), can produce fine carbon particles which react with inorganic chlorides or organically bound chlorine in the temperature range of 250 to 500 C to produce PCDD/PCDF. This process is known as de-novo synthesis and is catalysed by the presence of metals such as copper or iron. Although PCDD/PCDF are destroyed at high temperature (above 850 C) in the presence of oxygen, the process of de-novo synthesis is still possible as the gases are cooled through the reformation window. This window can be present in abatement systems and in cooler parts of the furnace e.g. the feed area. Care taken in the design of cooling systems to minimise the residence time in the window is practised to prevent de-novo synthesis.
2.3.
Releases to other media
Process, surface and cooling water can be contaminated by suspended solids, metal compounds and oils. Most process and cooling water is recycled. Waste-water treatment methods are used before discharge. By-products and residues are recycled in the process as these contain recoverable quantities of copper and other non-ferrous metals. Waste material generally consists of acid slimes which are disposed of on site. Care must be taken to ensure the proper disposal of slimes in order to minimize copper and dioxins exposure to the environment.
3.
Recommended processes
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Process design and configuration is influenced by the variation in feed material and quality control. Processes considered as best available techniques for smelting and reduction include the blast furnace, the mini-smelter (totally enclosed), the sealed submerged electric arc furnace, and ISA smelt. The top-blown rotary furnace (totally enclosed) and Pierce-Smith converter are best available techniques for converting. The submerged electric arc furnace is sealed and is cleaner than other designs if the gas extraction system is adequately designed and sized. The use of blast furnaces for scrap melting is becoming less common due to difficulties in economically preventing pollution. Shaft furnaces without a coal/coke feed are being used instead (Personal Communication, February 2006). Clean copper scrap devoid of organic contamination can be processed using the reverberatory hearth furnace, the hearth shaft furnace or Contimelt process. These are considered to be best available techniques in configurations with suitable gas collection and abatement systems. No information is available on alternative processes to smelting for secondary copper processing.
4.
4.1.
Primary and secondary measures

Primary measures
Primary and secondary measures of PCDD/PCDF reduction and elimination are discussed below. Primary measures are regarded as pollution prevention techniques to reduce or eliminate the generation and release of persistent organic pollutants. Possible measures include: 4.1.1.Presorting of feed material The presence of oils, plastics and chlorine compounds in the feed material should be avoided to reduce the generation of PCDD/PCDF during incomplete combustion or by de novo synthesis. Feed material should be classified according to composition and possible contaminants. Storage, handling and pretreatment techniques will be determined by feed size distribution and contamination. Methods to be considered are (European Commission 2001, p. 232): Oil removal from feed (for example, thermal decoating and de-oiling processes followed by afterburning to destroy any organic material in the off-gas); Use of milling and grinding techniques with good dust extraction and abatement. The resulting particles can be treated to recover valuable metals using density or pneumatic separation; Elimination of plastic by stripping cable insulation (for example, possible cryogenic techniques to make plastics friable and easily separable); Sufficient blending of material to provide a homogeneous feed in order to promote steady-state conditions. Additional techniques for oil removal are solvent use and caustic scrubbing. Cryogenic stripping can be used to remove cable coatings. 4.1.2.Effective process control Process control systems should be utilized to maintain process stability and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation, such as maintaining furnace temperature above 850 C to destroy PCDD/PCDF. Ideally, PCDD/PCDF emissions would be monitored continuously to ensure reduced releases. Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (for example, waste incineration), but research is still developingongoing in this fieldfor applications to other sources. In the absence of continuous PCDD/PCDF monitoring, other variables such as temperature, residence time, gas
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compositionnents and fume collection damper controls should be continuously monitored and maintained to establish optimum operating conditions for the reduction of PCDD/PCDF emissions.
4.2.
Secondary measures
Secondary measures are pollution control techniques. These methods do not eliminate the generation of contaminants, but serve as a means to contain, and prevent or reduce emissions. 4.2.1.Fume and gas collection Air emissions should be controlled at all stages of the process, from material handling, smelting and material transfer points, to limitcontrol the potential emissions of PCDD/PCDF. Sealed furnaces are essential to contain fugitive emissions while permitting heat recovery and collecting off-gases for process recycling. Proper design of hooding and ductwork is essential to trap fumes. Furnace or reactor enclosures may be necessary. If primary extraction and enclosure of fumes is not possible, the furnace should be enclosed so that ventilation air can be extracted, treated and discharged. Roofline collection of fume should be avoided due to high energy requirements. The use of intelligent damper controls can improve fume capture, and reduce fan sizes and hence costs. Sealed charging cars or skips used with a reverberatory furnace can significantly reduce fugitive emissions to air by containing emissions during charging (European Commission 2001, p. 187 188). 4.2.2.High-efficiency dust removal The smelting process generates large quantitieshigh volumes of particulate matter with highlarge surface areas on which PCDD/PCDF can adsorb. These dusts with their associatedand metal compounds should be removed to reduce PCDD/PCDF emissions. Fabric filters are the most effective technique, althoughwhile wet or dry scrubbers and ceramic filters canare also to be considered. Collected dust must be treated in high-temperature furnaces to destroy PCDD/PCDF and recover metals. Fabric filter operations should be constantly monitored by devices to detect bag failure. Other relevant technology developments include online cleaning methods and use of catalytic coatings to destroy PCDD/PCDF (European Commission 2001, p. 139140). 4.2.3.Afterburners and quenching Afterburners (used post-combustion) should be operatused at a minimum temperature of 950 C to ensure full combustion of organic compounds (Hbner et al. 2000). This stage is to be followed by rapid quenching of hot gases to temperatures below 250 C. Oxygen injection in the upper portion of the furnace will also promote complete combustion (European Commission 2001, p. 189). It has been observed that PCDD/PCDF are formed, on a net basis, in the temperature range of 250 to 500 C. Theyse are destroyed above 850 C in the presence of oxygen. HowerverYet, de novo synthesis remainsis still possible as the gases are cooled through the reformation window present in abatement systems and cooler areas of the furnace if the necessary precursors and metal catalysts are still present. Proper operation of cooling systems to minimize thereformation time during which exhaust gases are within the de novo synthesis temperature range should be implemented (European Commission 2001, p. 133). 4.2.4.Adsorption on activated carbon Activated carbon treatment should be considered for PCDD/PCDF removal from smelter off-gases. Activated carbon possesses a large surface area on which PCDD/PCDF can be adsorbed. Off-gases can be treated with activated carbon using fixed or moving bed reactors, or by injection of carbon particulate into the gas stream followed by removal as a filter dust using high-efficiency dust removal systems such as fabric filters.
5.
5.1.
Emerging research
Catalytic oxidation
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Catalytic oxidation is an emerging technology used in waste incinerators to eliminate PCDD/PCDF emissions. This process should be considered by secondary base metals smelters as it has proven effective for PCDD/PCDF destruction in waste incinerators. However, catalytic oxidation can, be subject to poisoning from trace metals and other exhaust gas contaminants.;, vValidation work would be necessary before use of this process. Catalytic oxidation processes organic compounds into water, carbon dioxide (CO 2) and hydrochloric acid using a precious metal catalyst to increase the rate of reaction at 370 to 450 C. In comparison, incineration occurs typically at 980 C. Catalytic oxidation has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and >99% efficiency, and should be considered. Off- Particulate matter should be removed from exhaust gases should be dedusted prior to catalytic oxidation for optimum efficiency. This method is effective for the vapour phase of contaminants. The resulting hydrochloric acid is treated in a scrubber while the water and CO2 are released to the air after cooling (Parvesse 2001). Fabric filters used for dust removal can also be treated with a catalytic coating to promote oxidation of organic compounds at elevated temperature.
6.
Measure
Summary of measures
Description Various recommended smelting processes should be considered for new facilities Considerations Processes to be considered include: Blast furnace, mini-smelter, topblown rotary furnace, sealed submerged electric arc furnace, ISA smelt, and the Pierce-Smith converter Reverberatory hearth furnace, the hearth shaft furnace and Contimelt process to treat clean copper scrap devoid of organic contamination Other comments These are considered to be best available techniques in configuration with suitable gas collection and abatement. The submerged electric arc furnace is sealed and can be cleaner than other designs if the gas extraction system is adequately designed and sized
Table 1. Measures for recommended processes for new secondary copper smelters
Table 2. Summary of primary and secondary measures for secondary copper smelters
Measure Primary measures Presorting of feed material The presence of oils, plastics and chlorine compounds in the feed material should be avoided to reduce the generation of PCDD/PCDF during incomplete combustion or by de novo synthesis Processes to be considered include: Oil removal from feed material Use of milling and grinding techniques with good dust extraction and abatement Elimination of plastic by stripping cable insulation Effective process control Process control systems should be utilized to maintain process stability PCDD/PCDF emissions may be minimized by controlling other variables such as temperature, Continuous emissions sampling of PCDD/PCDF has been demonstrated for Thermal decoating and deoiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas Description Considerations Other comments

Measure Description and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation Considerations residence time, gas compositionnents and fume collection damper controls after having established optimum operating conditions for the reduction of PCDD/PCDF
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Other comments some sectors (for example, waste incineration), but research is still developongoing for applications to other sourcesin this field
Secondary measures Fume and gas collection Effective fume and off-gas collection should be implemented in all stages of the smelting process to capture PCDD/PCDF emissions Processes to be considered include: Sealed furnaces to contain fugitive emissions while permitting heat recovery and collecting off-gases. Furnace or reactor enclosures may be necessary Proper design of hooding and ductwork to trap fumes High-efficiency dust removal Dusts and metal compounds should be removed as this material possesses high surface area on which PCDD/PCDF easily adsorb. Removal of these dusts would contribute to the reduction of PCDD/PCDF emissions Afterburners should be used at temperatures > 950 C to ensure full combustion of organic compounds, followed by rapid quenching of hot gases to temperatures below 250 C Processes to be considered include: Fabric filters (most effective method) Wet/dry scrubbers and ceramic filters Dust removal is to be followed by afterburners and quenching. Collected dust must be treated in high-temperature furnaces to destroy PCDD/PCDF and recover metals Roofline collection of fume is to be avoided due to high energy requirements
Afterburners and quenching
Considerations include: PCDD/PCDF formation at 250500 C, and destruction > 850 C with O2 Requirement for sufficient O2 in the upper region of the furnace for complete combustion Need for proper design of cooling systems to minimize reformation time
De novo synthesis is still possible as the gases are cooled through the reformation window
Adsorption on activated carbon
Activated carbon treatment should be considered as this material possesses large surface area on which PCDD/PCDF can be adsorbed from smelter off-gases
Processes to be considered include: Treatment with activated carbon using fixed or moving bed reactors Injection of powdered carbon particulate into the gas stream followed by removal as a filter dust
Lime/carbon mixtures can also be used
Emerging research Catalytic Catalytic oxidation is an Considerations include: Catalytic oxidation has
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Measure oxidation

Description emerging technology for sources in this sector (demonstrated technology for incinerator applications) which should be considered due to its high efficiency and lower energy consumption. Catalytic oxidation transforms organic compounds into water, CO2 and hydrochloric acid using a precious metal catalyst Considerations Process efficiency for the vapour phase of contaminants Hydrochloric acid treatment using scrubbers while water and CO2 are released to the air after cooling Other comments been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and >99% efficiency. Particulate matter should be removed from Offexhaust gases should be dedusted prior to catalytic oxidation for optimum efficiency
7.
Achievable performance levels
The achievable performance level 2 for emissions of PCDD/PCDF from secondary copper smelters is < 0.51 ng I-TEQ/Nm3.
References
A.J. Gunson, Yue Jian, Artisanal Mining in The People's Republic of China, Mining, Minerals and Sustainable Development (MMSD), International Institute for Environment and Development (IIED), September 2001
EPA (United States Environmental Protection Agency). 1995. Secondary Copper Smelting, Refining and Alloying. Background Report AP-42, Section 12.9. www.epa.gov/ttn/chief/ap42/ch12/final/c12s09.pdf. European Commission. 2001. Reference Document on Best Available Techniques in the NonFerrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es.
Feng Xinbin, Qui Guangle, Li Guanghui, Li Ping, Wang Shaofeng, Mercury Emissions from Artisanal Zinc and Mercury Smelting in Guizhou, PR China, Goldschmidt Conference Abstracts 2005, The Geochemistry of Mercury, page A705
Hbner C., Boos R., Bohlmann J., Burtscher K. and Wiesenberger H. 2000. State-of-the-Art Measures for Dioxin Reduction in Austria. Vienna. www.ubavie.gv.at/publikationen/Mono/M116s.htm. Parvesse T. 2001. Controlling Emissions from Halogenated Solvents. Chemical Processing. Chemical Processing [Chem. Process.]. Vol. 64, no. 4, pp. 48-51. Apr 2001/. Personal communication from Expert Group Best Available Techniques Best Environmental
Practices, Finland Member, February 2006
1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines. The operating oxygen concentration conditions of exhaust gases are used for metallurgical sources.
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Personal communication, Member, Japan, Expert Group Meeting, 1 December, 2006
UNEP, Compilation of comments received from Parties and others on the draft Guidelines on Best Available Techniques and provisional Guidance on Best Environmental Practices, October 14, 2005
http://www.pops.int/documents/meetings/bat_bep/EGBATBEP1/meetingdocs/EGBATBE P_1_inf5.pdf UNEP Environment Program News Centre, http://www.unep.org/Documents.Multilingual/Default.asp? DocumentID=284&ArticleID=3204&l=en, as read on January 20, 2006 UNEP Environment Program News Centre, http://www.unep.org/Documents.Multilingual/Default.asp? DocumentID=284&ArticleID=3204&l=en, as read on January 20, 2006 Xinbin Feng, Xianwu Bi, Guangle Qiu, Guanghui Li, Shunlin Tang, Mercury Pollution in Guizhou, China - A status Report, http://pbc.eastwestcenter.org/abstracts2005/abstract2005fengxinbin.htm, as read on December 29th, 2005
20
21
(ii)
Sinter plants in the iron and steel industry
Summary
Sinter plants in the iron and steel industry are a pretreatment step in the production of iron whereby fine particles of iron ores and, in some plants, secondary iron oxide wastes (collected dusts, mill scale) are agglomerated by combustion. Sintering involves the heating of fine iron ore with flux and coke fines or coal to produce a semi-molten mass that solidifies into porous pieces of sinter with the size and strength characteristics necessary for feeding into the blast furnace. PCDD and PCDF appear to be formed in the iron sintering process via de novo synthesis. PCDF generally dominate in the waste gas from sinter plants. The PCDD/PCDF formation mechanism appears to start in the upper regions of the sinter bed shortly after ignition, and then the dioxins, furans and other compounds condense on cooler burden beneath as the sinter layer advances along the sinter strand towards the burn-through point. Primary measures identified to prevent or minimize the formation of PCDD/PCDF during iron sintering include the stable and consistent operation of the sinter plant, continuous parameter monitoring, recirculation of waste gases, minimization of feed materials contaminated with persistent organic pollutants or contaminants leading to formation of such pollutants, and feed material preparation. Secondary measures identified to control or reduce releases of PCDD/PCDF from iron sintering include adsorption/absorption (for example, activated carbon injection) and high-efficiency dedusting, as well as fine wet scrubbing of waste gases combined with effective treatment of the scrubber waste waters and disposal of waste-water sludge in a secure landfill. The achievable performance level for an iron sintering plant operating according to best available techniques: < 0.2 ng TEQ/Nm 3.
1.
Process description
Iron sintering plants are associated with the manufacture of iron and steel, often in integrated steel mills. The sintering process is a pretreatment step in the production of iron whereby fine particles of iron ores and, in some plants, secondary iron oxide wastes (collected dusts, mill scale) are agglomerated by combustion. Agglomeration of the fines is necessary to enable the passage of hot gases during the subsequent blast furnace operation (UNEP 2003, p. 60). Sintering involves the heating of fine iron ore with flux and coke fines or coal to produce a semimolten mass that solidifies into porous pieces of sinter with the size and strength characteristics necessary for feeding into the blast furnace. Moistened feed is delivered as a layer onto a continuously moving grate or strand. The surface is ignited with gas burners at the start of the strand and air is drawn through the moving bed, causing the fuel to burn. Strand velocity and gas flow are controlled to ensure that burn-through (i.e., the point at which the burning fuel layer reaches the base of the strand) occurs just prior to the sinter being discharged. The solidified sinter is then broken into pieces in a crusher and is air cooled. Product outside the required size range is screened out, oversize material is recrushed, and undersize material is recycled back to the process. Sinter plants that are located in a steel plant recycle iron ore fines from the raw material storage and handling operations and from waste iron oxides from steel plant operations and environmental control systems. Iron ore may also be processed in on-site sinter plants (Environment Canada 2001, p. 18).
22
A blast furnace is a vertical furnace using tuyeres to blast heated or cold air into the furnace burden to smelt the contents. Sinter is charged into the top of the blast furnace in alternating layers with coke.
The flexibility of the sintering process permits conversion of a variety of materials, including iron ore fines, captured dusts, ore concentrates, and other iron-bearing materials of small particle size (for example, mill scale) into a clinker-like agglomerate (Lankford et al. 1985, p. 305306). Waste gases are usually treated for dust removal in a cyclone, electrostatic precipitator, wet scrubber or fabric filter. Figure 1 provides a schematic of an iron sintering plant using a wet scrubbing systemer. It has been suggested that this diagram does not represent the entire steel industry regarding secondary sinter off-gas cleaning; that wet scrubbing systems will be shut down and replaced by fabric filters with injection of hydrated lime / activated carbon / zeolite etc.; and that due to problems and the costs of the waste water treatment this process can only be used effectively where the waste water (after filtering and dilution to the salt concentration of the sea water) may be released to the ocean (Personal Communication, February 2006). Figure 1. Process diagram of a sinter plant using a web scrubbing system
W a te r S in te r M a c h in e ESP
M a in F a n E m is s io n M o n ito r in g Q uench Fan W a te r F in e S c r u b b e r s
M a s h in g S ta g e S lu d g e W a te r P r o c e s s A ir
M a s h in g W a te r
R e c y c lin g F e -C o m p o n e n ts N a t. G as R e h e a tin g T h ic k e n e r S lu d g e T a n k F lo a tin g S lu d g e to B F S lu d g e C le a n e d W a te r Depot
D is c h a r g e W a te r
W a te r T re a tm e n t
S la g Im m o b ilis a tio n
Source: Hofstadler et al. 2003.
2.
As regards emissions of chemicals listed in Annex C of the Stockholm Convention, iron sintering has been identified as a source of PCDD and PCDF. The formation and release of hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB) are less understood from this potential source.
2.1.
Releases to air
2.1.1.General information on emissions from iron sintering plants
SECTION V. Guidelines/guidance by source category: Part II of Annex C The following information is drawn from Environment Canada 2001, p. 2325.
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Emissions from the sintering process arise primarily from materials-handling operations, which result in airborne dust, and from the combustion reaction on the strand. Combustion gases from the latter source contain dust entrained directly from the strand along with products of combustion such as CO, CO 2, SOx, NOx, and particulate matter. The concentrations of these substances vary with the quality of the fuel and raw materials used and combustion conditions. Atmospheric emissions also include volatile organic compounds (VOCs) formed from volatile material in the coke breeze, oily mill scale, etc., and dioxins and furans, formed from organic material under certain operating conditions. Metals are volatilized from the raw materials used, and acid vapours are formed from the halides present in the raw materials. Combustion gases are most often cleaned in electrostatic precipitators (ESPs), which significantly reduce dust emissions but have minimal effect on the gaseous emissions. Water scrubbers, which are sometimes used for sinter plants, may have lower particulate collection efficiency than ESPs but higher collection efficiency for gaseous emissions. Significant amounts of oil in the raw material feed may create explosive conditions in the ESP. Sinter crushing and screening emissions are usually controlled by ESPs or fabric filters. Wastewater discharges, including runoff from the materials storage areas, are treated in a wastewater treatment plant that may also be used to treat blast furnace wastewater. Solid wastes include refractories and sludge generated by the treatment of emission control system water in cases where a wet emission control system is used. Undersize sinter is recycled to the sinter strand. 2.1.2.Emissions of PCDD and PCDF (William Lemmon and Associates Ltd. 2004, p. 2021) The processes by which PCDD/PCDF are formed are complex. PCDD/PCDF appear to be formed in the iron sintering process via de novo synthesis. PCDF generally dominate in the waste gas from sinter plants. The PCDD/PCDF formation mechanism appears to start in the upper regions of the sinter bed shortly after ignition, and then the dioxin/furan and other compounds condense on cooler burden beneath as the sinter layer advances along the sinter strand towards the burn-through point. The process of volatilization and condensation continues until the temperature of the cooler burden beneath rises sufficiently to prevent condensation and the PCDD/PCDF exit with the flue gas. This appears to increase rapidly and peak just before burn-through and then decrease rapidly to a minimum. This is supported by the dioxin/furan profile compared to the temperature profile along the sinter strand in several studies. The quantity of PCDD and PCDF formed has been shown to increase with increasing carbon and chlorine content. Carbon and chloride are present in some of the sinter feed materials typically processed through a sinter plant. 2.1.3.Research findings of interest
(William Lemmon and Associates Ltd. 2004)

It appears that the composition of the feed mixture has an impact on the formation of PCDD/PCDF, i.e., increased chlorine content results in increased PCDD/PCDF formation while the replacement of coke as a fuel with anthracite coal appears to reduce PCDD/PCDF concentration. The form of the solid fuel may also impact furan emissions. Coal, graphite, and activated coke in a Japanese laboratory research programme reduced pentachlorinated dibenzofuran emissions by approximately 90%.
The operating parameters of the sintering process appear to have an impact on the formation of PCDD/PCDF. (William Lemmon and Associates Ltd. 2004)
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2.2.
No information was identified on releases of chemicals listed in Annex C from iron sintering operations to other media such as through waste water or collected dusts.
3.
Alternatives
In accordance with the Stockholm Convention, when consideration is being given to proposals for construction of a new iron sintering plant, priority consideration should be given to alternative processes, techniques or practices that have similar usefulness but avoid the formation and release of chemicals listed in Annex C. Adoption of alternative processes, techniques or practices can have implications on other parts of the mill, careful assessment is needed on a case by case basis. Alternative processes to iron sintering include: The FASTMET process: This process converts iron oxide pellet feed, oxide fines, and/or steel mill wastes into metallic iron, and produces a direct reduced iron product suitable for use in a blast furnace. Emission concentration of PCDD and PCDF from the FASTMET process is reported to be < 0.1 ng TEQ/m3.3 Direct reduction processes: This technique, also known as Direct Reduction Iron (DRI) or Hot Briquetted Iron (HBI), processes iron ore to produce a direct reduced iron product that can be used as a feed material to steel-manufacturing electric arc furnaces, iron-making blast furnaces, or steel-making basic oxygen furnaces. Natural gas is reformed to make hydrogen and carbon dioxide, where hydrogen is the reductant used to produce the direct reduced iron. The availability and cost of natural gas will impact the feasibility of using this technique. Two new direct reduction processes for iron ore fines, Circored and Circofer are available. Both processes use a proven two-stage configuration, combining a Circulating Fluidized Bed (CFB) with a bubbling Fluidized Bed (FB). The Circored process uses hydrogen as reductant. The first-of-its-kind Circored plant was built in Trinidad for the production of 500,000 t/a of HBI and commissioned in 1999. In the Circofer process, coal is used as reductant. (Personal Communication, February 2006). In some direct reduction process systems (eg. FASTMET ), various carbon sources can be used as the reductant. Examples of carbon sources that may be used include: coal, coke breeze and carbon bearing steeel mill wastes (blast furnace dust, sludge, BOF dust, mill scale, EAF dust, sinter dust). This process converts iron oxide pellet feed, oxide fines, and/or steel mill wastes into metallic iron, and produces a direct reduced iron product suitable for use in a blast furnace. Emission concentration of PCDD and PCDF from this process is reported to be < 0.1 ng TEQ/m3.4 Direct smelting processes: Direct smelting replaces the traditional combination of sinter plant, coke oven and blast furnace to produce molten iron. A number of direct smelting processes are evolving and are at various stages of development and commercialization.
4.
Primary and secondary measures for reducing emissions of PCDD and PCDF from iron sintering processes are outlined below. Much of this material has been drawn from William Lemmon and Associates Ltd. 2004.
3
1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines. 1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines.
25
The extent of emission reduction possible with implementation of primary measures only is not readily known. It is therefore recommended that consideration be given to implementation of both primary and secondary measures at existing plants.
4.1.
Primary measures
Primary measures are understood to be pollution prevention measures that will prevent or minimize the formation and release of chemicals listed in Annex C. These are sometimes referred to as process optimization or integration measures. Pollution prevention is defined as: The use of processes, practices, materials, products or energy that avoid or minimize the creation of pollutants and waste, and reduce overall risk to human health or the environment (see section III.B of the present guidelines). Primary measures have been identified that may assist in preventing and minimizing the formation and release of chemicals listed in Annex C. Emission reductions associated with implementation of the following primary measures only is not known. It is recommended that the following measures be implemented together with appropriate secondary measures to ensure the greatest minimization and reduction of emissions possible. Identified primary measures include the following: 4.1.1.Stable and consistent operation of the sinter strand Research has shown that PCDD/PCDF are formed in the sinter bed itself, probably just ahead of the flame front as the hot gases are drawn through the bed. Disruptions to flame front (i.e., nonsteady-state conditions) have been shown to result in higher PCDD/PCDF emissions. Sinter strands should be operated to maintain consistent and stable process conditions (i.e., steadystate operations, minimization of process upsets) in order to minimize the formation and release of PCDD, PCDF and other pollutants. Operating conditions requiring consistent management include strand speed, bed composition (consistent blending of revert materials, minimization of chloride input), bed height, use of additives (for example, addition of burnt lime may help reduce PCDD/PCDF formation), minimization of oil content in mill scale, minimization of air in-leakage through the strand, ductwork and off-gas conditioning systems, and minimization of strand stoppages. This approach will also result in beneficial operating performance improvements (for example, productivity, sinter quality, energy efficiency) (European Commission 2000, p. 47; IPPC 2001, p. 39). 4.1.2.Continuous parameter monitoring A continuous parameter monitoring system should be employed to ensure optimum operation of the sinter strand and off-gas conditioning systems. Various parameters are measured during emission testing to determine the correlation between the parameter value and the stack emissions. The identified parameters are then continuously monitored and compared to the optimum parameter values. Variances in parameter values can be alarmed and corrective action taken to maintain optimum operation of the sinter strand and emission control system. Operating parameters to monitor may include damper settings, pressure drop, scrubber water flow rate, average opacity and strand speed. Operators of iron sintering plants should prepare a site-specific monitoring plan for the continuous parameter monitoring system that addresses installation, performance, operation and maintenance, quality assurance and record keeping, and reporting procedures. Operators should keep records documenting conformance with the identified monitoring requirements and the operation and maintenance plan (EPA 2003). 4.1.3.Recirculation of off-gases Recycling of sinter off-gas (waste gas) has been shown to minimize pollutant emissions, and reduce the amount of off-gas requiring end-of-pipe treatment. Recirculation of part of the off-gas from the entire sinter strand, or sectional recirculation of off-gas, can minimize formation and release of pollutants. For further information on this technique see ECSC 2003 and European Commission 2000, p. 5662.
26
Recycling of iron sintering off-gases can reduce emissions of PCDD/PCDF, NO x and SO2. 4.1.4.Feed material selection Unwanted substances should be minimized in the feed to the sinter strand. Unwanted substances include persistent organic pollutants and other substances associated with the formation of PCDD/PCDF, HCB and PCB (for example, chlorine/chlorides, carbon, precursors and oils). A review of feed inputs should be conducted to determine their composition, structure, and concentration of substances associated with persistent organic pollutants and their formation. Options to eliminate or reduce the unwanted substances in the feed material should be identified. For example: Removal of the contaminant from the material (for example, de-oiling of mill scales); Substitution of the material (for example, replacement of coke breeze with anthracite); Avoidance of the use of the contaminated material (for example, avoid processing electrostatic precipitator sinter dusts, which have been shown to increase PCDD/PCDF formation and release) (Kasai et al. 2001); Specification of limits on permissible concentrations of unwanted substances (for example, oil content in feed should be limited to less than 0.02%) (EPA 2003). Documented procedures should be developed and implemented to carry out the appropriate changes. 4.1.5.Feed material preparation Fine feed materials (for example, collected dusts) should be adequately agglomerated before they are placed on the sinter strand and feed materials should be intimately mixed or blended. These measures will minimize formation and entrainment of pollutants in the waste gas, and will also minimize fugitive emissions. 4.1.6.Urea injection Tests using urea injection to suppress formation of dioxins and furans have been conducted at an iron sintering plant in the United Kingdom. Controlled quantities of urea prills were added to the sinter strand, and this technique is thought to prevent or reduce both PCDD/PCDF and sulphur dioxide emissions. The trials indicate that PCDD/PCDF formation was reduced by approximately 50%. It is estimated that a 50% reduction in PCDD/PCDF would achieve a 0.5 ng TEQ/m 3 emission concentration. Capital costs are estimated at UK0.5 to 1.0 million per plant (approximately US$0.9 million to $1.8 million) (Entec UK Ltd. 2003, p. D10D20). At Canadas only sinter plant, operated by Stelco Inc. in Hamilton, Ontario, trials have been completed using a new similar process in order to reduce dioxins emissions. Stelco found that sealing the furnace to reduce the amount of oxygen and adding a small amount of urea interfered with the chemical reaction that produces dioxins, resulting in reduced emissions. This new process configuration, combined with air-scrubbing systems released 177 pg/m 3 of dioxins in a test. This result surpasses the 2005 Canada-wide Standard limit of 500 pg/Rm 3 and is below the 200 pg/Rm3 limit for 2010. It also represents a 93% reduction from the 1998 measured levels of 2700 pg/Rm 3. The improvement clearly does not depend on scrubbing dioxins out of the stack gases, but is thought to result from "true pollution prevention", as chlorine is needed to produce dioxins and the urea releases ammonia, which captures chlorides in the dust, reducing its availability for dioxin formation. (The Hamilton Spectator, March 1, 2006)
4.2.
Secondary measures
27
Secondary measures are understood to be pollution control technologies or techniques, sometimes described as end-of-pipe treatments. Primary measures identified earlier should be implemented together with appropriate secondary measures to ensure the greatest minimization and reduction of emissions possible. Measures that have been shown to effectively minimize and reduce PCDD and PCDF emissions include: 4.2.1.Removal techniques 4.2.1.1. Adsorption/absorption and high-efficiency dedusting This technique involves sorption of PCDD/PCDF to a material such as activated carbon, together with effective particulate matter (dedusting) control. For regenerative activated carbon technology (William Lemmon and Associates Ltd. 2004) an electrostatic precipitator is used to reduce dust concentration in the off-gases prior to entry to the activated carbon unit. The waste gas passes through a slowly moving bed of char granules which acts as a filter/adsorption medium. The used char is discharged and transferred to a regenerator, where it is heated to elevated temperatures. PCDD/PCDF adsorbed to the char are decomposed and destroyed within the inert atmosphere of the regenerator. This technique has been shown to reduce emissions to 0.1 to < 0.3 ng TEQ/m3. Another sorption technique is the use of lignite or activated carbon injection, together with a fabric filter. PCDD/PCDF are sorbed onto the injected material, and the material is collected in the fabric filter. Along with good operation of the sinter strand, this technique is associated with PCDD/PCDF emission concentrations ranging from 0.1 to 0.5 ng TEQ/m 3 (IPPC 2001, p. 135). 4.2.1.2. Fine wet scrubbing system The Airfine scrubbing system, developed by Voest Alpine Industries (Austria), has been shown to effectively reduce emission concentrations to 0.2 to 0.4 ng TEQ/m 3. The scrubbing system uses a countercurrent flow of water against the rising waste gas to scrub out coarse particles and gaseous components (for example, sulphur dioxide (SO 2)), and to quench the waste gas. (An electrostatic precipitator may also be used upstream for preliminary dedusting.) Caustic soda may be added to improve SO2 absorption. A fine scrubber, the main feature of the system, follows, employing highpressure mist jet co-current with the gas flow to remove impurities. Dual flow nozzles eject water and compressed air (creating microscopic droplets) to remove fine dust particles, PCDD and PCDF (William Lemmon and Associates Ltd. 2004, p. 2930; European Commission 2000, p. 7274). This technique should be combined with effective treatment of the scrubber waste waters and waste-water sludge should be disposed of in a secure landfill (European Commission 2000). 4.2.2.General measures The following measures can assist in minimizing pollutant emissions, but should be combined with other measures (for example, adsorption/absorption, recirculation of off-gases) for effective control of PCDD/PCDF formation and release. 4.2.2.1. Dedusting Removal of particulate matter from the sinter off-gases It has been suggested that effective removal of dust can help reduce emissions of PCDD and PCDF. Fine particles in the sinter off-gas have an extremely large surface area for adsorption and condensation of gaseous pollutants, including PCDD and PCDF (Hofstadler et al. 2003). The best available technique for dedusting removal of particulate matter is the use of fabric filters to remove particulate matter. Use of fFabric filters used atfor sinter plants areis associated with particulate matter emission concentrations of < 10 to < 30 mg/m 3 (UNECE 1998; IPPC 2001, p. 131). Other dedustingparticulate control options that are commonly used for sinter plant off-gases include electrostatic precipitators and wet scrubbers, however their p. Particulate removal efficienciesy areis not as high as for fabric filters. Good performance of electrostatic precipitators and high-efficiency wet gas scrubbers is associated with particulate matter concentrations of < 30 to 50 mg/m3 (IPPC 2001; William Lemmon and Associates Ltd. 2004, p. 26; UNECE 1998).
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Adequately sized capture and particulate emissiondedusting controls for both the feed and discharge ends should be required and put in place. 4.2.2.2. Hooding of the sinter strand Hooding of the sinter strand reduces fugitive emissions from the process, and enables use of other techniques, such as waste gas recirculation.
5.
5.1.
Emerging research
Catalytic oxidation
Selective catalytic reduction has been used for controlling NO x emissions from a number of industrial processes, including iron sintering. Modified selective catalytic reduction technology (i.e., increased reactive area) and select catalytic processes have been shown to decompose PCDD and PCDF contained in off-gases, probably through catalytic oxidation reactions. This may be considered an emerging technique with potential for reducing emissions of persistent organic pollutants from iron sintering plants and other applications. A study investigating stack emissions from four sinter plants noted lower concentrations of PCDD/PCDF (0.995 2.06 ng TEQ/Nm3) in the stack gases of sinter plants with selective catalytic reduction than a sinter plant without (3.10 ng TEQ/Nm 3), and that the PCDD/PCDF degree of chlorination was lower for plants with selective catalytic reduction. It was concluded that selective catalytic reduction did indeed decompose PCDD/PCDF, but would not necessarily be sufficient as a stand alone PCDD/PCDF destruction technology to meet stringent emission limits. Add-on techniques (for example, activated carbon injection) may be required (Wang et al. 2003, p. 1123 1129). Catalytic oxidation can, subject to catalyst selection, be subject to poisoning from trace metals and other exhaust gas contaminants. Validation work would be necessary before use of this process. Further study of the use of selective catalytic reduction and other catalytic oxidation techniques at iron sintering applications is needed to determine its value and effectiveness in destroying and reducing PCDD/PCDF released from this source.
Urea injection
Tests using urea injection to suppress formation of dioxins and furans have been conducted at an iron sintering plant in the United Kingdom. Controlled quantities of urea prills were added to the sinter strand, and this technique is thought to prevent or reduce both PCDD/PCDF and sulphur dioxide emissions. The trials indicate that PCDD/PCDF formation was reduced by approximately 50%. It is estimated that a 50% reduction in PCDD/PCDF would achieve a 0.5 ng TEQ/m 3 emission concentration. Capital costs are estimated at UK0.5 to 1.0 million per plant (approximately US$0.9 million to $1.8 million) (Entec UK Ltd. 2003, p. D10D20).
6.
Summary of measures
Tables 1 and 2 present a summary of the measures discussed in previous sections. Table 1. Alternatives and requirements for new iron sintering plants
Measure Alternative processes Description Priority consideration should be given to alternative processes with potentially less environmental impacts than traditional iron sintering Considerations Examples include: Pelletisation PlantsFASTMET Direct reduction of iron (FASTMETC, Circored and Circofer) Direct smelting Other comments

Measure Performance requirements Description New iron sintering plants should be permitted to achieve stringent performance and reporting requirements associated with best available techniques Considerations Consideration should be given to the primary and secondary measures listed in Table 2 below Other comments
29
Performance requirements for achievement should include: < 0.2 ng TEQ/Rm3 for PCDD/PCDF < 20 mg/Rm3 for particulate matter
Table 2. Summary of primary and secondary measures for iron sintering plants
Measure Primary measures Stable and consistent operation of the sinter plant The sinter strand should be operated to maintain stable consistent operating conditions (e.g., steady-state conditions, minimization of process upsets) to minimize formation of PCDD, PCDF and other pollutants Conditions to optimize operation of the strand include: Minimization of stoppages Consistent strand speed Bed composition Bed height Additives (e.g., burnt lime) Minimization of oil content Minimization of air inleakage Continuous parameter monitoring A continuous parameter monitoring system should be employed to ensure optimum operation of the sinter strand and off-gas conditioning systems. Operators should prepare a site-specific monitoring plan for the continuous parameter monitoring system and keep records that document conformance with the plan Waste gases should be recycled back to the sinter strand to minimize pollutant emissions and reduce the amount of off-gas requiring end-of-pipe treatment A review of feed materials and identification of alternative inputs and/or procedures to minimize unwanted inputs should be conducted. Correlations between parameter values and stack emissions (stable operation) should be established. Parameters are then continuously monitored in comparison to optimum values. System can be alarmed and corrective action taken when significant deviations occur Recirculation of the waste gases can entail recycling of part of the off-gas from the entire sinter strand, or sectional recirculation of offgas Examples include: Removal of the contaminant from the material (e.g., de-oiling of mill scales) This technique will result in only a modest reduction of PCDD/PCDF This approach will have co-benefits such as increased productivity, increased sinter quality and improved energy efficiency Description Considerations Other comments
Recirculation of waste gases
Feed material selection: Minimization of feed materials contaminated
30
Measure with persistent organic pollutants or leading to their formation

Description Documented procedures should be developed and implemented to carry out the appropriate changes Considerations Substitution of the material (e.g., replacement of coke breeze with anthracite) Avoid use of the material (e.g., collected sinter electrostatic precipitator dust) Specification of limits on permissible concentrations of unwanted substances (e.g., oil content in feed should be limited to less than 0.02%) Other comments
Feed material preparation
Fine material (e.g., collected dusts) should be agglomerated before being placed on the sinter strand. Feed materials should be intimately mixed before placement on the sinter strand
These measures will help reduce entrainment of pollutants in the waste gas, and minimize fugitive emissions
Secondary measures The following secondary measures can effectively reduce emissions of PCDD/PCDF and should be considered as examples of best available techniques Adsorption/ absorption and high-efficiency dedusting Use of this technique should include an adsorption stage together with high-efficiency particulate control as key components of the off-gas conditioning system Two adsorption techniques have been demonstrated: Regenerative activated carbon technology whereby off-gases are first cleaned by electrostatic precipitator, and passed through moving adsorption bed (char) to both adsorb PCDD/PCDF and to filter particulates. Adsorptive material is then regenerated Injection of activated carbon, lignite or other similar adsorptive material into the gas stream followed by fabric filter dedusting Fine wet scrubbing of waste gases Use of this technique should include a preliminary countercurrent wet scrubber to quench gases and remove larger particles, followed by a The fine wet scrubbing system under the trade name Airfine, as developed by Voest Alpine Industries, has These techniques are associated with the following emission concentration levels: < 0.3 ng TEQ/m3 0.1 to 0.5 ng TEQ/ m3

Measure Description fine scrubber using high pressure mist jet co-current with off-gases to remove fine particles and impurities Considerations Other comments
31
been shown to reduce emission concentrations to 0.2 to 0.4 ng TEQ/m3
The following secondary measures should not be considered best available techniques on their own. For effective minimization and reduction of PCDD, PCDF and other persistent organic pollutants, the following should be employed in concert with other identified measures Dedusting Removal of particulate matter fromof waste gases Waste gases should be treateddedusted using highefficiency techniques, as this can help minimize PCDD/PCDF emissions. A recommended best available technique for particulate controldedusting is the use of fabric filters. Feed and discharge ends of the sinter strand should be adequately hooded and controlled to capture and mitigatededust fugitive emissions The sinter strand should be hooded to minimize fugitive process emissions Fabric filters have been shown to reduce sinter offgas particulate emissions to < 10 to < 30 mg/m3 Other particulate control dedusting techniques used include electrostatic precipitators and highefficiency scrubbers. Good performance of these technologies is associated with particulate concentrations of < 30 to 50 mg/m3
Hooding of the sinter strand
Hooding of the strand will enable use of other measures, such as waste gas recirculation
7.
Achievable levels were identified for emissions of PCDD/PCDF only. No levels were identified for other chemicals listed in Annex C or for releases to other media. The achievable performance levels for emissions of PCDD/PCDF from iron sintering plants are identified in Table 3. Table 3. Achievable performance for emissions of PCDD/PCDF
Source type New plants Adsorption/absorption and high-efficiency dedusting Fine wet scrubbing system Emission limit value5 < 0.2 ng TEQ/Nm3 0.1 to< 0.5 ng TEQ/Nm3 0.2 to < 0.4 ng TEQ/Nm3
References
5
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ECSC (European Coal and Steel Community). 2003. The Impact of ECSC Steel Research on Steel Production and Sustainability. www.stahlonline.de/medien_lounge/medieninformationen/hintergrundmaterial.htm. Entec UK Ltd. 2003. Development of UK Cost Curves for Abatement of Dioxins Emissions to Air, Final Report. Draft for consultation, November 2003. Environment Canada. 2001. Environmental Code of Practice for Integrated Steel Mills CEPA 1999 Code of Practice. Public Works and Government Services, Canada. EPA (United States Environmental Protection Agency). 2003. National Emission Standards for Hazardous Air Pollutants: Integrated Iron and Steel Manufacturing: Final Rule . 40 CFR Part 63, Federal Register 68:97. EPA, Washington, D.C. www.epa.gov. European Commission. 2000. Reference Document on Best Available Techniques for the Production of Iron and Steel. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Hofstadler K. et al. 2003. Dioxin at Sinter Plants and Electric Arc Furnaces Emission Profiles and Removal Efficiency. Voest Alpine Indstrienlagenbau GmbH, Austria. g5006m.unileoben.ac.at/downloads/Dioxin.doc. IPPC (European Integrated Pollution Prevention and Control Bureau). 2001. Guidance for the Coke, Iron and Steel Sector. Sector Guidance Note IPPC S2.01. UK Environment Agency. Kasai E. et al. 2001. Effect of Additives on the Dioxins Emissions in the Iron Ore Sintering Process. ISIJ International 41:1. Lankford W.T., Samways N.L., Craven R.F. and MacGannon H.E. (eds.) 1985. The Making, Shaping and Treating of Steel. 10th Edition. Association of Iron and Steel Engineers, USA. Personal communication from Expert Group Best Available Techniques Best Environmental Practices, Finland Member, February 2006 The Hamilton Spectator, Canada. March 1, 2006 UNECE (United Nations Economic Commission for Europe). 1998. Best Available Techniques for Controlling Emission of Heavy Metals. Annex III, Protocol to the 1979 Convention on LongRange Transboundary Pollution on Heavy Metals. UNECE, Geneva. www.unece.org. UNEP (United Nations Environment Programme). 2003. Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. UNEP, Geneva. www.pops.int/documents/guidance/Toolkit_2003.pdf. UNEP, September 16, 2005. Overview and Summary of Outcomes from the Regional Consultations on the Draft Guidelines on Best Available Techniques (BAT) and Best Environmental Practices (BEP) relevant to Article 5 and Annex C of the Stockholm Convention on Persistent Organic Pollutants (POPs), February April 2005. UNEP, Geneva. http://www.pops.int/documents/meetings/bat_bep/EGBATBEP1/meetingdocs/EGBATBEP_ %201_inf_4_final.pdf UNEP, October 14, 2005. Compilation of comments received from Parties and others on the draft Guidelines on Best Available Techniques and provisional Guidance on Best Environmental Practices,
http://www.pops.int/documents/meetings/bat_bep/EGBATBEP1/meetingdocs/EGBATBE P_1_inf5.pdf
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Wang L.-C. et al. 2003. Emission of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans from Stack Flue Gases of Sinter Plants. Chemosphere 50:9. William Lemmon and Associates Ltd. 2004. Research on Technical Pollution Prevention Options for Iron Sintering. Prepared for the Canadian Council of Ministers of the Environment, Canada. www.ccme.ca/assets/pdf/df_is_p2_ctxt_p2_strtgy_e.pdf .
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(iii) Secondary aluminium production

Summary
Secondary aluminium smelting involves the production of aluminium from used aluminium products processed to recover metals by pre-treatment, smelting and refining. Fuels, fluxes and alloys are used, while magnesium removal is practised by the addition of chlorine, aluminium chloride or chlorinated organics. Chemicals listed in Annex C of the Stockholm Convention probably result from organics in the feed, chlorine compounds and temperatures between 250 and 500 C. Best available techniques include high-temperature advanced furnaces, oil- and chlorine-free feeds (if alternatives are available), afterburners with rapid quench, activated carbon adsorption and dedusting fabric filters. The achievable performance level for secondary aluminium smelters: < 0.51 ng I-TEQ/Nm3.
1.
Process description
Processes used in secondary aluminium smelting are dependent on feed material. Pre-treatment, furnace type and fluxes used will vary with each installation. Production processes involve scrap pre treatment and smelting/refining. Pre-treatment methods include mechanical, pyrometallurgical and hydrometallurgical cleaning. Smelting is conducted using reverberatory or rotary furnaces. Induction furnaces may also be used to smelt the cleaner aluminium feed materials. Reverberatory furnaces consist of two sections: a smelting chamber heated by a heavy oil burner and an open well where aluminium scraps of various sizes are supplied. Rotary furnaces consist of a horizontal cylindrical shell mounted on rollers and lined with refractory material. The furnace is fired from one end usually using gas or oil as the fuel. Feed consists of process scrap, used beverage cans, foils, extrusions, commercial scraps, turnings and old rolled or cast metal. Skimmings and salt slags from the secondary smelting process are also recycled as feed. Pre-sorting of scrap into desired alloy groups can reduce processing time. Scrap is often contaminated with oil or coatings which must be removed to reduce emissions and improve melting rate (European Commission 2001, p. 279). The following summary of the process is drawn from EPA 1994: Most secondary aluminium recovery facilities use batch processing in smelting and refining operations. The melting furnace is used to melt the scrap, and remove impurities and entrained gases. The molten aluminium is then pumped into a holding furnace. Holding furnaces are better suited for final alloying, and for making any additional adjustments necessary to ensure that the aluminium meets product specifications. Pouring takes place from holding furnaces, either into molds or as feedstock for continuous casters. Smelting and refining operations can involve the following steps: charging, melting, fluxing, demagging, degassing, alloying, skimming, and pouring. Charging consists of placing pre-treated aluminium scrap into a melted aluminium pool (heel) that is maintained in melting furnaces. The scrap, mixed with flux material, is normally placed into the furnace charging well, where heat from the molten aluminium surrounding the scrap causes
35
it to melt by conduction. Flux materials combine with contaminates and float to the surface of the aluminium, trapping impurities and providing a barrier (up to 6 inches thick) that reduces oxidation of the melted aluminium. To minimize aluminium oxidation (melt loss), mechanical methods are used to submerge scrap into the heel as quickly as possible. Demagging reduces the magnesium content of the molten charge. In the past, when demagging with liquid chlorine, chlorine was injected under pressure to react with magnesium as the chlorine bubbled to the surface. The pressurized chlorine was released through carbon lances directed under the heel surface, resulting in high chlorine emissions. A more recent chlorine aluminium demagging process has replaced the carbon lance procedure. Chlorine gas is metered into the circulation pump discharge pipe. It is anticipated that reductions of chlorine emissions (in the form of chloride compounds) will be reported in the future. Other chlorinating agents or fluxes, such as anhydrous aluminium chloride or chlorinated organics, are used in demagging operations. Degassing is a process used to remove gases entrained in molten aluminium. High-pressure inert gases are released below the molten surface to violently agitate the melt. This agitation causes the entrained gasses to rise to the surface to be absorbed in the floating flux. Alloying combines aluminium with an alloying agent in order to change its strength and ductility. The skimming operation physically removes contaminated semisolid fluxes (dross, slag, or skimmings) by ladling them from the surface of the melt. Figure 1. Secondary aluminium smelting
Pretreatment Smelting/refining
Chlorine Flux Fuel
Products
Reverberatory smelting/refining (chlorine)

Fluorine Flux Fuel Alloy ingots Billets Notched bars Shot Hot metal
Reverberatory smelting/refining (fluorine) Treated aluminium scrap

Flux Fuel
Crucible smelting/refining
Induction smelting/refining
Hardeners
Electricity
Flux
Source: EPA 1994.
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Artisinal and other small scale aluminium recovery processes are used in a number of countries. Achievable performance limits are not applicable to artisinal and small scale aluminium recovery processes as the processes used cannot be considered best available techniques or best environmental practices and ideally would not be practised at all. Current practice includes melting largely unsorted scrap in small crucibles or furnaces typically housed in areas with inadequate ventilation. The crucible or furnace may be fired with charcoal, oil, waste oil or coal depending on economies and the local fuel supply situation. In larger furnaces, the melt may be treated with fluxes and degasifying chemicals to improve the quality of the molten metal. Artisinal and other small scale aluminium recovery processes may release many chemicals into the environment, including POPs; these processes should be discouraged. However, in many countries, artisinal and other small scale aluminium recovery processes are practiced. Certain measures can be put in place in order to reduce the amount of pollutants released into the environment. Using the proper air pollution controls on larger scale secondary aluminium smelting operations, instead of artisinal processes, should be encouraged. Measures to reduce POPs emissions and other pollutants from artisinal processes include: pre-sorting of scrap material, selecting a better fuel supply (oil or gas fuels instead of coal), adequate ventilation, filtration of exhaust gases, proper management of wastes and proper choice of degassifiers. These measures can be achieved by education and outreach programs working with craft groups and town authorities. Manual scrap sorting is feasible in some economies rather than mechanical sorting, and with proper training and supervision this could be highly effective. Pre-sorting of scrap can lead to improvements in energy consumption and product quality and reduce the amount of slag to be disposed of. The drying of feed materials and the pre-warming of refractories can reduce hydrogen production in the melt and therefore can improve product quality without the use of chemicals. Proper ventilation by extraction of fumes and off-gases through a chimney and hood enclosure around the crucible, thereby providing natural draught and some dispersion, will improve the quality of combustion and reduce occupational exposure of workers to pollutants. Filters, dry scrubbers or wet scrubbers for particle abatement can be effective at pollution control but require a reliable electricity supply to power the fans. Wet scrubbers require appropriate arrangements for the collection, treatment and safe disposal of effluent. All pollution control systems require appropriate residue handling arrangements and disposal routes to be in place before installation. If effluent treatment is not in place then dry air pollution control devices should be preferred. However, storage of fine particulate matter is demanding in many environments and appropriate storage and waste arrangements are required for the captured material until a safe disposal route is identified. Co-location of facilities and regional cooperation to manage and dispose wastes would be beneficial. The use of hexachloroethane as a degasifier for reducing melts has been thought to lead to significant release of POPs. The use of potassium fluoride or potassium aluminium fluoride as a degassing agent has been used successfully in some larger plants. Other large plants have successfully used chlorine as a degasifier, however at these locations appropriate handling and safety arrangements are in place including appropriately trained staff.(Personal Communication, February 2006)
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2.
The generation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) is probable due to the presence of organic contaminants and plastics in the feed material with the addition of chlorine and chlorides during the smelting process.
2.1.
General information on emissions from secondary aluminium smelters
(European Commission 2001, p. 294300) Potential emissions to air include dust, metal compounds, chlorides, nitrogen oxides (NO x), sulphur dioxide (SO2) and organic compounds such as PCDD/PCDF and carbon monoxide (CO). Ammonia can also be generated from the improper storage, treatment and transport of skimmings. Chlorine compounds can be removed using wet or dry scrubbers and their formation minimized by good control and the use of mixtures of chlorine and inert gases. Low-NOx burners and low-sulphur fuels can be used to decrease emissions of NOx and SO2. After burning is used to destroy organic materials that escapes the combustion zone, while injection of treatment materials such as lime, sodium bi-carbonate and carbon is also practised. Most installations then use (high efficiency) bag filters or ceramic filters to remove dust and emissions can lie in the range 0.6 to 20 mg/Nm 3. A spark arrester or cooling chamber often precedes them to provide filter protection. Energy recovery can be practised, most commonly re-cuperative burners are used (European Commission 2001).
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Figure 2: Input and output from secondary aluminium production

NB smoke and dust can be associated with organic compounds such as VOC and dioxins (IPPC 2001)
2.2.
PCDD/PCDF are formed during aluminium smelting through incomplete combustion or by de novo synthesis when organic and chlorine compounds such as oils and plastics are present in the feed material. Secondary feed often consists of contaminated scrap. The presence of oils and other organic materials on scrap or other sources of carbon (partially burnt fuels and reductants, such as coke), can produce fine carbon particles which react with inorganic chlorides or organically bound chlorine in the temperature range of 250 to 500 C to produce PCDD/PCDF. This process is known as de-novo synthesis and is catalysed by the presence of metals such as copper or iron. Although PCDD/PCDF are destroyed at high temperature (above 850 C) in the presence of oxygen, the process of de-novo synthesis is still possible as the gases are cooled through the reformation window. This window can be present in abatement systems and in cooler parts of the furnace e.g. the feed area. Care taken in the design of cooling systems to
39
minimise the residence time in the window is practised to prevent de-novo synthesis (European Commission 2001, p. 133). Poor combustion of fuel or the organic content of the feed material can result in the emission of organic materials. The provision of effective burner and furnace to controls is used to optimise combustion. Peak combustion rates from included organic materials need to be taken into account if they are fed to the furnace. It is reported that pre-cleaning of scrap removes much of the organic material and improves the melting rate. The use of chlorine mixtures for degassing and magnesium removal and the use of chlorides (salt flux) will provide a source of chlorine for the potential formation of PCDD/PCDF (European Commission 2001, p. 297). Based on information obtained from Japanese secondary aluminum operations, emissions have been found to vary according to the furnace type employed. The highest-emitting furnace type in this study was the open well reverberatory furnace. These units were found to average 0.38 ng TEQ/Nm3. These results are believed to relate to the fact that this is the only furncace design which permits the introduction of large pieces of scrap material, and this material is often the most contaminated with organic compounds which may contribute to PCDD/PCDF formation (Government of Japan, 2005).
2.3.

Production of aluminium from secondary raw materials is essentially a dry process. Discharge of wastewater is usually limited to cooling water, which is often re-circulated, and rainwater run-off from surfaces and roofs. The rainwater run-off can be contaminated by open storage of raw materials such as oily scrap and deposited solids. Salt slags arise when mixtures of sodium and potassium chloride are used to cover the molten metal to prevent oxidation, increase yield and increase thermal efficiency. These slags are generally produced in rotary furnaces and can have an environmental impact if they are deposited on land. Skimmings are used as a raw material in other parts of the secondary aluminium industry and are sometimes pre-treated by milling and air classification to separate aluminium from aluminium oxide. Spent filters from metal treatment are usually disposed. In some cases when sodium bicarbonate is used for gas cleaning, solid residues can be recovered with the salt flux. Alternatively filter dust can be treated thermally to destroy dioxins. Furnace linings and dust can be recovered in the salt slag treatment processes or disposed.
(European Commission 2001, p. 294300)
3.
Process design and configuration is influenced by the variations in feed material and quality control. Processes considered as best available practices are the reverberatory furnace, rotary and tilting rotary furnaces, the induction furnace and the Meltower shaft furnace. All techniques should be applied in conjunction with suitable gas collection and abatement systems. No information is available on alternative processes to smelting for secondary aluminium processing.
4.
4.1.

Primary measures
Primary and secondary measures for PCDD/PCDF reduction and elimination are discussed below. Primary measures are regarded as pollution prevention techniques to reduce or eliminate the generation and release of persistent organic pollutants. Possible measures include: 4.1.1.Pre-sorting of feed material
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The presence of oils, plastics and chlorine compounds in the feed material should be avoided to reduce the generation of PCDD/PCDF during incomplete combustion or by de novo synthesis. Sorting of feed material should be conducted prior to smelting to suit furnace type and abatement and to permit the transfer of unsuitable raw materials to other facilities better suited for their treatment. This will prevent or minimize the use of chloride salt fluxes during smelting. Scrap material should be cleaned of oils, paints and plastics during pre-treatment. The removal of organic and chlorine compounds will reduce the potential for PCDD/PCDF formation. Methods used include the swarf centrifuge, swarf drying or other thermal decoating techniques. Thermal decoating and de-oiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas (European Commission 2001, p. 310). Scrap sorting using laser and eddy current technology is being tested. These methods could provide more efficient selection of materials for recycling and the ability to produce desired alloys in recycling plants (European Commission 2001, p. 294300). 4.1.2.Effective process control Process control systems should be utilized to maintain process stability and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation, such as maintaining furnace temperature above 850 C to destroy PCDD/PCDF. Ideally, PCDD/PCDF emissions would be monitored continuously to ensure reduced releases. Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (for example, waste incineration), but research is still developing in this field. In the absence of continuous PCDD/PCDF monitoring, other variables such as temperature, residence time, gas components and fume collection damper controls should be continuously monitored and maintained to establish optimum operating conditions for the reduction of PCDD/PCDF.
4.2.
Secondary measures
Secondary measures are pollution control techniques. These methods do not eliminate the generation of contaminants, but serve as a means to contain and prevent emissions. 4.2.1.Fume and gas collection Fume and off-gas collection should be implemented in the control of air emissions from all stages of the process. The use of sealed feeding systems and furnaces should be practised. Fugitive emissions should be controlled by maintaining negative air pressure within the furnace to prevent leaks. If a sealed unit is not possible, hooding should be used. Furnace or reactor enclosures may be necessary. Where primary extraction and enclosure of fumes is not practicable, the furnace should be enclosed so that ventilation air can be extracted, treated and discharged (European Commission 2001, p. 187188). Additional benefits of fume and off-gas collection from rooflines include reducing exposure of fumes and heavy metals to the workforce. 4.2.2.High-efficiency dust removal Particulate matter generated during the smelting process should be removed as this material possesses a large surface area on which PCDD/PCDF can adsorb. Proper isolation and disposal of these dusts will aid in PCDD/PCDF control. Collected particulate should be treated in hightemperature furnaces to destroy PCDD/PCDF and recover metals. Methods to consider are the use of fabric filters, wet and dry scrubbers and ceramic filters. Scrubbing off-gases with sodium bicarbonate will remove chlorides produced by the salt flux, resulting in sodium chloride, which can then be removed by fabric filters to be recharged to the furnace. In addition, use of a catalytic coating on fabric filter bags could destroy PCDD/PCDF by oxidation while collecting particulate matter on which these contaminants have adsorbed (European Commission 2001, p. 294300). 4.2.3.Afterburners and quenching
41
Afterburners (post-combustion) should be used at a minimum temperature of 950 C to ensure full combustion of organic compounds (Hbner et al. 2000). This stage is to be followed by rapid quenching of hot gases to temperatures below 250 C. Oxygen injection in the upper portion of the furnace will promote complete combustion (European Commission 2001, p. 189). It has been observed that PCDD/PCDF are formed in the temperature range of 250 to 500 C. They are destroyed above 850 C in the presence of oxygen. Yet, de novo synthesis is still possible as the gases are cooled through the reformation window present in abatement systems and cooler areas of the furnace. Proper operation of cooling systems to minimize reformation time should be implemented (European Commission 2001, p. 133). A benefit of cooling the flue gases before scrubbbing would be reduced gas volume, hence reducing the size of abatement equipment, the duct size and the energy needs for gas movement. 4.2.4.Adsorption on activated carbon Activated carbon treatment should be considered as this material is an ideal medium on which PCDD/PCDF can adsorb due to its large surface area. Off-gas treatment techniques include using fixed or moving bed reactors or injection of carbon into the gas stream followed by high-efficiency dust removal systems such as fabric filters. Lime/carbon mixtures can also be used. 4.2.5. Catalyst-Coated Filter Japanese researchers have used a catalyst-coated filter on an experimental basis, and results are encouraging. This filter system consists of two filters, one to collect the soot and a second which is coated with a catalyst to decompose dioxins and furans. The experiemtnal work has demonstrated that the catalyst was effective at decomposing dioxins and furans at temperatures in the range of 180 to 200 C. 4.3 Best Environmental Practices
The following guidelines are derived from the Japan Aluminium Alloy Refiners Assocation (March 2004) and may be considered as best environmental practices:
Concrete operation guidelines are shown below. The following main items are common to these guidelines.
1. Do not purchase anything that are likely to generate smoke. Melt materials gradually. 2. Perform smelting and combustion with no soot or smoke generation. 3. Perfectly burn generated soot and smoke promptly. 4. Quickly cool down exhaust gas at high or middle temperatures to 170 oC or below promptly. 5. CO control in exhaust gas (CO 50 ppm, air-fuel ratio management) <Concrete operation guidelines> 1. Matters Related to Materials and Scraps Reinforce sorting on and after accepting materials. (1) Sort and eliminate resin and oil (2) Sort and eliminate foreign substances and resin after shredder processing. (3) Return materials where resin or oil is stuck. Do not accept them at discount prices. 2. At Time of Combustion and Smelting at Smelting Chamber (1) Avoid turning the burner ON and OFF as much as possible in order to reduce imperfect combustion and soot generation. (2) Supply materials while the burner is ON, and set generated smoke and soot in flame for secondary combustion.
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3. At Time of Combustion and Smelting in Open Well (1) Adjust the air-fuel ratio by measuring the CO and O2 concentration in flue exhaust gas. (2) In order to heat and burn smoke and soot generated from materials supplied to the open well, put the smoke and soot in burner flame. (3) Adjust the supply of smelting materials according to the extent of smoke and flame (soot) generation. Equalize the supply of burnable material (repetitively and little by little). Keep the combustion space with no imperfect combustion. Do not leak smoke from the exhaust gas hood. (4) Maintain the performance of the dust collector (with regular inspection and bag replacement). 4. At Time of Demagnesium Processing (1) Maintain the interval between the extinguishment of the burner and the start of chlorine processing, and between the completion of chlorine processing and burner ignition. For 5 to 10 minutes, while performing air suction (residual gas discharge). (2) Make improvement in efficiency by an increase in the initial temperature of molten metal processing. (3) Sort combined materials according to the quantity of Mg contained. (4) Standardize the quantity of chlorine and that of flux used. 5. At Time of Drying Turnings (1) Demand improvement in cut dust with excessive cutting oil (cutting oil with a high chlorine content). (2) Reheat at high temperature, maintain the exhaust gas of the drying furnace, and quickly cool down the exhaust gas (i.e., keep good temperature control). (3) Measure the CO concentration in exhaust gas regularly. 6. At Time of Paint Removal and Baking of Can Scraps (UBC) (1) Removal of mixing foreign substances, such as resin and resin bags. (2) Stable operation of the reheating furnace at constant circulation and exhaust gas temperature. 7. General (1) Maintenance and inspection of the capacity of the dust collector, bag replacement, shaking cycle, and suction pressure. (2) Regular implementation of in-house environmental education for smelting workers. (3) Targeting at the DXNs concentration in exhaust gas (< 1 ng-TEQ/Nm3) for existing facilities.
5.
5.1.
Emerging research
Catalytic oxidation
Catalytic oxidation is an emerging technology used in waste incinerators to eliminate PCDD/PCDF emissions. This process should be considered by secondary base metals smelters as it has proven effective for PCDD/PCDF destruction in waste incinerators. However, catalytic oxidation can, subject to catalyst selection, be subject to poisoning from trace metals and other exhaust gas contaminants. Validation work would be necessary before use of this process. Catalytic oxidation processes organic compounds into water, carbon dioxide (CO 2) and hydrochloric acid using a precious metal catalyst to increase the rate of reaction between 370 and 450 C, whereas incineration occurs typically at 980 C. Catalytic oxidation has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and 99% efficiency, and should be considered. Off-gases should be dedusted treated for particulate removal prior to catalytic oxidation for optimum efficiency. This method is effective for the vapour phase of contaminants. The resulting hydrochloric acid is treated in a scrubber while the water and CO 2 are released to the air after cooling (Parvesse 2001).
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6.
Measure
Summary of measures
Description Various recommended smelting processes should be considered for new facilities Considerations Processes to be considered include: reverberatory furnace, rotary and tilting rotary furnaces, induction furnace, and Meltower shaft furnace Other comments All techniques should be applied in conjunction with suitable gas collection and abatement systems
Table 1. Measures for recommended processes for new secondary aluminium smelters
Table 2. Summary of primary and secondary measures for secondary aluminium smelters
Measure Primary measures Presorting of feed material The presence of oils, plastics and chlorine compounds in the feed material should be avoided to reduce the generation of PCDD/PCDF during incomplete combustion or by de novo synthesis Processes to be considered include: Prevention or minimization of the use of chloride salts where possible Cleaning scrap material of oils, paints and plastics during pretreatment Using thermal decoating techniques such as the swarf centrifuge or swarf dryer Sorting of feed material should be conducted prior to smelting to suit furnace type and abatement and to permit the transfer of unsuitable raw materials to other facilities better suited for their treatment. Thermal decoating and deoiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (e.g. waste incineration), but research is still developing in this field Description Considerations Other comments
Effective process control
Process control systems should be utilized to maintain process stability and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation
PCDD/PCDF emissions may be minimized by controlling other variables such as temperature, residence time, gas components and fume collection damper controls after having established optimum operating conditions for the reduction of PCDD/PCDF
Secondary measures Fume and gas collection Effective fume and off-gas collection should be implemented in the capture of air emissions from all stages of the process Processes to be considered include: Use of sealed feeding systems and furnaces Control of fugitive emissions by maintaining negative air pressure within the furnace to prevent leaks Where primary extraction and enclosure of fumes is not practicable, the furnace should be enclosed so that ventilation air can be extracted, treated and discharged
44
Measure

Description Considerations Use of hooding if a sealed unit is not possible Use of furnace or reactor enclosures Other comments
High-efficiency dust removal
Particulate matter generated during the smelting process should be removed as this material possesses large surface area on which PCDD/PCDF can adsorb. Proper isolation and disposal of these dusts will aid in PCDD/PCDF control Afterburners should be used at temperatures > 950 C to ensure full combustion of organic compounds, followed by rapid quenching of hot gases to temperatures below 250 C
Processes to be considered include: Fabric filters, wet/dry scrubbers and ceramic filters Catalytic coatings on fabric filter bags to destroy PCDD/PCDF by oxidation while collecting particulate matter on which these contaminants have adsorbed Considerations include: PCDD/PCDF formation at 250to 500 C, and destruction > 850 C with O2 Requirement for sufficient O2 in the upper region of the furnace for complete combustion Need for proper design of cooling systems to minimize reformation time
Collected particulate should be treated in high-temperature furnaces to destroy PCDD/PCDF and recover metals
Activated carbon treatment should be considered as this material is an ideal medium on which PCDD/PCDF can adsorb due to its large surface area
Processes to be considered include: Treatment with activated carbon using fixed or moving bed reactors Injection of carbon into the gas stream followed by high-efficiency dedusting methods such as fabric filters
Emerging research Catalytic oxidation Catalytic oxidation is an emerging technology which should be considered due to its high efficiency and lower Considerations include: Process efficiency for the vapour phase of contaminants Hydrochloric acid treatment using scrubbers while water Has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and 99% efficiency. Off-gases should be dedusted

Measure Description energy consumption. Catalytic oxidation transforms organic compounds into water, carbon dioxide (CO2) and hydrochloric acid using a precious metal catalyst Considerations and CO2 are released to the air after cooling Other comments
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prior to catalytic oxidation for optimum efficiency
7.
The achievable performance level6 for emissions of PCDD/PCDF from secondary aluminium smelters is < 0.51 ng I-TEQ/Nm3.
References
EPA (United States Environmental Protection Agency). 1994. Secondary Aluminium Operations. Background Report AP-42, Section 12.8. www.epa.gov/ttn/chief/ap42/ch12/final/c12s08.pdf. European Commission. 2001. Reference Document on Best Available Techniques in the NonFerrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Feng Xinbin, Qui Guangle, Li Guanghui, Li Ping, Wang Shaofeng, Mercury Emissions from Artisanal Zinc and Mercury Smelting in Guizhou, PR China, Goldschmidt Conference Abstracts 2005, The Geochemistry of Mercury, page A705 Government of Japan, Ministry of Economy, Trade and Industry. Technical Information on Measures for Dioxins Discharge Control at Secondary Aluminum Refineries . November 2005 Hbner C., Boos R., Bohlmann J., Burtscher K. and Wiesenberger H. 2000. State-of-the-Art Measures for Dioxin Reduction in Austria. Vienna. www.ubavie.gv.at/publikationen/Mono/M116s.htm. Integrated Pollution Prevention and Control (IPPC), Reference Document on Best Available Techniques in the Non Ferrous Metals Industries, December 2001 Parvesse T. 2001. Controlling Emissions from Halogenated Solvents. Chemical Processing [Chem. Process.]. Vol. 64, no. 4, pp. 48-51. Apr 2001Chemical Processing.
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Personal communication from Expert Group Best Available Techniques Best Environmental Practices, Finland Member, February 2006 Personal communication from Expert Group Best Available Techniques Best Environmental Practices, UK Member, February 2006
Personal communication, Member, Japan, Expert Group Meeting, 1 December, 2006 New Operation Guidelines to Suppress DXNs Emissions Exhaust Gas, Japan Aluminium Alloy Refiners Association, March 30, 2004
UNEP, Compilation of comments received from Parties and others on the draft Guidelines on Best Available Techniques and provisional Guidance on Best Environmental Practices, October 14, 2005
http://www.pops.int/documents/meetings/bat_bep/EGBATBEP1/meetingdocs/EGBATBE P_1_inf5.pdf UNEP Environment Program News Centre, http://www.unep.org/Documents.Multilingual/Default.asp? DocumentID=284&ArticleID=3204&l=en, as read on January 20, 2006 Xinbin Feng, Xianwu Bi, Guangle Qiu, Guanghui Li, Shunlin Tang, Mercury Pollution in Guizhou, China - A status Report, http://pbc.eastwestcenter.org/abstracts2005/abstract2005fengxinbin.htm, as read on December 29th, 2005
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(iv) Secondary zinc production

Summary
Secondary zinc smelting involves the production of zinc from materials such as dusts from copper alloy production and electric arc steel making, and residues from steel scrap shredding and galvanizing processes. als in the environment. Production processes include feed sorting, pretreatment cleaning, crushing, sweating furnaces to 364 C, melting furnaces, refining, distillation and alloying. Oils and plastics in feed, and temperatures between 250 and 500 C, may give rise to chemicals listed in Annex C of the Stockholm Convention. Best available techniques include feed cleaning, maintaining temperatures above 850 C, fume and gas collection, afterburners with quenching, activated carbon adsorption and fabric filter dedusting. The achievable performance level for secondary zinc smelters: < 0.51 ng I-TEQ/Nm3.
1.
(EPA 1981)
Process description
Secondary zinc smelting involves the processing of zinc scrap from various sources. Feed material includes dusts from copper alloy production and electric arc steel making, residues from steel scrap shredding, and scrap from galvanizing processes. The process method is dependent on zinc purity, form and degree of contamination. Scrap is processed as zinc dust, oxides or slabs. The three general stages of production are pretreatment, melting and refining. During pretreatment scrap is sorted according to zinc content and processing requirements, cleaned, crushed and classified by size. A sweating furnace is used to heat the scrap to 364 C. At this temperature only zinc is melted, while other metals remain solid. The molten zinc is collected at the bottom of the sweat furnace and recovered. The leftover scrap is cooled, recovered and sold to other processors. Pretreatment can involve leaching with sodium carbonate solution to convert dross and skimmings to zinc oxide, to be reduced to zinc metal. The zinc oxide product is refined at primary zinc smelters. Melting processes use kettle, crucible, reverberatory, reduction and electric induction furnaces. Impurities are separated from molten zinc by flux materials. Agitation allows flux and impurities to float on the surface as dross, which can be skimmed off. The remaining zinc is poured into moulds or transferred in a molten state for refining. Alloys can be produced from pretreated scrap during sweating and melting. Refining removes further impurities in clean zinc alloy scrap and in zinc vaporized during the melt phase in retort furnaces. Distillation involves vaporization of zinc at temperatures from 982 to 1,249 C in muffle or retort furnaces and condensation as zinc dust or liquid zinc. Several forms can be recovered depending on temperature, recovery time, absence or presence of oxygen and equipment used during zinc vapour condensation. Pot melting is a simple indirect heat melting operation whereby the final alloy cast into zinc alloy slabs is controlled by the scrap input into the pot. Distillation is not involved.
48
Final products from refining processes include zinc ingots, zinc dust, zinc oxide and zinc alloys. Figure 1 shows the production process in diagrammatic form. Figure 1. Secondary zinc smelting
Pretreatment
Die-cast products, residues, skimmings, other mixed scrap Sweating: Reverberatory Rotary Muffle Kettle (pot)
Melting
Refining/alloying
Alloying Alloy
Fuel Sweated scrap (melt or ingots) Fuel
Melting: Kettle (pot) Crucible Reverberatory
Flux Fuel Alloying agent Distillation: Retort Muffle Zinc ingot, zinc dust
Flux
Fuel Fuel Water Graphite rod distillation
Clean scrap Zinc alloys Contaminated zinc oxide baghouse dust
Electric resistance sweating
Electric induction melting
Electricity
Water
Flux
Electricity
Distillation Oxidation: Retort Muffle
Zinc oxide
Fuel Crushing/ screening
Air Water Retort reduction
Zinc
Residues, skimmings
Sodium carbonate leaching
Crude zinc oxide to primary smelters
Fuel Water Carbon monoxide
Water
Sodium carbonate
Source: EPA 1981.
Artisinal and small enterprise metal recovery activities may play a significant international role, in particular in developing countries and countries with economies in transition. These activities may contribute significantly to pollution and have negative health impacts. For example, artisinal zinc smelting is an important atmospheric mercury emission source. The technique used to smelt both zinc and mercury are very simple. The ores are heated in a furnace for a few hours, and zinc metal and liquid mercury are produced. In many cases there are no pollution control devices employed at all during the melting process. Other metals that are known to be produced by artisinal and small enterprise metal recovery activities include antimony, iron, lead, manganese, tin, tungsten, gold, silver, copper, and aluminum. These are not considered best available techniques or best environmental practices. However, as a minimum, appropriate ventilation and material handling should be carried out.
49
2.
The formation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) may be possible if plastics and oils are present in the feed material.
2.1.
General information on emissions from secondary zinc smelters
Air emissions from secondary zinc smelting can escape as stack or fugitive emissions, depending on the facility age or technology. Main contaminants are sulphur dioxide (SO 2), other sulphur compounds and acid mists, nitrogen oxides (NO x), metals (especially zinc) and their compounds, dusts and PCDD/PCDF. SO2 is collected and processed into sulphuric acid in acid plants when processing secondary material with high sulphur content. Fugitive SO 2 emissions can be controlled by good extraction and sealing of furnaces. NOx can be reduced using low-NOx or oxy-fuel burners. Particulate matter is collected using high-efficiency dust removal methods such as fabric filters and returned to the process (European Commission 2001, p.359368).
2.2.
PCDD/PCDF are formed during base metals smelting through incomplete combustion or by de novo synthesis when organic and chlorine compounds such as oils and plastics are present in the feed material. Secondary feed often consists of contaminated scrap. The processing of impure scrap such as the non-metallic fraction from shredders is likely to involve production of pollutants including PCDD/PCDF. Relatively low temperatures are used to recover lead and zinc (340 and 440C). Melting of zinc may occur with the addition of fluxes including zinc and magnesium chlorides (UNEP 2003, p. 78). The low temperatures used in zinc smelting fall directly within the 250 to 500 C range in which PCDD/PCDF are generated. The addition of chloride fluxes provides a chlorine source. Formation is possible in the combustion zone by incomplete combustion of organic compounds and in the offgas treatment cooling section through de novo synthesis. PCDD/PCDF adsorb easily onto particulate matter such as dust, filter cake and scrubber products and can be discharged to the environment through air emissions, waste water and residue disposal. Although PCDD/PCDF are destroyed at high temperature (above 850 C) in the presence of oxygen, the process of de-novo synthesis is still possible as the gases are cooled through the reformation window. This window can be present in abatement systems and in cooler parts of the furnace e.g. the feed area. Care taken in the design of cooling systems to minimise the residence time in the window is practised to prevent de-novo synthesis (European Commission 2001, p. 133). A report prepared by the Government of Japan studied dioxin reduction technologies and their effects in secondary zinc production facilities of Japan. Various exhaust gas technologies were introduced in line with guidelines on BAT/BEP at five existing facilities. Dioxin emissions were found to vary depending on the type of furnace employed. Dioxin discharge concentrations before and after the introduction of technologies, were found to range from 0.91-40.00 ng TEQ/Nm 3 and 0.32-11.700 ng TEQ/Nm3, respectively. When a state-of-the-art two-step bag filter and two-step activated carbon injection system was introduced into the reduction furnace at one facility, dioxin concentration was reduced from 3.30 ng TEQ/Nm 3 to 0.49 ng TEQ/Nm3 (Government of Japan, 2005).
2.3.
Waste water originates from process effluent, cooling water and run-off and is treated using wastewater treatment techniques. Process residues are recycled, treated using downstream methods to recover other metals, or safely disposed.
50
3.
Variation in feed material and desired product quality influences process design and configuration. These processes should be applied in combination with good process control, gas collection and abatement systems. Processes considered to be best available practices include: Physical separation, melting and other high temperature treatment techniques followed by the removal of chlorides. The use of Waelz kilns, cyclone or converter type furnaces to raise the temperature to volatilise the metals and then form the oxides that are then recovered from the gases in a filtration stage (European Commission 2001, p. 396). No information is available on alternative processes to smelting for secondary zinc processing.
4.
4.1.

Primary measures
Primary and secondary measures of PCDD/PCDF reduction and elimination are discussed below. Primary measures are regarded as pollution prevention techniques to reduce or eliminate the generation and release of persistent organic pollutants. Possible measures include: 4.1.1.Presorting of feed material Oils and plastics in zinc scrap should be separated from the furnace feed to reduce the formation of PCDD/PCDF from the incomplete combustion of organic compounds or by de novo synthesis. Methods for feed storage, handling and pretreatment are influenced by material size distribution, contaminants and metal content. Milling and grinding, in conjunction with pneumatic or density separation techniques, can be used to remove plastics. Thermal decoating and de-oiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas (European Commission 2001, p. 232). 4.1.2.Effective process control Process control systems should be utilized to maintain process stability and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation, such as maintaining furnace temperature above 850 C to destroy PCDD/PCDF. Ideally, PCDD/PCDF emissions would be monitored continuously to ensure reduced releases. Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (for example, waste incineration), but research is still developing in this field. In the absence of continuous PCDD/PCDF monitoring, other variables such as temperature, residence time, gas components and fume collection damper controls should be continuously monitored and maintained to establish optimum operating conditions for the reduction of PCDD/PCDF.
4.2.
Secondary measures
Secondary measures are pollution control techniques to contain and prevent emissions. These methods do not prevent the formation of contaminants. 4.2.1.Fume and gas collection Effective fume and off-gas collection should be implemented in all stages of the smelting process to capture PCDD/PCDF emissions. The fume collection systems used can exploit furnace-sealing systems and be designed to maintain a suitable furnace [vacuum] that avoids leaks and fugitive emissions. Systems that
51
maintain furnace sealing or hood deployment can be used. Examples are through hood additions of material, additions via tuyeres or lances and the use of robust rotary valves on feed systems. An [effective] fume collection system capable of targeting the fume extraction to the source and duration of any fume will consume less energy. BAT for gas and fume treatment systems are those that use cooling and heat recovery if practical before a fabric filter (European Commission 2001, p. 397). 4.2.2.High-efficiency dust removal Dusts and metal compounds generated from the smelting process should be removed as this particulate matter possesses high surface area on which PCDD/PCDF easily adsorb. Removal of these dusts would contribute to the reduction of PCDD/PCDF emissions. Techniques to be considered are the use of fabric filters, wet and dry scrubbers and ceramic filters. Collected particulate matter is usually recycled in the furnace. Fabric filters using high-performance materials are the most effective option. Innovations regarding this method include bag burst detection systems, online cleaning methods, and catalytic coatings to destroy PCDD/PCDF (European Commission 2001, p. 139140). 4.2.3.Afterburners and quenching Afterburners (post-combustion) should be used at a minimum temperature of 950 C to ensure full combustion of organic compounds (Hbner et al. 2000). This stage is to be followed by rapid quenching of hot gases to temperatures below 250 C. Oxygen injection in the upper portion of the furnace will promote complete combustion (European Commission 2001, p. 189). It has been observed that PCDD/PCDF are formed in the temperature range of 250 to 500 C. These are destroyed above 850 C in the presence of oxygen. Yet, de novo synthesis is still possible as the gases are cooled through the reformation window present in abatement systems and cooler areas of the furnace. Operation of cooling systems to minimize reformation time should be implemented (European Commission 2001, p. 133). 4.2.4.Adsorption on activated carbon Activated carbon treatment should be considered for PCDD/PCDF removal from smelter off-gases. Activated carbon possesses large surface area on which PCDD/PCDF can be adsorbed. Off-gases can be treated with activated carbon using fixed or moving bed reactors, or injection of carbon particulate into the gas stream followed by removal as a filter dust using high-efficiency dust removal systems such as fabric filters.
5.
5.1.
Emerging research
Catalytic oxidation
Catalytic oxidation is an emerging technology used in waste incinerators to eliminate PCDD/PCDF emissions. This process should be considered by secondary base metals smelters as it has proven effective for PCDD/PCDF destruction in waste incinerators. Catalytic oxidation can, subject to catalyst selection, be subject to poisoning from trace metals and other exhaust gas contaminants. Validation work would be necessary before use of this process. Catalytic oxidation processes organic compounds into water, carbon dioxide (CO 2) and hydrochloric acid using a precious metal catalyst to increase the rate of reaction at 370 to 450 C. In comparison, incineration occurs typically at 980 C. Catalytic oxidation has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and 99% efficiency, and should be considered. Off-gases should be dedusted treated for particulate removal prior to catalytic oxidation for optimum efficiency. This method is effective for the vapour phase of contaminants. The resulting hydrochloric acid is treated in a scrubber while the water and CO 2 are released to the air after cooling (Parvesse 2001).
52
6.
Summary of measures
Measure Description Various recommended smelting processes should be considered for new facilities Considerations Processes to be considered include: Physical separation, melting and other high-temperature treatment techniques followed by the removal of chlorides The use of Waelz kilns, cyclone- or converter-type furnaces to raise the temperature to volatilize the metals and then form the oxides that are then recovered from the gases in a filtration stage Other comments These processes should be applied in combination with good process control, gas collection and abatement systems
Table 1. Measures for recommended processes for new secondary zinc smelters
Recommended Processes
Table 2. Summary of primary and secondary measures for secondary zinc smelters
Measure Primary measures Presorting of feed material Oils and plastic in zinc scrap should be separated from the furnace feed to reduce the formation of PCDD/PCDF from incomplete combustion or by de novo synthesis Processes to be considered include: Milling and grinding, in conjunction with pneumatic or density separation techniques, can be used to remove plastics Oil removal conducted through thermal decoating and de-oiling processes PCDD/PCDF emissions may be minimized by controlling other variables such as temperature, residence time, gas components and fume collection damper controls, after having established optimum operating conditions for the reduction of PCDD/PCDF Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (e.g. waste incineration), but research is still developing in this field Thermal decoating and de-oiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas Description Considerations Other comments
Secondary measures Fume and gas collection Effective fume and offgas collection should be implemented in all stages of the smelting process to capture PCDD/PCDF emissions Processes to be considered include: Furnace-sealing systems to maintain a suitable furnace vacuum that avoids leaks and fugitive emissions Best available techniques for gas and fume treatment systems are those that use cooling and heat recovery if practical

Measure Description Considerations Use of hooding Hood additions of material, additions via tuyeres or lances and the use of robust rotary valves on feed systems High-efficiency dust removal Dusts and metal compounds should be removed as this material possesses high surface area on which PCDD/PCDF easily adsorb. Removal of these dusts would contribute to the reduction of PCDD/PCDF emissions Afterburners should be used at temperatures > 950 C to ensure full combustion of organic compounds, followed by rapid quenching of hot gases to temperatures below 250 C Processes to be considered include: Use of fabric filters, wet/dry scrubbers and ceramic filters
53
Other comments before a fabric filter except when carried out as part of the production of sulphuric acid
Fabric filters using highperformance materials are the most effective option. Collected particulate matter should be recycled in the furnace
Considerations include: PCDD/PCDF formation at 250 to 500 C, and destruction > 850 C with O2 Requirement for sufficient O2 in the upper region of the furnace for complete combustion Need for proper design of cooling systems to minimize reformation time
Activated carbon treatment should be considered as this material is an ideal medium for adsorption of PCDD/PCDF due to its large surface area
Processes to be considered include: Treatment with activated carbon using fixed or moving bed reactors Injection of carbon particulate into the gas stream followed by removal as a filter dust
Emerging research Catalytic oxidation Catalytic oxidation is an emerging technology which should be considered due to its high efficiency and lower energy consumption. Catalytic oxidation transforms organic compounds into water, CO2 and hydrochloric acid using a precious metal catalyst Considerations include: Process efficiency for the vapour phase of contaminants Hydrochloric acid treatment using scrubbers while water and CO2 are released to the air after cooling Catalytic oxidation has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and 99% efficiency. Off-gases should be dedusted treated for particulate removal prior to catalytic oxidation for optimum efficiency
54
55
7.
The achievable performance level7 for emissions of PCDD/PCDF from secondary zinc smelters is < 0.51 ng I-TEQ/Nm3.8
References
EPA (United States Environmental Protection Agency). 1981. Secondary Zinc Processing. Background Report AP-42, Section 12.14. epa.gov/ttn/chief/ap42/ch12/final/c12s14.pdf.
European Commission. 2001. Reference Document on Best Available Techniques in the Non-Ferrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Feng Xinbin, Qui Guangle, Li Guanghui, Li Ping, Wang Shaofeng, Mercury Emissions from Artisanal Zinc and Mercury Smelting in Guizhou, PR China, Goldschmidt Conference Abstracts 2005, The Geochemistry of Mercury, page A705 Government of Japan, Ministry of Economy, Trade and Industry. Report on Dioxin Reduction Technologies and their Effects in Secondary Zinc Production Facilities of Japan. November 2005.
Hbner C., Boos R., Bohlmann J., Burtscher K. and Wiesenberger H. 2000. State-of-the-Art Measures for Dioxin Reduction in Austria. Vienna. http://www.umweltbundesamt.at/fileadmin/site/publikationen/M116.pdf. Parvesse T. 2001. Controlling Emissions from Halogenated Solvents. Chemical Processing [Chem. Process.]. Vol. 64, no. 4, pp. 48-51. Apr 2001 Chemical Processing. /.
Personal communication, Member, Japan, Expert Group Meeting, 1 December, 2006

UNEP (United Nations Environment Programme). 2003. Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. UNEP, Geneva.
www.pops.int/documents/guidance/Toolkit_2003.pdf
UNEP, Compilation of comments received from Parties and others on the draft Guidelines on Best Available Techniques and provisional Guidance on Best Environmental Practices, October 14,
7
1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines. The operating oxygen concentration conditions of exhaust gases are used for metallurgical sources. 1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines.
56 2005
http://www.pops.int/documents/meetings/bat_bep/EGBATBEP1/meetingdocs/EGBATBE P_1_inf5.pdf UNEP Environment Program News Centre, http://www.unep.org/Documents.Multilingual/Default.asp? DocumentID=284&ArticleID=3204&l=en, as read on January 20, 2006 Xinbin Feng, Xianwu Bi, Guangle Qiu, Guanghui Li, Shunlin Tang, Mercury Pollution in Guizhou, China - A status Report, http://pbc.eastwestcenter.org/abstracts2005/abstract2005fengxinbin.htm, as read on December 29th, 2005
Section VI. Guidance/Guidelines by source category Source categories in Part III of Annex C
VI.B Thermal processes in the metallurgical industry not mentioned in Annex C, Part II
(i) Secondary lead production
Summary
Secondary lead smelting involves the production of lead and lead alloys, primarily from scrap automobile batteries, and also from other used lead sources (pipe, solder, drosses, lead sheathing). Production processes include scrap pretreatment, smelting and refining. Oils and plastics in feed, and temperatures between 250 and 500 C, may give rise to chemicals listed in Annex C of the Stockholm Convention. Best available techniques include the use of plastic-free and oil-free feed material, high furnace temperatures above 850 C, effective gas collection, afterburners and rapid quench, activated carbon adsorption, and dedusting fabric filters. The achievable performance level for secondary lead smelters: < 0.1 ng I-TEQ/Nm 3.
1.
Process description
The following summary of the process is drawn from Environmental Protection Agency (United States EPA) 1986. Figure 1 summarizes the process in diagrammatic form. Secondary lead smelters produce lead and lead alloys from lead-bearing scrap material. More than 60 percent of all secondary lead is derived from scrap automobile batteries. Other raw materials used in secondary lead smelting include wheel balance weights, pipe, solder, drosses, and lead sheathing. Secondary lead smelting includes 3 major operations: scrap pre-treatment, smelting, and refining. Scrap pre-treatment is the partial removal of metal and nonmetal contaminants from leadbearing scrap and residue. Processes used for scrap pre-treatment include battery breaking, crushing, and sweating. Battery breaking is the draining and crushing of batteries, followed by manual separation of the lead from nonmetallic materials. This separated lead scrap is then sweated in a gas- or oil-fired reverberatory or rotary furnace to separate lead from metals with higher melting points. Rotary furnaces are usually used to process low-lead-content scrap and residue, while reverberatory furnaces are used to process high-lead-content scrap. The partially purified lead is periodically tapped from these furnaces for further processing in smelting furnaces or pot furnaces. Smelting produces lead by melting and separating the lead from metal and non-metallic contaminants and by reducing oxides to elemental lead. Smelting is carried out in blast, reverberatory, and rotary kiln furnaces. In blast furnaces pre-treated scrap metal, rerun slag, scrap iron, coke, recycled dross, flue dust, and limestone are used as charge materials to the furnace. The process heat needed to melt the lead is produced by the reaction of the charged coke with blast air that is blown into the furnace. Some of the coke combusts to melt the charge, while the remainder reduces lead oxides to elemental lead. As the lead charge melts, limestone and iron float to the top of the molten bath and form a flux that retards oxidation of the product lead. The molten lead flows from the furnace into a holding pot at a nearly continuous rate. Refining and casting the crude lead from the smelting furnaces can consist of softening, alloying, and oxidation depending on the degree of purity or alloy type desired. These
SECTION VI. Guidance/guidelines by source category: Part III of Annex C
59
operations can be performed in reverberatory furnaces; however, kettle-type furnaces are most commonly used. Alloying furnaces simply melt and mix ingots of lead and alloy materials. Antimony, tin, arsenic, copper, and nickel are the most common alloying materials. Oxidizing furnaces, either kettle or reverberatory units, are used to oxidize lead and to entrain the product lead oxides in the combustion air stream for subsequent recovery in high-efficiency baghouses. Figure 1. Secondary lead smelting
Pretreatment
Smelting
Refining
Fume
Kettle (softening) refining

Dust & fume Fume
Soft lead ingots
SO2
Reverberatory smelting
Storage
Kettle (alloying) refining
Alloys
Flux
Fuel
Sawdust
Pretreated scrap
Recycled dust, rare scrap, fuel
Dust & fume
Crude lead bullion
Alloyin g agent
Fume
Blast furnace smelting
Kettle oxidation
Fume Fuel Air
Battery lead oxide
Limestone, recycled dust, coke, slag residue, lead oxide, scrap iron, pure scrap, return slag
Reverberatory oxidation
Red lead oxide Pb3O4 Yellow lead oxide PbO
Fuel
Air
Source: EPA 1986.
2.
The formation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) is probably due to the presence of chlorine from plastics and trace oils in the feed material.
2.1.
General information on emissions from secondary lead smelters
Air emissions from secondary lead smelting can escape as stack or fugitive emissions, depending on the facility age or technology. Main contaminants are sulphur dioxide (SO 2), other sulphur compounds and acid mists, nitrogen oxides (NO x), metals (especially lead) and their compounds, dusts and PCDD/PCDF. SO2 is collected and processed into sulphuric acid in acid plants. Fugitive
60
SO2 emissions can be controlled by good extraction and sealing of furnaces. NO x can be reduced using low-NOx or oxy-fuel burners. Particulate matter is collected using high-efficiency dust removal methods such as fabric filters and returned to the process (European Commission 2001, p. 359368).
2.2.
PCDD/PCDF are formed during base metals smelting through incomplete combustion or by de novo synthesis when organic and chlorine compounds such as oils and plastics are present in the feed material. The process is described in European Commission 2001, p. 133: PCDD/PCDF or their precursors may be present in some raw materials and there is a possibility of de-novo synthesis in furnaces or abatement systems. PCDD/PCDF are easily adsorbed onto solid matter and may be collected by all environmental media as dust, scrubber solids and filter dust. The presence of oils and other organic materials on scrap or other sources of carbon (partially burnt fuels and reductants, such as coke), can produce fine carbon particles which react with inorganic chlorides or organically bound chlorine in the temperature range of 250 to 500 C to produce PCDD/PCDF. This process is known as de-novo synthesis and is catalysed by the presence of metals such as copper or iron. Although PCDD/PCDF are destroyed at high temperature (above 850 C) in the presence of oxygen, the process of de-novo synthesis is still possible as the gases are cooled through the reformation window. This window can be present in abatement systems and in cooler parts of the furnace e.g. the feed area. Care taken in the design of cooling systems to minimise the residence time in the window is practised to prevent de-novo synthesis.
2.3.
Waste water originates from process effluent, cooling water and run-off and is treated using waste-water treatment techniques. Process residues are recycled, treated using downstream methods to recover other metals, or safely disposed.
3.
Variation in feed material and desired product quality influences process design and configuration. These processes should be applied in combination with good process control, gas collection and abatement systems. Processes considered as best available techniques include the blast furnace (with good process control), the ISA Smelt/Ausmelt furnace, the top-blown rotary furnace, the electric furnace and the rotary furnace (European Commission 2001, p. 379). The submerged arc electric arc furnace is a sealed unit for mixed copper and lead materials. It is cleaner than other processes if the gas extraction system is well designed and sized (European Commission, p. 395). The injection of fine material via the tuyeres of a blast furnace has been successfully used and reduces the handling of dusty material and the energy involved in returning the fines to a sinter plant (European Commission, p. 404). This technique minimizes dust emissions during charging and thus reduces the release of PCDD/PCDF through adsorption on particulate matter. No information is available on alternative processes to smelting for secondary lead processing.
4.
Primary and secondary measures of PCDD/PCDF reduction and elimination are discussed below.
Guidelines on BAT and Guidance on BEP Environment Canada Revision April 28, 2006
61
4.1.
Primary measures
Primary measures are regarded as pollution prevention techniques to reduce or eliminate the generation and release of persistent organic pollutants. Possible measures include: 4.1.1.Presorting of feed material Scrap should be sorted and pretreated to remove organic compounds and plastics to reduce PCDD/PCDF generation from incomplete combustion or by de novo synthesis. Whole battery feed or incomplete separation should be avoided. Feed storage, handling and pretreatment techniques will be determined by material size, distribution, contaminants and metal content. Milling and grinding, in conjunction with pneumatic or density separation techniques, can be used to remove plastics. Oil removal can be achieved through thermal decoating and de-oiling processes. Thermal decoating and de-oiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas (European Commission 2001, p. 232). 4.1.2.Effective process control Process control systems should be utilized to maintain process stability and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation, such as maintaining furnace temperature above 850 C to destroy PCDD/PCDF. Ideally, PCDD/PCDF emissions would be monitored continuously to ensure reduced releases. Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (for example, waste incineration), but research is still developing in this field. In the absence of continuous PCDD/PCDF monitoring, other variables such as temperature, residence time, gas components and fume collection damper controls should be continuously monitored and maintained to establish optimum operating conditions for the reduction of PCDD/PCDF. Particular attention is needed for the temperature measurement and control for furnaces and kettles used for melting the metals in this group so that fume formation is prevented or minimised (European Commission 2001, p. 390).
4.2.
Secondary measures
Secondary measures are pollution control techniques to contain and prevent emissions. These methods do not prevent the formation of contaminants. 4.2.1.Fume and gas collection Fume and off-gas collection should be implemented in all stages of the smelting process to control PCDD/PCDF emissions. The fume collection systems used can exploit furnace-sealing systems and be designed to maintain a suitable furnace depression that avoids leaks and fugitive emissions. Systems that maintain furnace sealing or hood deployment can be used. Examples are through hood additions of material, additions via tuyeres or lances and the use of robust rotary valves on feed systems. An [efficient] fume collection system capable of targeting the fume extraction to the source and duration of any fume will consume less energy. BAT for gas and fume treatment systems are those that use cooling and heat recovery if practical before a fabric filter except when carried out as part of the production of sulphuric acid (European Commission 2001, p. 397). 4.2.2.High-efficiency dust removal Dusts and metal compounds generated from the smelting process should be removed. This particulate matter possesses high surface area on which PCDD/PCDF easily adsorb. Removal of these dusts would contribute to the reduction of PCDD/PCDF emissions. Techniques to be considered are the use of fabric filters, wet and dry scrubbers and ceramic filters. Collected particulate should be recycled in the furnace.
62
Fabric filters using high-performance materials are the most effective option. Innovations regarding this method include bag burst detection systems, online cleaning methods and catalytic coatings to destroy PCDD/PCDF (European Commission 2001, p. 139140). 4.2.3.Afterburners and quenching Afterburners (post-combustion) should be used at a minimum temperature of 950 C to ensure full combustion of organic compounds (Hbner et al. 2000). This stage is to be followed by rapid quenching of hot gases to temperatures below 250 C. Oxygen injection in the upper portion of the furnace will promote complete combustion (European Commission 2001, p. 189). It has been observed that PCDD/PCDF are formed in the temperature range of 250 to 500 C. These are destroyed above 850 C in the presence of oxygen. Yet, de novo synthesis is still possible as the gases are cooled through the reformation window present in abatement systems and cooler areas of the furnace. Proper operation of cooling systems to minimize reformation time should be implemented (European Commission 2001, p. 133). 4.2.4.Adsorption on activated carbon Activated carbon treatment should be considered for PCDD/PCDF removal from smelter off-gases. Activated carbon possesses large surface area on which PCDD/PCDF can be adsorbed. Off-gases can be treated with activated carbon using fixed or moving bed reactors, or injection of carbon particulate into the gas stream followed by removal as a filter dust using high-efficiency dust removal systems such as fabric filters.
5.
5.1.
Emerging research
Catalytic oxidation
Catalytic oxidation is an emerging technology used in waste incinerators to eliminate PCDD/PCDF emissions. This process should be considered by secondary base metals smelters as it has proven effective for PCDD/PCDF destruction in waste incinerators. Catalytic oxidation can, subject to catalyst selection, be subject to poisoning from trace metalsand other exhaust gas contaminants. Validation work would be necessary before use of this process. Catalytic oxidation processes organic compounds into water, carbon dioxide (CO 2) and hydrochloric acid using a precious metal catalyst to increase the rate of reaction at 370 to 450 C. In comparison, incineration occurs typically at 980 C. Catalytic oxidation has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and 99% efficiency, and should be considered. Off-gases should be dedusted treated for particulate removal treated for particulate removal prior to catalytic oxidation for optimum efficiency. This method is effective for the vapour phase of contaminants. The resulting hydrochloric acid is treated in a scrubber while the water and CO2 are released to the air after cooling (Parvesse 2001).
6.
Summary of measures
Measure Description Various recommended smelting processes should be considered for new facilities Considerations Processes to be considered include: Blast furnace (with good process control), ISA Smelt/Ausmelt furnace, topblown rotary furnace, electric furnace and rotary furnace Other comments These processes should be applied in combination with good process control, gas collection and abatement systems
Table 1. Measures for new secondary lead smelters
Environment Canada Revision April 28, 2006

Measure Description Considerations Submerged electric arc furnace (it is a sealed unit for mixed copper and lead materials, cleaner than other processes if the gas extraction system is well designed and sized) Injection of fine material via the tuyeres of a blast furnace reduces handling of dusty material Other comments
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Table 2. Summary of primary and secondary measures for secondary lead smelters
Measure Primary measures Presorting of feed material Scrap should be sorted and pretreated to remove organic compounds and plastics to reduce PCDD/PCDF generation from incomplete combustion or by de novo synthesis Processes to be considered include: Avoidance of whole battery feed or incomplete separation Milling and grinding, followed by pneumatic or density separation techniques, to remove plastics Oil removal conducted through thermal decoating and de-oiling processes PCDD/PCDF emissions may be minimized by controlling other variables such as temperature, residence time, gas components and fume collection damper controls after having established optimum operating conditions for the reduction of PCDD/PCDF Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (e.g. waste incineration), but research is still developing in this field. Particular attention is needed for the temperature measurement and control for furnaces and kettles used for melting the metals in this group so that fume formation is prevented or minimized Thermal decoating and de-oiling processes for oil removal should be followed by afterburning to destroy any organic material in the off-gas Description Considerations Other comments
Secondary measures Fume and gas collection Fume and off-gas collection should be implemented in all stages of the smelting process to capture Processes to be considered include: Furnace-sealing systems to maintain a suitable furnace vacuum that avoids leaks and Best available techniques for gas and fume treatment systems are those that use cooling and heat
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Measure

Description PCDD/PCDF emissions Considerations fugitive emissions Use of hooding Hood additions of material, additions via tuyeres or lances and the use of robust rotary valves on feed systems Other comments recovery if practical before a fabric filter
Dusts and metal compounds should be removed as this material possesses high surface area on which PCDD/PCDF easily adsorb. Removal of these dusts would contribute to the reduction of PCDD/PCDF emissions Afterburners should be used at temperatures > 950 C to ensure full combustion of organic compounds, followed by rapid quenching of hot gases to temperatures below 250 C
Processes to be considered include: Use of fabric filters, wet/dry scrubbers and ceramic filters
Fabric filters using high-performance materials are the most effective option. Collected particulate matter should be recycled in the furnace
Considerations include: PCDD/PCDF formation at between 250 and 500 C, and destruction > 850 C with O2 Requirement for sufficient O2 in the upper region of the furnace for complete combustion Need for proper design of cooling systems to minimize reformation time
Activated carbon treatment should be considered as this material is an ideal medium for adsorption of PCDD/PCDF due to its large surface area
Processes to be considered include: Treatment with activated carbon using fixed or moving bed reactors Injection of carbon particulate into the gas stream followed by removal as a filter dust
Emerging research Catalytic oxidation Catalytic oxidation is an emerging technology which should be considered due to its high efficiency and lower energy consumption. Catalytic oxidation transforms organic compounds into water, CO2 and hydrochloric acid using a precious metal catalyst Considerations include: Process efficiency for the vapour phase of contaminants Hydrochloric acid treatment using scrubbers while water and CO2 are released to the air after cooling Catalytic oxidation has been shown to destroy PCDD/PCDF with shorter residence times, lower energy consumption and 99% efficiency. Off-gases should be dedusted treated for particulate removal prior to catalytic oxidation for optimum efficiency
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7.
Achievable performance level
The achievable performance level for emissions of PCDD/PCDF from secondary lead smelters is < 0.1 ng I-TEQ/Nm3.9
References
EPA (United States Environmental Protection Agency). 1986. Secondary Lead Processing. Background Report AP-42, Section 12.11. www.epa.gov/ttn/chief/ap42/ch12/final/c12s11.pdf. European Commission. 2001. Reference Document on Best Available Techniques in the NonFerrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Hbner C., Boos R., Bohlmann J., Burtscher K. and Wiesenberger H. 2000. State-of-the-Art Measures for Dioxin Reduction in Austria. Vienna. www.ubavie.gv.at/publikationen/Mono/M116s.htm. Parvesse T. 2001. Controlling Emissions from Halogenated Solvents. Chemical Processing [Chem. Process.]. Vol. 64, no. 4, pp. 48-51. Apr 2001 Chemical Processing. /.
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(ii)
Primary aluminium production
Summary
Primary aluminium is produced directly from the mined ore, bauxite. The bauxite is refined into alumina through the Bayer process. The alumina is reduced into metallic aluminium by electrolysis through the Hall-Hroult process (either using self-baking anodes Sderberg anodes or using prebaked anodes). Primary aluminium production is generally thought not to be a significant source of chemicals listed in Annex C of the Stockholm Convention. However, contamination with PCDD and PCDF is possible through the graphite-based electrodes used in the electrolytic smelting process. Possible techniques to reduce the production and release of chemicals listed in Annex C from the primary aluminium sector include improved anode production and control, and using advanced smelting processes. The achievable performance level in this sector should be < 0.1 ng TEQ/Nm3.
1.
Process description
Primary aluminium production refers to aluminium produced directly from the mined ore, bauxite. The bauxite is refined into alumina by the Bayer process, and then the alumina is reduced by electrolysis (the Hall-Hroult process) into metallic aluminium. This section does not cover the secondary aluminium processes, which is covered in section V.D (iii) of the present guidelines.
1.1.
The Bayer process: Refining bauxite to alumina
Bauxite is converted to alumina using the Bayer process (Figure 1). The bauxite ore is dried, crushed and ground into a powder and mixed with a solution of caustic soda to extract the alumina at elevated temperatures and pressures in digesters. A slurry is produced which contains dissolved sodium aluminate and a mixture of metal oxides, called red mud, which is removed in thickeners. The red mud is washed to recover the chemicals and is disposed of. The aluminate solution is cooled and seeded with alumina to crystallize the hydrated alumina in precipitator tanks. The crystals are washed and then calcined in rotary kilns or fluid bed/fluid flash calciners to produce the aluminium oxide or alumina, which is a white powder resembling table salt (Figure 1).
1.2.
The Hall-Hroult process: Reduction by electrolysis of alumina to aluminium
Aluminium is produced from alumina by electrolysis in a process known as the Hall-Hroult process. The alumina is dissolved in an electrolytic bath of molten cryolite (sodium aluminium fluoride). An electric current is passed through the electrolyte and flows between the anode and cathode. Molten aluminium is produced, deposited at the bottom of the electrolytic cell or pot, and periodically siphoned off and transferred to a reverberatory holding furnace. There it is alloyed, fluxed and degassed to remove trace impurities. Finally, the aluminium is cast or transported to the fabricating plants.
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Figure 1. Simplified flow sheet for alumina production
Source: Aluminium Association of Canada.
1.3.
Production of aluminium
There are two types of technologies used for the production of aluminium (Figure 2): those using self-baking anodes (Sderberg anodes) and those using prebaked anodes. The older Sderberg anodes are made in situ from a paste of calcined petroleum coke and coal tar pitch, and are baked by the heat from the molten electrolytic bath. As the anode is consumed, more paste descends through the anode shell in a process that does not require anode changes. Alumina is added periodically to Sderberg cells through holes made by breaking the crust alumina and frozen electrolyte which covers the molten bath. Depending on the placement of the anode studs, these are known as vertical stud Sderberg or horizontal stud Sderberg cells or pots. Automatic point feeding systems are used in upgraded plants, eliminating the need for regular breaking of the crust. Prebaked anodes are manufactured in a carbon plant from a mixture of calcined petroleum coke and coal tar pitch, which is formed into a block and baked in an anode furnace. The prebaked anode production plants are often an integrated part of the primary aluminium plant. The prebaked anodes are gradually lowered into the pots as they are consumed, and need to be replaced before the entire block has been consumed. The anode remnants, known as anode butts, are cleaned and returned to the carbon plant for recycling. Depending on the method of feeding the alumina into the electrolytic cells, the cells are called side-worked prebake or centre-worked prebake. For sideworked prebake cells, the alumina is fed to the cells after the crust is broken around the perimeter. For centre-worked prebake cells, the alumina is fed to the cells after the crust is broken along the centre line or at selected points on the centre line of the cell. The cathode typically has to be replaced every five to eight years because of deterioration, which can allow the molten electrolyte and aluminium to penetrate the cathode conductor bar and steel shell. The spent cathode, known as spent pot lining, contains hazardous and toxic substances such as cyanides and fluorides which must be disposed of properly. Molten alumina is periodically withdrawn from the cells by vacuum siphon and is transferred to crucibles. The crucibles containing liquid metal are transported to the casting plant, where the aluminium is transferred to the holding furnaces. Alloying elements are added in these furnaces. Dross (skimmings) formed by the oxidation of molten aluminium is skimmed off, and sealed containers are used to minimize further oxidation of the dross. Nitrogen and argon blanketing is used. This is followed by removal of sodium, magnesium, calcium and hydrogen. The treatment gas used varies depending on the impurities. Argon or nitrogen is used to remove hydrogen; mixtures of chlorine with nitrogen or argon are used to remove metallic impurities.
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Figure 2. General schematic of the electrolytic process for aluminium production
Source: Aluminium Association of Canada.
2.
Primary aluminium production is unlikely to be a significant source of releases of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF), although contamination is possible through the graphite-based electrodes (AEA Technology Environment 1999, p. 63). PCDD/PCDF release levels are generally thought to be low and the main interest is in the thermal processing of scrap materials (UNEP 2003, p. 73). This is discussed further in Section 2.3 below.However, monitoring data at a primary aluminium production facility in Russia observed high annual emissions for PCDD/PCDF releases to air and land (Kucherenko et al. 2001).
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2.1.
Emissions of PCDD/PCDF
There is limited information available on PCDD/PCDF formation from primary aluminium processes. Some literature suggests that initial emissions testing indicates that PCDD/PCDF are not considered significant from this sector. It is reported that it is unlikely that the Sderberg and prebaked processes release significantly different emissions per ton of aluminium produced (AEA Technology Environment 1999, p. 63). Test results on emission sources and abatement units associated with prebaked anode manufacturing indicate that PCDD are not significant from these sources. However, if chlorine compounds or additives are used, emissions will need to be examined (European Commission 2001, p. 669). Some studies have tested for PCDD in fume from the casting process because the use of chlorine for degassing and the presence of carbon from the combustion gases may lead to the formation of PCDD. Results from primary smelter cast houses have shown that releases are significantly below 1 gram per year (European Commission 2001, p. 289). The potential for PCDD/PCDF formation during the refining processes for both primary and secondary aluminium production has not been fully investigated. It has been recommended that this source be quantified (European Commission 2001, p. 318).
2.2.
Releases to land
The production of primary aluminium from ores is not thought to produce significant quantities of PCDD/PCDF (New Zealand Ministry for the Environment 2000). The Review of Dioxin Releases to Land and Water in the UK states that there may be the possibility of graphite-based electrodes having some PCDD/PCDF contamination (UK Environment Agency 1997). Swedish data suggest that the spent sludge from the cells may contain 7.8 ng Nordic-TEQ kg -1. However, if the cathode is high-purity carbon material and the reduction process does not involve chlorine or chloride materials, it is unlikely that PCDD/PCDF will be present. Metal reclaim fines may contain PCDD/PCDF because chlorine or chlorine-based products are used to degas the fraction of the aluminium that is poured into the extrusion billets.
2.3.
Research findings of interest
Limited information exists on the unintentional formation of PCDD/PCDF from this sector. It has been suggested that primary aluminium productionIt is not considered to be a significant source of releases. A paper (Anglesey Aluminium Dioxin and Furan Emission Survey, July 2000) reports non-detect levels for dioxins and furans emissions. However, aThe 2001 Russian study of the PCDD/PCDF emissions in the city of Krasnoyarsk did however concluded that the aluminium factory was responsible for 70% of industrial PCDD/PCDF emissions to air and 22% of industrial releases to land. More studies in this area would be needed in order to show whether or not primary aluminium production is a significant source of dioxins and furans. 2.4. General information on releases from primary aluminium plants
Greenhouse gases are a major pollutant from aluminium production and result from fossil fuel combustion, carbon anode consumption, and perfluorocarbons from anode effects. In addition to greenhouse gases, aluminium smelters also discharge other atmospheric emissions, as well as some solid wastes (spent potliners) and liquid effluents (SNC-Lavalin Environment 2002, p. 3:14). The use of carbon anodes leads to emissions of sulphur dioxide (SO 2), carbonyl sulphide (COS), polycyclic aromatic hydrocarbons (PAHs) and nitrogen oxides (NO x). Most of the sulphur in the carbon anode is released as COS, which is not entirely oxidized to SO 2 before being emitted at the potroom gas scrubber stacks. Sulphur emissions are predominately in the form of SO2 with a minor component of COS. The emission of
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sulphur gases from aluminium reduction is expected to rise with the increasing sulphur content of petroleum cokes used for anode manufacture. PAHs are the result of incomplete combustion of hydrocarbons found in certain pitch used to form the anodes. The use of prebake anodes has virtually eliminated the emissions of PAHs, mainly associated with Sderberg anodes. The NOx emissions mainly come from the combustion of fuel in the anode baking furnace (SNC-Lavalin Environment 2002, p. 3:14). The electrolysis of alumina also leads to the emission of fluorides (particulate fluorides and gaseous HF) and other particulates. The removal of fluorides from the cell gases in modern alumina injection dry scrubber systems is now greater than 99% efficient and the final fluoride emissions from modern prebake smelters are significantly lower. Anode changing and cooling of spent anode butts are the most important sources of fugitive fluoride emissions from an aluminium smelter and these are estimated to 4 to 5 times greater than stack emissions (after the scrubber) (SNC-Lavalin Environment 2002, p. 3:16). The anode effect results in generation of perfluorocarbons in smelting pots when the concentration of alumina falls below a certain level due to the lack of fresh feed. The carbon anode preferentially reacts with the fluorine in the cryolite solution because there is insufficient oxygen available from the alumina. When this event occurs, carbon tetrafluoride (CF 4) and hexafluoroethane (C2F6) are produced, along with a surge in voltage. The amount of perfluorocarbons generated depends on the efficiency of feed control in the pot. For pots not equipped with proper controls, perfluorocarbon emissions from anode effects can be the largest source, accounting for over 50% of the total smelter emissions (on a CO 2-equivalent basis). Practically any point-fed, computer-controlled pot can operate at low anode effect frequency. Older technologies, such as horizontal stud and vertical stud Sderberg cells, have higher perfluorocarbon generation rates. These technologies typically do not have individual pot sensing systems and the feed is usually a non-automated bulk system. The process control techniques in modern prebaked smelters are such that perfluorocarbon emissions can be reduced to less than 5% of the total greenhouse gas emissions from the smelter. CO 2 emissions from anode consumption are the next largest source for pots without modern controls (SNC-Lavalin Environment 2002, p. 3:1011). Table 1. Emissions, effluents, by-products and solid wastes from primary aluminium production
Process Alumina refining Anode production Air emissionsa Particulate Particulates, fluorides, polycyclic aromatic hydrocarbons, SO2, PCDD/PCDFb CO, CO2, SO2, fluorides (gaseous and particulate), perfluorocarbons (CF4, C2F6), polycyclic aromatic hydrocarbons, PCDD/PCDFb Effluents Waste water containing starch, sand, and caustic Waste water containing suspended solids, fluorides, and organics Wet air pollution control effluents (wet electrostatic precipitator) By-products and solid wastes Red mud, sodium oxalate Carbon dust, tar, refractory waste Spent potliners, wet air pollution control wastes, sludges
Aluminium smelting
a. Excluding combustion-related emissions. b. Based on the Krasnoyarsk study (Kucherenko et al. 2001). Source: Energetics Inc. 1997.
3.
New primary aluminium plants
The Stockholm Convention states that when consideration is being given to proposals for construction of a new primary aluminium plant, priority consideration should be given to
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alternative processes, techniques or practices that have similar usefulness but which avoid the formation and release of the identified substances.
3.1.
Alternative processes to primary aluminium smelting (emerging technologies)
There are a number of research initiatives currently under way to produce primary aluminium while concurrently reducing energy consumption and emissions (European Commission 2001, p. 335; SNC-Lavalin Environment 2002; Welch 1999; USGS 2001; BCS Inc. 2003, p. 4158). These initiatives include: Inert anodes: Carbon-free anodes that are inert, dimensionally stable, that are slowly consumed, and produce oxygen instead of CO2. The use of inert anodes eliminates the need for an anode carbon plant (and emissions of polycyclic aromatic hydrocarbons from the process); Wettable cathodes: New cathode materials or coatings for existing cathode materials that allow for better energy efficiency; Vertical electrodes low-temperature electrolysis (VELTE): The process uses a non-consumable metal alloy anode, a wetted cathode and an electrolytic bath, which is kept saturated with alumina at the relatively low temperature of 750 C by means of free alumina particles suspended in the bath. This technology could produce primary aluminium metal with lower energy consumption, lower cost, and lower environmental degradation than the conventional Hall-Hroult process; Drained cell technology: Features the coating of aluminium cell cathodes with titanium dibromide and eliminating the metal pad, which reduces the distance between anode and cathode, thereby lowering the required cell voltage and reducing heat loss; Carbothermic technology: Carbothermic reduction produces aluminium using a chemical reaction that takes place within a reactor and requires much less physical space than the Hall-Hroult reaction. This process would result in significantly reduced electrical consumption, and the elimination of perfluorocarbon emissions resulting from carbon anode effects, hazardous spent pot liners, and hydrocarbon emissions associated with the baking of consumable carbon anodes; Kaolinite reduction technology: The production of aluminium by reduction of aluminium chloride using clays holds appeal because the raw materials are readily available and inexpensive. The thermodynamics also provide high-speed conversion reactions with lower electrical demand and no bauxite residue is produced.
4.
Primary and secondary measures for reducing emissions of PCDD/PCDF from primary aluminium production processes are outlined below. The extent of emission reduction possible with the implementation of primary measures only is not readily known. It is therefore recommended that consideration be given to implementation of both primary and secondary measures at existing plants. Note that no secondary measures have been developed specifically for primary aluminium smelters to control the unintentional formation of PCDD/PCDF. The following are general measures that may result in lower pollutant emissions at primary aluminium smelters, including releases of PCDD/PCDF.
4.1.
Primary measures
Primary measures are understood to be pollution prevention measures that prevent or minimize the formation and release of the identified substances (particulates, fluorides, polycyclic aromatic hydrocarbons, sulphur dioxide, carbon dioxide, carbon monoxide, and perfluorocarbons). Note that
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there are no primary measures identified for PCDD/PCDF. These are sometimes referred to as process optimization or integration measures. Pollution prevention is defined as: The use of processes, practices, materials, products or energy that avoid or minimize the creation of pollutants and waste, and reduce overall risk to human health or the environment. (See section III.B of the present guidelines.) For new smelters, using the prebake technology rather than the Sderberg technology for aluminium smelting is a significant pollution prevention measure (World Bank 1998). The use of centre-worked prebaked cells with automatic multiple feeding points is considered to be a best available technique for the production of primary aluminium (European Commission 2001, p. 325). Point feeders enable more precise, incremental feeding for better cell operation. They are generally located at the centre of the cell and thereby cut down on the diffusion required to move dissolved alumina to the anodic reaction sites. The controlled addition of discrete amounts of alumina enhances the dissolution process, which aids in improving cell stability and control, minimizing anode effects, and decreasing the formation of undissolved sludge on the cathode. In the jargon of modern commerce, point feeders enable just-in-time alumina supply to permit optimum cell operation. Point feeder improvements continue to be made as more accurate cell controllers become available (BCS Inc. 2003, p. 47). Advanced process controllers are also being adopted by industry to reduce the frequency of anode effects and control operational variables, particularly bath chemistry and alumina saturation, so that cells remain at their optimal conditions (BCS Inc. 2003). Primary measures which may assist in reducing the formation and release of the identified substances include (European Commission 2001, p. 326, 675676): An established system for environmental management, operational control and maintenance; Computer control of the electrolysis process based on active cell databases and monitoring of cell operating parameters to minimize the energy consumption and reduce the number and duration of anode effects; If local, regional or long-range environmental impacts require SO 2 reductions, the use of low-sulphur carbon for the anodes or anode paste if practicable, or an SO 2 scrubbing system.
4.2.
Secondary measures
Secondary measures are understood to be pollution control technologies or techniques, sometimes described as end-of-pipe treatments. Note that the following are not considered secondary measures specific to minimization of PCDD/PCDF releases, but for pollutant releases generally. The following measures have been shown to effectively reduce releases from primary aluminium production and should be considered best available techniques (European Commission 2001, p. 326, 675676): Feed preparation: Enclosed and extracted grinding and blending of raw materials, fabric filters for abatement; Complete hood coverage of the cells, which is connected to a gas exhaust and filter. The use of robust cell covers and adequate extraction rates. Sealed anode butt cooling system; Better than 99% fume collection from cells on a long-term basis. Minimization of the time taken for opening covers and changing anodes; Gases from the primary smelting process should be treated to remove dust, fluorides and hydrogen fluoride using an alumina scrubber and fabric filter. The scrubbing
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SECTION V. Guidelines/guidance by source category: Part II of Annex C efficiency for total fluoride should be > 99.8%, and the collected alumina used in the electrolytic cells; Use of low-NOx burners or oxy-fuel firing. Control of firing of furnaces to optimize the energy use and reduce polycyclic aromatic hydrocarbons and NO x emissions; If there is an integrated anode plant the process gases should be treated in an alumina scrubber and fabric filter system and the collected alumina used in the electrolytic cells. Tars from mixing and forming processes can be treated in a coke filter; Destruction of cyanides, tars and hydrocarbons in an afterburner if they have not been removed by other abatement techniques; Use of wet or semi-dry scrubbing to remove SO2 if necessary; Use of biofilters to remove odorous components if necessary; Use of sealed or indirect cooling systems.
5.
Summary of measures
Tables 2 and 3 present a summary of the measures discussed in previous sections. Table 2. Measures for new primary aluminium production plants
Measure Alternative processes Description Priority should be given to alternative processes with less environmental impacts than tradition primary aluminium production plants Considerations Examples include: Inert anodes Wettable cathodes Vertical electrodes lowtemperature electrolysis Drained cell technology Carbothermic technology Kaolinite reduction technology Prebake technology The use of centre-worked prebaked cells with automatic multiple feeding points is considered a best available technique New primary aluminium production plants should be required to achieve stringent performance and reporting requirements associated with best available technologies and techniques Consideration should be given to the primary and secondary measures listed in Table 3 No performance requirements have been determined for releases of PCDD/PCDF from primary aluminium plants Other comments These processes are still in the development phase
Performance requirements
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Table 3. Summary of primary and secondary measures for primary aluminium production plants
Measure Primary measures Environmental management system, operational control and maintenance Computer-controlled process and monitoring Feed selection: Use of low sulphur carbon for anodes or anode paste Secondary measures Feed preparation: Enclosed grinding and blending of raw materials. Use of fabric filters Complete hood coverage of cells Fume collection and treatment To prevent the releases of particulates To minimize energy consumption and reduce number and duration of anode effects To control sulphur dioxide emissions, if necessary SO2 scrubbing system may be used Description Considerations Other comments
The use of hoods that completely cover cells to collect gases to the exhaust and filter Fume collection efficiency should be greater than 99%. Gases should be treated to remove dust, fluorides and HF using an alumina scrubber and fabric filter The firing of the furnace should be optimized to reduce emissions of polycyclic aromatic hydrocarbons and NOx Process gases from anode plant should be treated in an alumina scrubber and fabric filter system To destroy cyanides, tars and polycyclic aromatic hydrocarbons if not removed by other abatement To remove SO2 if necessary To remove odorous components if necessary The alumina should be used in the electrolytic cells. Tars can be treated in a coke filter The time taken for opening the covers and changing the anodes should be minimized
Low NOx burners or oxy-fuel firing
Alumina scrubber
Afterburner
Wet or semi-dry scrubbing Biofilters
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6.
The achievable performance level for emissions of PCDD/PCDF in the primary aluminium sector is < 0.1 ng TEQ/Nm3.10
References
AEA Technology Environment. 1999. Releases of Dioxins and Furans to Land and Water in Europe. Prepared for Landesumweltamt Nordrhein-Westfalen, Germany, on behalf of European Commission DG Environment. Aluminium Association of Canada. www.aac.aluminium.qc.ca/frameset/index_en.html. Anglesey Aluminum Dioxin and Furan Emission Survey July 2000, ESP Environmental, ExCAL House, Capel Hendre Industrial Estate, Ammanford, Carmarthenshire, SA18 3SJ, Tel: 01269 831606, Fax: 01269 841867 BCS Inc. 2003. U.S. Energy Requirements for Aluminum Production: Historical Perspectives, Theoretical Limits and New Opportunities. Prepared under contract for the United States Department of Energy, Energy Efficiency and Renewable Energy. Energetics Inc. 1997. Energy and Environmental Profile of the U.S. Aluminum Industry. Prepared for the United States Dept of Energy, Office of Industrial Technologies, Maryland. www.eere.energy.gov/industry/aluminum. European Commission. 2001. Reference Document on Best Available Techniques in the NonFerrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Kucherenko A., Kluyev N., Yufit S., Cheleptchikov A. and Brodskj E. 2001. Study of Dioxin Sources in Krasnoyarsk, Russia. Organohalogen Compounds 53:275278. New Zealand Ministry for the Environment. 2000. New Zealand Inventory of Dioxin Emissions to Air, Land and Water, and Reservoir Sources. www.mfe.govt.nz/publications/hazardous/dioxinemissions-inventory-mar00.pdf. SNC-Lavalin Environment. 2002. Evaluation of Feasibility and Roadmap for Implementing Aluminium Production Technologies That Reduce/Eliminate Greenhouse Gases and Other Emissions. Prepared for Environment Canada. UK Environment Agency. 1997. A Review of Dioxin Releases to Land and Water in the UK . Research and Development Publication 3. Environment Agency, Bristol, United Kingdom. UNEP (United Nations Environment Programme). 2003. Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. UNEP, Geneva. www.pops.int/documents/guidance/Toolkit_2003.pdf. USGS (United States Geological Survey). 2001. Aluminium Case Study. Appendix 2, Technological Advancement: A Factor in Increasing Resource Use . Open-File Report 01-197. pubs.usgs.gov/of/2001/of01-197 . Welch B.J. 1999. Aluminum Production Paths in the New Millennium. Journal of Metals 51:5. www.tms.org/pubs/journals/JOM/9905/Welch-9905.html. World Bank. 1998. Industry Sector Guidelines Aluminum Manufacturing. In: Pollution Prevention and Abatement Handbook. World Bank, Washington, D.C
10
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(iii) Magnesium production

Summary
Magnesium is produced either from raw magnesium chloride with molten salt electrolysis, or magnesium oxide reduction with ferrosilicon or aluminium at high temperatures, as well as through secondary magnesium recovery (for example, from asbestos tailings). The addition of chlorine or chlorides, the presence of carbon anodes and high process temperatures in magnesium production can lead to the formation of chemicals listed in Annex C of the Stockholm Convention and their emission in air and water. Alternative techniques may include the elimination of the carbon source by using non-graphite anodes, and the application of activated carbon. However, achievable performance depends on the type of process and controls utilized.
1.
Process description
There are two major process routes utilized for production of magnesium metal. The first process recovers magnesium chloride from the raw materials and converts it to metal through molten salt electrolysis. The second type of process involves reducing magnesium oxide with ferrosilicon or aluminium at high temperatures. Examples of the two types of processes are described below. Magnesium can also be recovered and produced from a variety of magnesium-containing secondary raw materials (VAMI 2004).
1.1.
Magnesium production process from magnesium oxide resources
The process allows magnesium to be produced from oxide raw materials: magnesite, brusite, serpentine and others. It is also suitable for magnesium production from raw materials containing magnesium sulphate or its mixture with chlorides, including sea water. In all cases chlorine produced by electrolysis is recycled and used for conversion of magnesium oxide or sulphate into magnesium chloride (VAMI 2004). Thermal processes for magnesium production are used in a number of countries, however these processes are not considered best available techniques nor best environmental practices. In countries where it is the only means of production, the following measures can be taken to reduce the POPs that are being released into the environment. Proper raw material selection: Knowledge of the composition of the raw materials can minimize fuel usage by avoiding excessive quantities of one reagent which is heated and then disposed of as waste. Control of the purity of raw materials through purchasing strategies and quality control processes of suppliers assist in minimizing the energy usage and hence POPs release through heating inserts. The selection of a process which minimizes energy consumption will minimize the production of POPs. Continuous processes tend to be more energy efficient as there is less heat used to return the reactor to operating temperatures between cycles. One widely used process available for license is the Magnatherm process which replaces the coal heating of the retort with electrical induction heating. In larger facilities coal flue gases may be passed through particle abatement. These require a reliable electricity supply. However, storage of fine particulate matter is demanding in many environments and appropriate storage and waste arrangements are required for the captured material until a safe disposal route is identified. Co-location of facilities and regional cooperation to manage and dispose wastes would be beneficial.
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The process consists of the following stages (see Figure 1): Leaching of raw material by hydrochloric acid and purification of the solution produced; Separation of magnesium chloride product in the form of synthetic carnallite or mixture of chlorides from said solution; Dehydration of said product in a fluidized bed by the stream of hot gases, containing hydrogen chloride, with production of solid dehydrated product, containing not more than 0.3 wt.% of magnesium oxide and water each; Feeding of said product into electrolyzers or head unit of flow line and its electrolysis, with production of magnesium and chlorine. Chlorine produced by electrolysis is fed into the burners of fluidized bed furnaces, where it is converted into hydrogen chloride (HCl). Waste gases of the fluidized bed furnaces, containing HCl, are either treated by water to produce hydrochloric acid, which is used for raw material leaching, or neutralized by aqueous suspension of magnesium oxide to produce magnesium chloride solution. Spent electrolyte forming in the course of electrolysis is used for synthetic carnallite production. All the waste products containing chlorine are utilized with the production of neutral oxides. It is a significant advantage of the process from an environmental point of view. Figure 1. Flow diagram of magnesium production process from magnesium oxide resources
Source: VAMI 2004.
1.2.
The Pidgeon process (thermal reduction process)
In the Pidgeon process, magnesium is produced from calcined dolomite under vacuum and at high temperatures using silicon as a reducing agent. In the process, the finely crushed dolomite (magnesium/calcium) carbonate is fed to rotary kilns where it is calcined, and where the carbon
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dioxide is driven off, leaving a product of calcined dolomite. The calcined dolomite is then pulverized in a roller mill prior to mixing with finely ground ferrosilicon and fluorspar. The fine calcined dolomite, ferrosilicon, and fluorspar are weighed in batch lots and mixed in a rotary blender. This mixture is then briquetted in briquetting presses (Noranda Magnesium website). Briquettes are then conveyed to the reduction furnaces. The reduction operation is a batch process releasing magnesium in vapour form, which condenses in the water-cooled section of the retort outside the furnace wall. After removal from the furnace, the magnesium crown is pressed from the sleeve in a hydraulic press. The residue from the reduction charge is removed from the retort and sent to a waste dump. Figure 2 illustrates the process in diagrammatic form.
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Figure 2. Process flow chart: Timminco magnesium plant

Magnesite
Crushing
Kiln fines (sales) Calcination Stack CO2, off-gases (to atmosphere)
Grinding Mixing Ferrosilicon
Briquetting
Retorting
Residue (to waste dump)
Melting Casting Billets
SF6
Magnesium ingots (to markets) Billets (to markets) Extrusions (to markets)
Extrusion Source: Hatch and Associates 1995.
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2.
2.1.

Emissions to air
2.1.1.General information on emission from magnesium production
Magnesium production facilities generate several types of pollutants, including dust, sulphur dioxide (SO2), nitrogen oxides (NOx), chlorine (Cl2), hydrochloric acid (HCl), and in several cases emission of sulphur hexafluoride (SF6) throughout the manufacturing process. Dust and sulphur dioxide are mainly emitted from the calcinations of dolomite and magnesium oxide (MgO), from pellet drying as well as from chlorination off-gas treatment. The source of nitrogen oxides emissions are dolomite and MgO calcinations and pellet drying. Chlorine and hydrochloric acid are released from electrolysis and chlorination processes, and the chlorination off-gas treatment system. While carbon dioxide is emitted from the whole manufacturing process, the source of sulphur hexafluoride discharges is the cast-house. 2.1.2.Emissions of PCDD and PCDF According to tests conducted on an electrolytic process in a magnesium production plant in Norway, the main process causing the formation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) was a furnace converting pellets of MgO and coke to magnesium chloride (MgCl2) by heating in a Cl2 atmosphere at 700800 C (Oehme, Man and Bjerke 1989; European Commission 2001). The purification of MgO using HCl and graphite blades (chlorination) or electrolysis of MgCl 2 using graphite electrodes are also possible other sources of PCDD/PCDF formation (UNEP 2003). Timminco Ltd, in Ontario, Canada, which utilizes the thermal reduction Pidgeon process technology, reported PCDD/PCDF release to air of 0.416 g TEQ/year (CCME 2003). Table 1 shows emissions to air from different magnesium production processes. Table 1. PCDD/PCDF emissions to air from different magnesium production processes
Process type Electrolytic Source From chlorination of offgas treatment From chlorination vent gas From electrolysis/chlorination Thermal Norsk Hydro process Reduction, refining and melting 0.08 Emissions11 (ng/Nm3) 0.8 0.8 Concentration (g TEQ/t) 12 28 13 3 < 1.0
11
1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines.
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Hydro Magnesium Canada reported a total of 0.456 g TEQ/year 12 emissions of PCDD/PCDF to air, broken down as shown in Table 2.
12
Hydro Magnesium Canada presentation at Electrolytic Magnesium Industry Bi-national Informative Meeting, Montreal, 12 December 2000, by Jean Laperriere, Environment Chief.
SECTION VI. Guidance/guidelines by source category: Part III of Annex C Table 2. Emissions of PCDD/PCDF by source: Hydro Magnesium Canada
Source Dissolving Dehydration Electrolysis Foundry HCl synthesis Mg remelting g TEQ/year 0.001 0.112 0.277 0.025 0.0003 0.050
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2.2.

2.2.1.Water
The main water pollutants in the magnesium manufacturing process are metal compounds as suspended solids. However, chlorinated hydrocarbons and PCDD/PCDF are also found in waste water from the magnesium electrolysis process (Table 3) Table 3. Releases of PCDD/PCDF to water from different magnesium production processes
Type Electrolytic Thermal Norsk Hydro process Source: Hydro Magnesium Canada. ng/m3 100 0.08 ug TEQ/t of Mg 13 3 < 0.1
2.2.2.Land The wet scrubbing process utilized in treatment of gas streams would be expected to generate residues containing PCDD/PCDF. A water treatment system that includes settling of these residues in a lagoon would then constitute a release to land (UNEP 2003).
3.
Alternative processes for magnesium production
Although process efficiency and productivity could be the main driving forces in the advancement and development of alternative new technologies, it is expected that environmental aspects will be given due consideration This means elimination or minimization of the formation of pollutants at source, and the incorporation of effective pollution abatement systems, should be part of the initial design of the project.
3.1.
Norsk Hydro dehydration process
Norsk Hydro has developed and successfully implemented a new technology, an MgCl 2 dehydration process, in its plant in Canada (European Commission 2001). Releases of pollutants, especially PCDD/PCDF, generated from this process are significantly lower than existing processes (Tables 1 and 3). The plant produces MgCl2 brine by dissolving magnesite rock in hydrochloric acid. Impurities such as aluminium, iron and manganese are removed from the leach liquor by purification. The brine is then subjected to evaporation and prilling and drying using the fluidized bed technique. This will result in an anhydrous MgCl2 product.
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Hydros electrolysis cells are operated at around 400 kA. The MgCl 2 prills are fed continuously from the dehydration plant into the electrolysis cells. This operation produces magnesium metal and chlorine gas. The chlorine gas is reacted with hydrogen to produce hydrochloric acid, which is recycled to the magnesite dissolving stage. The molten magnesium is cast under controlled conditions. The final products are pure metal and alloys in the form of ingots and grinding slabs.
3.2.
Norandas magnesium recovery from asbestos tailings
A new technology in use by Noranda 13 involves recovery of magnesium from asbestos tailings (Noranda Inc. website). The process description is as follows: Transforming serpentine into high-grade magnesium: In Norandas proprietary magnesium process, serpentine undergoes a series of chemical processes and filtration steps to produce a very pure anhydrous magnesium chloride. This is electrolytically reduced in state-of-the-art highefficiency cells into magnesium and chlorine. The chlorine is completely captured and recycled. The companys projections for its environmental performance include emission levels of no more than 0.09 g TEQ of PCDD/PCDF to air, using an activated carbon adsorption system. Feed preparation: Norandas magnesium process starts with crysotile serpentine (3MgO2SiO22H2O), a mining residue containing 23% magnesium. The material is already mined and above ground, adjacent to the plant. Serpentine is crushed, screened and magnetically separated. The material is then leached with hydrochloric acid to create magnesium chloride brine, along with a silica and iron residue. Brine purification: To purify the magnesium chloride solution, the brine goes through further purification steps to remove major impurities such as boron. The impurities are extracted from the brine by precipitation. Fluid bed drying: High-purity brine is dried to produce granular magnesium chloride. This yields partially dehydrated magnesium chloride (MgCl 2). HCl is recycled for use in the leaching phase. Melt chlorinator: The magnesium chloride granules are melted in an electrolyte and treated by a chlorination process involving the injection of gaseous HCl. The acid and water are recovered in the process for use in the leaching phase. Electrolytic cell: Metallic magnesium is produced through electrolysis by sending a strong electrical current through the electrolyte. The chlorine gas that is produced during the electrolysis phase is washed and combined with hydrogen and thereby reconverted into acid, which will be reconverted into gas and reused for the chlorination process. Casting: The metallic magnesium is tapped and then cast in ingots. Purification of emissions: The production facility is equipped with gas scrubbers throughout the process to purify the process and ventilation emissions. The chlorine is completely captured, recycled and returned to the process. Emissions are washed to extract particles and other contaminants before being released into the atmosphere. The process releases no water effluent to the environment.
4.
4.1.

Primary measures
The electrolysis process is of most interest from the point of view of PCDD/PCDF emissions because of the presence of carbon and of chlorine in the process and the high temperature conditions. Primary measures that may assist in reducing the formation and release of the identified substances include eliminating the carbon source by substituting the graphite by non-graphite anodes, possibly metal anodes. Replacement of graphite anodes by metal anodes took place in the chlorine industry at the start of the 1970s, and very minor amounts of PCDF were formed (Eurochlor 2001).
13
In April 2003 this plant was shut down for an indefinite time due to market conditions.
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The new MgCl2 dehydrating process has been found to produce much lower levels of PCDD/PCDF (Tables 1 and 3). It is expected that in the proposed Cogburn magnesium project in British Columbia the STI/VAMI technology will produce less chlorinated hydrocarbons than produced at Magnola due to the absence of chlorinators. See subsection 5 below for additional information.
4.2.
Secondary measures
Treatment of effluents using techniques such as nanofiltration and use of specially designed containment for solid residues and effluents; Treatment of off-gases by cleaning of the off-gas from the chlorinators in a series of wet scrubbers and wet electrostatic precipitators before incineration, and using bag filters to clean and remove entrained salts from the magnesium electrolysis process; Use of activated carbon: In the Cogburn magnesium project, there are two chlorinated hydrocarbon removal systems; both are based on activated carbon removal of chlorinated hyrdocarbons in liquid effluents.
Measures include:
5.
5.1.
Emerging research
The Cogburn magnesium project
A Cogburn magnesium project in British Columbia is expected to utilize the STI/VAMI electrolytic cell technology for the decomposition of MgCl 2 to magnesium metal and chlorine gas (Figure 3). Presently in the magnesium industry, this is done largely in monopolar diaphragmless electrolytic cells. The STI/VAMI technology is based on a flow-through design in which all the cells in the cell hall are linked together. Each cell is fed individually. The magnesium and electrolyte flow from one cell to the next via a system of enclosed launders. The magnesium is collected at the end of the flow line in a separator cell, and is siphoned out for casting at the cast house. This system is currently utilized at the Dead Sea magnesium plant in Israel (Hatch and Associates 2003).
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Figure 3. Simplified flow diagram: Cogburn magnesium plant
Source: Hatch and Associates 2003.
6.
Summary of measures
Tables 4 and 5 present a summary of the measures discussed in previous sections. Table 4. Summary of primary measures for magnesium plants
Measure Alternative processes Description Priority consideration should be given to alternative processes with less environmental impacts than traditional magnesium manufacturing processes Considerations Examples include: Norsk Hydros MgCl2 brine dehydration process Elimination of carbon source: replaces graphite with non-graphite anode Smelter should ensure that only high-grade scrap, free of contaminants, is used
Feed quality
Increasing availability of magnesium scrap and other magnesium-containing raw materials would make it attractive for smelters to use it in their process The calcinations of dolomite creates significant amount of dust
Pre-treatment techniques
Use of gas suspension calciner could reduce it significantly
SECTION VI. Guidance/guidelines by source category: Part III of Annex C Table 5. Summary of secondary measures for magnesium plants
Measure Treatment of off-gases Description Off-gases from chlorination furnaces in magnesium plants contain pollutants such as PCDD, PCDF and chlorinated hydrocarbons Considerations Use of wet scrubbers and wet electrostatic precipitators remove aerosols, followed by incineration to destroy PCDD/PCDF and other volatile organic compounds. Activated carbon is also used to absorb pollutants Removal of solids by flocculation, sedimentation and filtration, followed by activated carbon injection to remove contaminants
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Treatment of effluent
Waste water collected from the various parts of the magnesium plant, such as the scrubbing effluent from the chlorination stage, contain PCDD/PCDF and chlorinated hydrocarbons
7.

Classification Air Emission factors: g TEQ/t of Mg Water 9,000 Land n.a. Product n.a. Residue 0
Table 6. Emission factors in the magnesium industry: PCDD/PCDF
Production using MgO/C thermal treatment in Cl2 no effluent, limited gas treatment Production using MgO/C thermal treatment Thermal reduction process n.a. Not applicable. n.d. Not determined. Source: UNEP 2003.
250
50 3
30 n.d.
n.a. n.a.
n.a. n.a.
n.a. n.a.
Table 7. Emission factors in the magnesium industry: Hexachlorobenzene (HCB)

Location Air Norsk Hydro, Posrgrunn* Norsk Hydro, Bcancour* Noranda, Asbestos** n.d. Not determined. 7003,000 90170 439300 Water n.d. 2.4 0 Emission factors: g/kg Land n.d. 60120 8003,000 Process generated n.d. n.d. Not estimated84,000 Volatilized from land n.d. n.d. ~6002,400
* Source: Bramley 1998. ** Source: Kemp 2004; note facility was operating at only 50% of design capacity and emission factor is believed to be overstated as a result.
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References
Bramley M.J. 1998. Dioxin and Hexachlorobenzene Releases from Magnesium Production in North America: Lessons from Norandas Magnola Project in Asbestos, Quebec. Greenpeace, Canada. CCME (Canadian Council of Ministers of the Environment). 2003. Status of Activities Related to Dioxins and Furans Canada-Wide Standards. CCME, Winnipeg. www.ccme.ca/assets/pdf/d_f_sector_status_rpt_e.pdf. Eurochlor. 2001. Effect of Dioxins on Human Health. http://www.eurochlor.org/chlorine/issues/dioxins.htm. European Commission. 2001. Reference Document on Best Available Techniques in the NonFerrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Hatch and Associates. 1995. Addendum to Primary NonFerrous Smelting and Refining Sector in Canada - Magnesium. Prepared for Environment Canada. Hatch and Associates. 2003. Binder No. 1 Project Summary For Production Feasibility Study For Cogburn Magnesium Plant. Prepared for Leader Mining International. www.leadermining.com/Binder_No1_Project_Summary.pdf. Noranda Inc. Noranda Magnesium A Production Breakthrough. my.noranda.com/Noranda/magnesium/Introducing+Noranda+Magnesium/A+Production+Breakthr ough/_A+Production+Breakthrough.htm. Noranda Magnesium. Magnesium Production: Thermal Reduction - Pidgeon Process. www.norandamagnesium.com/. Norsk Hydro. 2001. Environmental Report 2001, Light Metals: Specific Values. www.hydro.com/de/global_commitment/environment/reports/light_metals_main.html. Oehme M., Man S. and Bjerke B. 1989. Formation of Polychlorinated Dibenzofurans and Dibenzo-p-dioxins by Production Processes for Magnesium and Refined Nickel. Chemosphere 18:78. Personal Communication, D. Kemp, 2004 Personal communication from Expert Group Best Available Techniques Best Environmental Practices, UK Member, February 2006 UNEP (United Nations Environment Programme). 2003. Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. UNEP, Geneva. www.pops.int/documents/guidance/Toolkit_2003.pdf. VAMI (Russian National Aluminium-Magnesium Institute). 2004. Magnesium Production Process from Magnesium Oxide Resources. http://www.vami.ru/processes/magnesium/sposob_proizvod_magnia_is_oksidnogo_siria.htm.
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(iv) Secondary steel production

Summary
Secondary steel is produced through direct smelting of ferrous scrap using electric arc furnaces. The furnace melts and refines a metallic charge of scrap steel to produce carbon, alloy and stainless steels at non-integrated steel mills. Ferrous feed materials may include scrap, such as shredded vehicles and metal turnings, or direct reduced iron. Chemicals listed in Annex C of the Stockholm Convention, such as PCDD and PCDF, appear to be most probably formed in the electric arc furnace steel-making process via de novo synthesis by the combustion of non-chlorinated organic matter such as polystyrene, coal and particulate carbon in the presence of chlorine donors. Many of these substances are contained in trace concentrations in the steel scrap or are process raw materials such as injected carbon. Primary measures include adequate off-gas handling and appropriate off-gas conditioning to prevent conditions leading to de novo synthesis formation of PCDD/PCDF. This may include post-combustion afterburners, followed by rapid quench of off-gases. Secondary measures include adsorbent injection (for example, activated carbon) and high-level dedusting with fabric filters. The achievable performance level using best available techniques for secondary steel production is < 0.1 ng/Nm3.
1.
1.1.
Process description
General process description
The direct smelting of iron-containing materials, such as scrap, is usually performed in electric arc furnaces, which play an important and increasing role in modern steelworks. The furnace melts and refines a metallic charge of scrap steel to produce carbon, alloy and stainless steels at nonintegrated (secondary steel) mills. An electric arc furnace is a cylindrical vessel with a dish-shaped refractory hearth and electrodes that lower from the dome-shaped, removable roof. Refractory bricks form the lining of the furnace. The walls typically contain water-cooled panels, which are covered to minimize heat loss. The electrodes may also be equipped with water-cooling systems. Electric arc furnace steel making consists of scrap charging, melting, refining, deslagging and tapping. In addition to scrap steel, the charge may include pig iron and alloying elements. As the steel scrap is melted, additional scrap may be added to the furnace. The electric arc furnace generates heat by passing an electric current between electrodes through the charge in the furnace. This energy is supplemented by natural gas, oxygen and other fuels. Other technologies used to smelt iron-containing materials are: cupola furnaces (hot and cold), induction furnaces, and blast furnaces. Cupola furnaces are used for the production of cast iron and cast steel. Cupola furnaces are cokeheated vertical furnaces that are charged batch-wise with raw materials, or sometimes charged continuously using vibrating chutes. The necessary heat for smelting of the charged materials is produced by means of coke combustion and air (hot or cold) blown in through tuyeres at the sides of the furnace. The actual smelting zone is found in the lower third of the vertical furnace. With regard to heat utilization the operation is similar to residential coal-fired stoves. The smelting capacity depends mainly on the air volume blown in for combustion, the amount of fuel and the diameter of the furnace. (The European Dioxin Emission Inventory Stage II, December 2000)
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Induction furnaces are simple crucibles or channels that are heated by an external electrical coil, channel induction furnaces are mainly used for melting items with large dimensions. Current is induced in the metal that has been charged into the furnace and heat is generated. The furnaces may be equipped with fume extraction hoods and dust abatement that can be used during drossing and pouring operations. Access to an induction furnace for charging and tapping means that a movable hooding system is often used. The hoods are robust so that they can withstand some mechanical impact. Alternatively, efficient fixed or lip extraction is used. The efficiency of this furnace can be low for some materials but can be increased particularly if the feed material is small. Large items can be cut to improve efficiency and also to allow the fume collection hoods to be deployed properly. Some continuous processes also retain a heel of molten metal in the bottom of the furnace between charges if the operation allows it. They may also be operated under vacuum, for example when melting super alloys, high alloyed steel, pure metals and in some cases for metal distillation. The temperature of the furnace can be automatically controlled to minimise the production of fume when melting volatile or oxidisable metals such as zinc or alloys containing zinc. These furnaces are also used to Hold molten metal for alloying and casting. The current induced in these furnaces causes the metal to be stirred electro-magnetically, which promotes mixing of the charge and any alloying materials that are added. (IPPC 2001) A blast furnace is a vertical furnace using tuyeres to blast heated or cold air into the furnace burden to smelt the contents. Sinter is charged into the top of the blast furnace in alternating layers with coke.
1.2.
Furnace feedstock
The major feedstock for the furnace is ferrous scrap, which may include ferrous scrap from inside the steelworks (for example, offcuts), cut-offs from steel product manufacturers (for example, vehicle builders) and capital or post-consumer scrap (for example, end-of-life vehicles and appliances) (European Commission 2000). Additional inputs are fluxes and additions like deoxidants or alloying elements. Direct reduced iron is also increasingly being used as a feedstock, due to both its low gangue content and variable scrap prices (European Commission 2000). Fluxing materials are added to combine with unwanted materials and form a slag. Slag removes the steel impurities (for example, silicon, sulphur and phosphorus) from the molten steel. Oxygen may be added to the furnace to speed up the steel-making process. At the end of a heat, the furnace tips forward and the molten steel is poured off.
1.3.
The electric arc furnace
Many steel plants increase productivity by using the electric arc furnace for the melting phase and a ladle metallurgy facility for the final refining and alloying phase. In some cases the steel ladle is taken to a vacuum degassing station where the gas content of the molten steel is reduced for quality requirements. The molten steel from the electric arc furnace or the ladle metallurgical facility is cast in a continuous casting machine to produce cast shapes including slabs, billets or beam blanks. In some processes, the cast shape is torch cut to length and transported hot to the hot rolling mill for further processing. Other steel mills have reheat furnaces. Steel billets are allowed to cool, and are then reheated in a furnace prior to rolling the billets into bars or other shapes. Production of steel from scrap consumes considerably less energy than production of steel from iron ores (EPRI 1997). Electric arc furnace steel manufacturing is an important recycling activity that contributes to the recovery of steel resources and waste minimization. The use of electric arc furnaces in the production of steel provides three major benefits: lower capital cost for a steel-making shop, significantly less energy required to produce steel compared to the coke oven/blast furnace/basic oxygen furnace method of the integrated steel makers, and avoidance of coke ovens.
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Electric arc furnace steel making is a dynamic batch process with steel tap-to-tap times of one hour or less for a heat except for stainless and specialty steel producers. The process is constantly changing from the removal of the furnace roof for charging the steel scrap to the meltdown of the steel scrap, with the resultant emissions from scrap contaminants such as oils and plastics, to the refining period, and finally tapping of the steel. The conditions within the electric arc furnace and the combustion processes vary throughout the heat production cycle. In recent years, more new and existing electric arc furnaces have been equipped with a system for preheating the scrap in the off-gas in order to recover energy. The so-called shaft technology and the Consteel process are the two proven systems that have been introduced. The shaft system can be designed to reheat 100% of the scrap (European Commission 2000). Some electric arc furnaces also use a water spray or evaporative cooling system to cool the hot offgases, and some use heat exchangers ahead of the emission control device. The furnaces may be equipped with dry, semi-wet or wet air pollution controls. Semi-wet and wet gas cleaning systems may be sources of waste water. Figure 1 shows the electric arc furnace and a generic fabric filter emission control system.
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Figure 1. Generic electric arc furnace emission control system
Canopy hood
Post Combustion Optional EAF
Evaporative Cooler Optional Spark Arrestor
Baghouse
Oxygen injection/ carbon injection/ oxyfuel burner
Stack Air-to-gas cooler Optional
Source: William Lemmon and Associates Ltd. 2004.
2.
2.1.

Emissions
2.1.1.PCDD/PCDF formation
Electric arc furnace steel making is a batch process that can result in fluctuating emissions during heating of the charge and from heat to heat. Gas handling systems vary from facility to facility, both in configuration and design. These factors contribute to a varying concentration in process offgases. As a high-temperature metallurgical process, particulate matter that contains a fine fume of metal and metal oxides is generated. High-efficiency pollution control systems are required to remove the fine particulate matter in the off-gases. Aromatic organohalogen compounds, including polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), chlorobenzenes and polychlorinated biphenyls (PCB) may be formed as a consequence of the thermal process and have been detected in electric arc furnace off-gas. The most important members of this group of compounds are PCDD/PCDF. Scrap preheating may result in higher emissions of aromatic organohalogen compounds. A report entitled Research on Technical Pollution Prevention Options for Steel Manufacturing Electric Arc Furnaces (William Lemmon and Associates Ltd. 2004), prepared for the Canadian Council of Ministers of the Environment, takes into account the United Nations Environment Programme (UNEP) document Formation of PCDD/PCDF An Overview (UNEP 2003), and provides an understanding of the basic formation mechanism of PCDD/PCDF. Information from this report is summarized below. 1. The processes by which PCDD/PCDF are formed are not completely understood. Most information about these substances in combustion processes has been obtained from laboratory experiments, pilot-scale systems and municipal waste incinerators.
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2. PCDD/PCDF appear to be most probably formed in the electric arc furnace steel-making process via de novo synthesis by the combustion of non-chlorinated organic matter such as polystyrene, coal and particulate carbon in the presence of chlorine donors. Many of these substances are contained in trace concentrations in the steel scrap or are process raw materials such as injected carbon. Ovaco has commented that it is well known that the emission of PCDD/F is very low when using stainless steel scrap as raw material: a fraction only of that of other EAFs. Possibly due to catalytic effects of compounds of Ni or Cr present in the dusts. 3. There is an inherent dualism of formation and dechlorination of PCDD/PCDF which occurs in the same temperature range and especially under the conditions present in the electric arc furnace. In general, dechlorination of PCDD/PCDF appears to take place at temperatures above 750 C in the presence of oxygen. As the temperature increases above 750 C, the rate of dechlorination increases and the required residence time decreases. 4. Increasing the oxygen concentrations results in increasing formation of PCDD/PCDF. It is not known whether this continues at elevated oxygen concentrations (for example, above 10% O2). Under pyrolytic conditions (oxygen deficiency) dechlorination of PCDD/PCDF occurs at temperatures above 300 C. 5. Some metals act as catalysts in the formation of PCDD/PCDF. Copper is a strong catalyst and iron is a weaker one. 6. Condensation starts in the 125 60 C range with the higher-chlorinated PCDD and increases very rapidly as the temperature drops. The lower-chlorinated PCDF are the last to condense, which explains why the tetra and penta PCDF constitute the majority of the PCDF in electric arc furnace emission tests. 7. Emission test results had higher PCDD/PCDF emission concentrations when the gas temperature exiting the gas conditioning system/ gas cooling device was consistently above 225 C, indicating that de novo synthesis had taken place in the gas conditioning system. 8. PCDF consistently accounted for 6090% of the PCDD/PCDF I-TEQ concentration in electric arc furnace emission tests. 9. Two furan congeners, 2,3,7,8-TCDF (tetrachlorodibenzofuran) and 2,3,4,7,8-TCDF, consistently accounted for 6075% of the PCDD/PCDF I-TEQ concentration in electric arc furnace emission tests. These results are comparable to the theoretical condensation calculations for PCDD/PCDF, as these two congeners would be the last to condense as the gas temperature decreases. 10. These latter findings indicate that there is a predominant PCDD/PCDF formation mechanism, de novo synthesis, for the electric arc furnace steel-making process. It appears likely that variations in the PCDD/PCDF fingerprint for the process are due to variations in the constituents of the scrap charge, varying conditions in the furnace resulting from changes in operating practices from heat to heat and plant to plant, varying conditions in the gas conditioning and cleaning system, and differences in baghouse collection efficiencies. Electric induction furnaces require cleaner scrap charges than electric arc furnaces can tolerate, and melt their charge using magnetic fields. While there are some similarities to electric arc furnaces, dioxin and furan generation in such units is expected to be significantly lower than from electric arc furnaces. With regard to emissions from cupola furnaces employed in cast iron and steel foundries, a German submission to the European Dioxin Inventory Stage II summarized the results of a study collecting data on 25 cold-blast cupolas located in Germany. Cold blast cupola furnaces (also
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termed cold air or cold wind cupolas) were identified in the Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases (UNEP 2001) as having a higher potential than other designs for significant emissions: For foundries, there are hardly any data available: testing in Germany (SCEP 1994) showed that hot air cupolas and induction furnaces fitted with fabric filters had low emissions to air, an emission factor of 0.03 g TEQ/t of product should be used. Cold air cupolas showed higher emissions and a factor of 1 g TEQ/t is used for plants with fabric filters. Limited testing on rotary drum furnaces showed higher levels again and a factor of 4.3 g TEQ/t is applied to plants with fabric filters for gas cleaning. Where cold air cupolas or rotary drum furnaces are used which do not have fabric filters or equivalent for gas cleaning a higher emission factor of 10 g TEQ/t should be used. If poor quality scrap (high contamination) or poorly controlled furnaces with gas cleaning other than effective fabric filters is found this should be noted. The more recent work reported for the European Dioxin Inventory Stage II focussed on wellcontrolled cold blast cupolas producing iron for castings, equipped with fabric filters for particulate emission control. This studyindicates that the range of the 18 individual emission samples obtained was 0.003 to 0.184 ng I-TEQ/Nm3, and that the three-run averages for four of the six furnaces tested were below 0.1 ng I-TEQ/Nm3 (the emission limit value for municipal waste incinerators). It also concluded that For all furnaces studied the average emission factor was found to amount to 0,35 g I-TEQ/t of smelted iron in the furnaces with a maximum value reaching 1,45 g I-TEQ/t (European Commission, 2000). The conclusions of this chapter of the document were ( Ibid): Looking at the concentrations found in the waste gases cold-blast cupola furnaces operated in iron and steel foundries cannot be considered as important sources of dioxins and furans due to their emitted total amounts of PCDDs and PCDFs. Thus, the results of the measurements agree with a few known data that existed before the investigations were started. Note however, that the emissions for North Rhine-Westphalia were extrapolated from only 6 furnaces. It cannot be said with certainty that these furnaces are representative for all cold-blast cupola furnaces operated in Germany. Within this project one furnace was found having PCDD and PCDF concentrations in the filter-collected dust of up to approximately 12 g I-TEQ/kg. This is considerably higher than from those plants where emissions were measured (highest concentration in the filter-collected dust from these plants was 0,4 g I-TEQ). In addition, a high temporal fluctuation of PCDD and PCDF concentrations in the filter-collected dusts became apparent. Therefore, despite of an indication of a positive correlation between the concentrations in the filter-collected dust and the concentrations in the waste gas obtained from measurement results it is not allowed to assume that this correlation may be extrapolated on furnaces with higher concentrations in the filter-collected dusts. For clarification, a further study programme would be necessary which, for example, would allow measurements of PCDD and PCDF concentrations in the filter-collected dust of a furnace over a longer period of time. From the observed interdependence of PCDD and PCDF emissions and the amounts of cast scrap and recycled material applied it can be concluded that the contaminants adhering to the cast scrap (remnants of paint, oils etc.) have an influence on the emissions. In order to reduce dioxin concentrations a decrease of the amount of cast scrap would make sense, however, this would considerably reduce the cost efficiency of foundries. The question arises, whether certain contaminants on the cast scrap play a major role in the development and emission of PCDDs and PCDFs. If this is so, it would require a selective elimination from the charged input material.
2.1.2.PCDD/PCDF research on electric arc furnaces
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Most of the research on PCDD/PCDF formation and control has been carried out for electric arc furnaces in Europe. The earliest reported work was by Badische Stahlwerke GmbH (BSW) in Kehl/Rheim, Germany, in the early 1990s (Weiss and Karcher 1996). Other European steel companies followed BSWs lead under regulatory pressure from national environmental agencies. A summary of the electric arc furnace operational findings follows: 1. The BSW research project confirmed that a high concentration of hydrocarbon material in the steel scrap significantly increased the emissions of volatile organic compounds and PCDD/PCDF. 2. Emission test results from BSW, ProfilARBED, Differdange and Gerdau Ameristeel Cambridge emission-testing programmes had higher PCDD/PCDF emission concentrations when the gas temperature exiting the gas conditioning system/ gas cooling device was consistently above 225 C, indicating that de novo synthesis had taken place in the gas conditioning system. 3. PCDF consistently accounted for 6090% of the PCDD/PCDF I-TEQ concentration in the Canadian electric arc furnace emission tests. Similar results have been reported in European emission tests of electric arc furnaces. 4. Two PCDF congeners, 2,3,7,8-TCDF and 2,3,4,7,8-TCDF, consistently accounted for 6075% of the PCDD/PCDF I-TEQ concentration in the Canadian electric arc furnace emission tests. Similar results have been reported in European emission tests of electric arc furnaces. These results are comparable to the theoretical condensation calculations for PCDD/PCDF, as these two congeners would be the last to condense as the gas temperature decreases. 5. The congener I-TEQ concentration distributions in the Canadian electric arc furnace emission tests were similar regardless of the total PCDD/PCDF I-TEQ concentrations. 6. The findings indicate that de novo synthesis is the predominant PCDD/PCDF formation mechanism for the electric arc furnace steel-making process. 7. It appears likely that variations in the PCDD/PCDF emission fingerprint for the electric arc furnace steel-making process are due to variations in the constituents of the scrap charge, varying conditions in the furnace resulting from changes in operating practices from heat to heat and plant to plant, varying conditions in the gas conditioning and cleaning system, and differences in baghouse collection efficiencies. There is insufficient publicly available information to determine the relative importance of these factors. 2.1.3.Review of electric arc combustion chemistry and PCDD/PCDF formation A review of the relationship of electric arc furnace combustion chemistry with PCDD/PCDF formation in the furnace may be summarized as follows: 1. PCDD/PCDF can be formed from related chlorinated precursors such as PCB, chlorinated phenols and chlorinated benzenes. 2. The environment inside a steel-making electric arc furnace is very complex and is constantly varying. The combustion chemistry produces conditions that are amenable to PCDD/PCDF formation. The hydrocarbons entering the furnace in the scrap may be vaporized, cracked, partially combusted or completely combusted, depending on the conditions in the furnace or parts of the furnace during or after charging. Other sources of carbon include injected carbon and the graphite electrodes. The dual processes of PCDD/PCDF formation and dechlorination may be proceeding at the same time if the oxygen concentration and temperature are such that some PCDD or PCDF congeners are being formed while other congeners are being dechlorinated.
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SECTION V. Guidelines/guidance by source category: Part II of Annex C 3. The research on optimization of internal post-combustion indicates that under normal steel-making operations, conditions favourable to PCDD/PCDF formation oxygen-rich atmosphere, reactive carbon particles and temperatures under 800 C are present in parts of the furnace during the meltdown phase and possibly for some time afterwards. Given that metals that act as catalysts are present and that trace amounts of chlorine may be present in some of the charge materials and fluxes, the conditions appear to be present for de novo synthesis to occur. Since ideal mixing conditions are not present, it appears that a portion of the PCDD/PCDF that are formed will leave the electric arc furnace in the off-gas without encountering sufficiently high temperatures for dechlorination to take place. 4. Most of the research on combustion chemistry and internal post-combustion in electric arc furnace steel making has aimed to increase productivity by taking advantage of fuels within the furnace such as hydrocarbons, carbon monoxide and hydrogen to replace electric energy with chemical energy, thus reducing the total energy input, which results in lower production costs per ton of product. 5. Scrap preheating may result in elevated emissions of chlorinated aromatic compounds such as PCDD/PCDF, chlorobenzenes, PCB, as well as polycyclic aromatic hydrocarbons, and other products of incomplete combustion from scrap contaminated with paints, plastics, lubricants or other organic compounds. The formation of these pollutants may be minimized by post-combustion within the furnace (as opposed to external post-combustion of the off-gas) by additional oxygen burners developed for burning the carbon monoxide and hydrocarbons, which recovers chemical energy. It has been suggested that scrap preheating increases the organic matter in the flue gas and maybe the formation of chlorinated compounds too. What happens to the emissions depends on total heat energy balance of the flue gas system. In Ovacos case, scrap preheating decreases the emission of PCDD/F (and most probably increases emission of light organic compounds). It depends on the fact that scrap preheating acts as an efficient gas cooler. Low gas temperature at the filter means that heavy organic compounds are separated with dust. (Ovaco, 2006) 6. Indications are that internal post-combustion may be a more attractive option than external post-combustion for PCDD/PCDF formation prevention.
2.2.
PCDD/PCDF releases in solid waste and waste-water sources
Most mills worldwide operate electric arc furnaces with dry off-gas cleaning systems (i.e., fabric filter dust collectors), which produce no process waste water that would require treatment. Some existing electric arc furnaces may be equipped with semi-wet air pollution control systems (European Commission 2000). Semi-wet systems apply water to the furnace off-gases in order to partially cool and condition the off-gases prior to particulate removal in an electrostatic precipitator. Sites are able to achieve zero waste-water discharge from semi-wet systems by balancing the applied water with water that evaporates in the conditioning process. Non-contact cooling water is the predominant water source; however, some facilities may use treated process water and plant service water (EPA 2002). Standards of some jurisdictions identify zero discharge as the best available technique for semi-dry gas cleaning systems. In some European Union countries wet scrubbers are used to clean the off-gases from electric arc furnaces at some mills. However, no information from these facilities is available on waste-water quantities and methods of treatment (European Commission 2000). Consequently, no findings were concluded as to best available techniques for treating and minimizing PCDD/PCDF releases from waste water from wet air pollution control systems. Residues in the form of dust collected by the dry air pollution control system for electric arc furnaces may contain trace levels of PCDD/PCDF.
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Cupola furnaces may be controlled by wet scrubbers or dry filter systems. The work done on cold blast cupola furnaces in North Rhine-Westphalia noted earlier found significant levels of PCDD/PCDF in some collected filter dust samples. The study found 7 samples below 0.1 g ITEQ/kg dry mass, 19 between 0.1 and 1.0 g/kg, and 8 above 1.0 g/kg. One sample had levels of approximately 12 g I-TEQ/kg dry mass. While these levels were sufficient that all of the majority (27) of the samples would have been considered contaminated for the purposes of a German guide requiring remediation of sites designated as childrens playgrounds (i.e., 0.1 ng I-TEQ/kg dry mass), none of the samples exceeded levels (100 g total PCDD/PCDF per kg dry mass) which would have triggered the requirement for special actions to be undertaken by plant operators under German ordinances on dangerous substances and prohibited chemicals. It was also determined that 15 samples would not have been permitted to be sold or traded under the provisions of the ordinance respecting dangerous substances (European Commission, 2000). No data has been located relating to dioxin levels in scrubber blow-down effluents from cupola furnace operations., although given the results noted above for dry collection systems there is a potential for dioxin releases to the environment from such streams.
3.
3.1.
Electric arc furnace process improvements and alternative processes for electric steel making
Process improvements
The electric arc furnace steel-making process has been undergoing change over the past decades. Research and development for electric arc furnace steel making, especially in Europe, is focused on furnace design improvements to increase productivity and energy efficiency, and to reduce steelmaking costs. There are two major driving forces reduction of steel-making costs as exemplified by increased productivity, and increased product quality as exemplified by quality demands from the automotive industry. Added to these is a third driving force environmental pressures. Productivity improvements have resulted in shorter tap-to-tap times, increased energy efficiency and increased use of chemical energy. Quality demands have been met through selection of scrap, furnace operating practices and increased use of ancillary processes such as ladle metallurgy and vacuum degassing. Environmental pressures include the requirements for PCDD/PCDF emission reduction and smog precursor reduction of substances such as fine particulate. One option for these producers is to use higher-quality scrap with lower contaminant levels (William Lemmon and Associates Ltd. 2004). A second option is to replace part of the scrap charge by direct reduced iron or similar products that are produced from iron ore and have contaminant concentrations lower than the lower-quality scrap steel grades. Merchant direct reduced iron production is increasing and the international market is growing, so greater availability may mean that some electric arc furnace steel makers have the option of buying direct reduced iron rather than on-site production. There is very limited available information on PCDD/PCDF emissions from the direct reduced iron process but, given the characteristics of the process, PCDD/PCDF emissions are likely to be very small. Information on the formation and emissions of PCDD/PCDF from the use of direct reduced iron in electric arc furnace steel making is not available. A third option is the use of hot metal in electric arc furnace steel making. This is forecast to increase as steel makers strive for shorter heat cycles and higher productivity (Fruehan 1998). Information on the impact of this option on PCDD/PCDF emissions is not available. With preheating of part of the scrap about 60 kWh/t can be saved; in the case of preheating the total scrap amount up to 100 kWh/t liquid steel can be saved. The applicability of scrap preheating depends on the local circumstances and has to be proved on a plant-by-plant basis. Advances in the electric arc furnace steel-making process often have collateral benefits, including the reduction of particulate matter and PCDD/PCDF emissions, except for scrap preheating as
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noted above. Usually the objective of advanced operating practices is improved operational and energy efficiency to increase productivity and thus increase production and reduce operating costs.
3.2.
Alternative processes
No alternative steel-making technology would replace the electric arc furnace for the high production operations of steel plants. While other electrode materials have been used for a few furnaces in the past, there are no alternatives to the graphite electrode at the present time.
4.
Primary and secondary measures for reducing emissions of PCDD/PCDF from electric arc furnaces are outlined in the ensuing section. Much of this material has been drawn from William Lemmon and Associates Ltd. 2004. Some of these also apply to cupola and electric induction furnaces. The extent of emission reductions possible with implementation of primary measures only is not readily known. Implementation of both primary and secondary measures at existing and new plants is probably necessary to achieve the desired emission levels. It should be feasible for all plants to implement some or all of the pollution prevention practices identified below.
4.1.
Primary measures for emissions
Primary measures, often called pollution prevention techniques, are able to avoid, suppress or minimize the formation of PCDD/PCDF or dechlorinate PCDD/PCDF in the electric arc furnace steel-making process. As a general measure, an integral part of a facilitys pollution prevention programme should include best environmental, operating and maintenance practices for all operations and aspects of the electric arc furnace steel-making process. The following list presents a range of options as primary measures; some may not be applicable to all furnace designs or plants, and some may require further investigation. This list of techniques has been developed based on work done with electric arc furnaces, and while many of the same principles are expected to hold for electric induction and cupola furnaces, they have not been documented for those applications. However, the fact that most of the existing test results for the other furnace types are below 0.1 ng I-TEQ/Nm3 indicates that a combination of these measures and the secondary measures listed below should be effective to limit emissions. 4.1.1.Raw material quality The major raw material used in the electric arc furnace steel-making process is iron or steel scrap. Contaminants, including oil, plastics and other hydrocarbons, are often present in the scrap. Pollution prevention practices to prevent or minimize the entry of contaminants into electric arc furnaces for iron and steel making include changes in material specifications, improved quality control programmes, changes in the types of raw materials (such as avoidance of oily scrap or cleaning oily scrap) and programmes to prevent the entry of contaminants. 4.1.2.Electric arc fFurnace operation Recent changes in electric arc furnace operational practices that have been adopted to improve operational and energy efficiency appear to have collateral benefits to reduce PCDD/PCDF or, in certain conditions, to dechlorinate PCDD/PCDF. Pollution prevention practices that appear to reduce PCDD/PCDF emissions include minimizing the duration of the roof being open for charging, reduction of air infiltration into the furnace and avoiding or minimizing operational delays. Condensation of PCDD/PCDF increases rapidly at temperatures below 125 C, starting with the higher-chlorinated dioxins. 4.1.3.Off-gas conditioning system design Off-gas conditioning includes the collection, cooling and ducting of electric arc furnace off-gases prior to cleaning in a baghouse. Off-gas conditioning system conditions may be conducive to de
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novo synthesis formation of PCDD/PCDF unless care is taken to avoid conditions leading to de novo synthesis. Pollution prevention techniques include an adequately sized system, maximization of off-gas mixing, rapid cooling of off-gas to below 200 C and development and implementation of good operating and maintenance practices. 4.1.4.Continuous parameter monitoring system A continuous parameter monitoring system based on optimizing the appropriate parameters for the operation of the gas conditioning system and documented operating and maintenance procedures should minimize the formation of PCDD/PCDF by de novo synthesis in the gas conditioning system.
4.2.
Secondary measures for emissions

4.2.1.Off-gas dust collection
Secondary measures, often called pollution control techniques, may be summarized as follows: Capturing all of the off-gas, including fugitive emissions, from the electric arc furnace area is an important part of the control system. Dust collection efficiency of primary and secondary emissions from the furnace should be maximized by a combination off-gas and hood system, or doghouse and hood system, or building air evacuation. 4.2.2.Fabric filter dust collectors (or baghouses) Some of the PCDD/PCDF in the electric arc furnace off-gases adsorb onto fine particulate matter. As the gas temperature decreases through the PCDD/PCDF condensation temperature of the various congeners, more of the PCDD/PCDF either adsorb onto the fine particulate matter or condense and form fine particulate matter. Well-designed fabric filters achieve less than 5 mg dust/Nm3 for new plants and less than 15 mg dust/Nm 3 for existing plants. Minimizing dust levels also minimizes PCDD/PCDF emissions. 4.2.3.External post-combustion system coupled with a rapid water quench This technique was the early PCDD/PCDF emission control technique applied to electric arc furnace steel making. External post-combustion systems were originally developed to combust carbon monoxide (CO) and hydrogen (H2) in the furnace off-gas in a refractory lined combustion chamber, usually with supplementary fuel. Subsequently a number of European electric arc furnace steel-making plants adopted the external post-combustion technology to dechlorinate PCDD/PCDF emissions by maintaining the post-combustion temperature above 800 C. This emission control technique is not able to consistently meet the Canada-wide standard of 100 pg TEQ/Nm 3 (0.1 ng TEQ/Nm3). It may not be feasible for some plants to install external post-combustion and improvements to gas conditioning systems due to site-specific space considerations. 4.2.4.Adsorbent injection This control technique was originally developed to control PCDD/PCDF emissions from waste incinerators. Sized lignite coke (activated carbon is a similar adsorbent) injection technology is used in a number of European electric arc furnace steel-making plants to supplement the fabric filter baghouse technology to achieve low PCDD/PCDF emission concentrations consistently. This technique also reduces emissions of mercury. Reported emission test results from electric arc furnace steel-making plants in Europe indicate that this technique, in combination with a highefficiency fabric filter baghouse, consistently achieves PCDD/PCDF emission concentrations of less than 0.1 ng TEQ/Nm3.14 The sized lignite coke is injected into the off-gas upstream of the baghouse. The coke (or activated carbon) adsorbs the PCDD/PCDF in the off-gas. Good mixing of the coke with the off-gas, and
14
1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa.
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appropriate sizing of the coke (to a size similar to particles in the gas stream), are essential for optimum PCDD/PCDF removal. Sized lignite coke production and activated carbon do not release captured PCDD/PCDF at normal product storage and landfill temperatures, and are resistant to leaching. Use of sized lignite coke as an adsorbent increases baghouse dust volume by 2%. Activated carbon or sized coke injection systems should be considered for use at steel plants to reduce emissions of PCDD/PCDF. Site-specific considerations, such as lack of available space, configuration of existing emission control systems and cost impacts may influence the feasibility of using this technique. Selective catalytic reduction technology used for removal of nitrogen oxides (No x) in other industrial sectors has been shown to reduce PCDD/PCDF emissions to significantly less than 0.1 ng I-TEQ/Nm3. This technology has not been applied to steel-making electric arc furnaces but may be in the future.
4.3.
Primary and secondary measures for solid wastes and waste water
The measures in this section generally apply for electric arc, electric induction, and cupola furnaces. With respect to solid wastes, electric arc furnace slag and filter dusts from any furnace should be recycled to the maximum extent possible. Filter dust from high-alloy steel production, where possible, may be treated to recover valuable metals. Excess solid waste should be disposed of in an environmentally sound manner. Ovaco has commented that the landfilling of EAF-dust is no longer allowed in most industrial countries. The standard method is recovery of valuable metals in a separate treatment process or processes outside the steel work. If stainless steel scrap is used as raw material, Cr, Ni, Zn and Pb are recovered, otherwise (for the main part of dust) Zn and Pb is separated only. The measured dioxin content of Ovacos dust is around 1300 pg I-TE/g and it represents 96% of the total amount synthesized in our process. If we use this concentration and 50000 t/a as a typical capacity of a treatment plant, the input material of it contains dioxins some 60 - 70 g I-TE per year. With respect to waste water, closed-loop water-cooling systems for electric arc furnace components avoid waste water being generated, or ensure it is recycled to the maximum extent possible to minimize waste volume for treatment. It has been suggested that EAF cooling water is carefully kept separated from molten steel of safety reasons (risk of explosions). (Ovaco, February 2006) Semi-dry emission control systems may be used at some plants. While replacement with dry dust collectors would be the desirable option, semi-dry systems can be designed to avoid the generation of waste water. Waste water may originate at electric arc furnace facilities that use wet scrubbing systems. The desired approach is the replacement of existing systems with dry dust collectors. If replacement of existing emission control systems is not feasible, the waste water would need treatment. However, standards for treated waste-water quality concerning PCDD/PCDF discharge levels or other parameters were not found.
5.
Summary of measures
Tables 1 and 2 present a summary of the measures discussed in previous sections.
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Table 1. Measures for new electric arc furnaces

Measure Process design Description Priority consideration should be given to the latest proven process designs based on process and emissions performance New electric arc furnaces should be required by the applicable jurisdiction to achieve stringent performance and reporting requirements associated with best available techniques Considerations An example is internal post-combustion design for a new electric arc furnace Consideration should be given to the primary and secondary measures listed in Table 2 Achievable emission limits should be specified as follows: < 0.1 ng TEQ/Rm3 for PCDD/PCDF < 5 mg/Rm3 for particulate matter Other comments
Table 2. Measures for new and existing electric arc furnaces

Measure Primary measures General operating practices An integral part of a facilitys pollution prevention programme should include best environmental, operating and maintenance practices for all operations and aspects of the electric arc furnace steel-making process A review of feed materials and identification of alternative inputs and/or procedures to minimize unwanted inputs should be conducted. Documented procedures should be developed and implemented to carry out the appropriate changes Generally applicable; part of an integrated concept for pollution prevention Description Considerations Other comments
Raw material quality
Generally applicable. Measures include changes in material specifications, improved quality control programmes, changes in the types of raw materials (such as avoidance of oily scrap) and programmes to prevent the entry of contaminants Collateral benefit is reduced PCDD/PCDF Other pollutants are reduced, including aromatic organohalogen compounds, carbon monoxide, hydrocarbons and greenhouse gases
Electric arc furnace operation
Minimizing the duration of the roof being open for charging, reduction of air infiltration into the furnace, and avoiding or minimizing operational delays
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Measure Off-gas conditioning

Description Design and installation of an adequately sized gas conditioning system based on optimum system parameters should prevent or minimize formation of PCDD/PCDF in the gas conditioning system. Development and implementation of documented operating and maintenance procedures should be developed to assist in optimizing the operation of the gas conditioning system A continuous parameter monitoring system should be employed to ensure optimum operation of the sinter strand and off-gas conditioning systems. Operators should prepare a sitespecific monitoring plan for the continuous parameter monitoring system and keep records that document conformance with the plan Considerations A reduction in de novo synthesis in the gas conditioning system has been linked to the rapid cooling of the furnace off-gases to below a range of 225 to 200 C Other comments
Continuous parameter monitoring
Correlations between parameter values and stack emissions (stable operation) should be established. Parameters are then continuously monitored in comparison to optimum values
System can be alarmed and corrective action taken when significant deviations occur
Secondary measures The following secondary measures can effectively reduce releases of PCDD/PCDF and serve as examples of best available techniques Off-gas collection Dust collection efficiency of primary and secondary emissions from the electric arc furnace should be maximized by a combination off-gas and hood system, or doghouse and hood system, or building air evacuation Well-designed fabric filters achieve low dust emissions. Procedures should be developed for the operation and maintenance of the fabric filter dust collector to optimize and improve collection performance, including optimization of fabric bag cleaning cycles, improved fabric bag material and preventive maintenance practices. A continuous temperature monitoring and alarm system should be provided to monitor the off-gas inlet temperature to the emission control device. A bag leak detection system should be provided with documented operating There is close correlation between the PCDD/PCDF content in collected dust of a fabric filter and dust concentration. Lower exhaust PCDD/PCDF levels accompany lower dust levels 98% efficiency or more of dust collection is achievable
Fabric filters
Maintaining the offgases in the baghouse to below 60 C will prevent PCDD/PCDF evaporation in the baghouse and collected dust. Enclosing the filter dust collection areas and transfer points minimizes fugitive dust

Measure Description and maintenance procedures for responding to monitoring system alarms Postcombustion of off-gas PCDD/PCDF formation may be minimized by post-combustion within the off-gas duct system or in a separate post-combustion chamber. Indications are that internal postcombustion may be a more attractive option than external post-combustion for PCDD/PCDF formation prevention Considerations
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Other comments
PCDD/PCDF that have been formed in the process undergo dechlorination reactions as the offgas is burned by the additional oxygen burners. This technique with a rapid water quench has been an early PCDD/PCDF emission control technique applied to electric arc furnace steel making
Adsorbent injection
Injection of activated carbon or similar adsorptive material into the off-gas upstream of high-efficiency fabric filters in electric arc furnaces at European steel-making plants has consistently achieved low levels of PCDD/PCDF emissions, according to data from demonstration projects Electric arc furnace slag and filter dust should be recycled to the extent possible. Filter dust from high-alloy steel production, where possible, may be treated to recover valuable metals. Best management practices should be developed and implemented for hauling and handling dust-generating solid wastes. Excess solid waste should be disposed of in an environmentally sound manner Closed-loop water-cooling systems for electric arc furnace components avoid waste water being generated. Recycle waste water to the maximum extent possible. Residual waste water should be treated. Semi-dry air pollution control systems These measures would be primarily associated with general pollution prevention and control practices rather than being applied specifically, or only, for the purpose of No standards were found on PCDD/PCDF limits for treated waste water discharged as final effluent from wet off-gas cleaning systems
Minimize solid waste generation
Minimize waste water
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Measure

Description can be designed to have zero discharge of excess waste water. Waste water from wet gas cleaning systems should be treated before discharging to the environment Considerations PCDD/PCDF Other comments
6.
The achievable performance level for emissions of PCDD/PCDF from secondary iron and steelmanufacturing electric arc, electric induction and cupola furnaces that incorporate best available techniques is < 0.1 ng I-TEQ/Nm3.15
References
EPA (United States Environmental Protection Agency). 2002. Development Document for Final Effluent Limitations Guidelines and Standards for the Iron and Steel Manufacturing Point Source Category. EPA, Washington, D.C. epa.gov/waterscience/ironsteel/pdf/tdd/complete.pdf. EPRI (Electric Power Research Institute). 1997. Understanding Electric Arc Furnace Operations. EPRI, Centre for Materials Production, Palo Alto, California. European Commission. 2000. Reference Document on Best Available Techniques for the Production of Iron and Steel. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. European Commission. 2000. The European Dioxin Emission Inventory Stage II, Volume 2, Destop studies and case studies. North Rhine Estphalia State Environmental Agency, NordrheinWestfalen, Germany. http://europa.eu.int/comm/environment/dioxin/pdf/stage2/volume_2.pdf European commission, Integrated Pollution Prevention and Control (IPPC), Reference Document on Best Available Techniques in the Non Ferrous Metals Industries, December 2001. Fruehan R.J. (ed.) 1998. The Making, Shaping and Treating of Steel 11 th Edition: Steelmaking and Refining Vol. AISE Steel Foundation, Pittsburgh, PA. Personal Communication, Ovaco, February 2006 Weiss D. and Karcher A. 1996. Evaluation and Reduction of Dioxin and Furan Emissions from Thermal Processes: Investigation of the Effect of Electric Arc Furnace Charge Materials and Emission Control Technologies on the Formation of Dioxin and Furan Emissions. Prepared for BSW. William Lemmon and Associates Ltd. 2004. Research on Technical Pollution Prevention Options for Steel Manufacturing Electric Arc Furnaces. Final Report. Prepared for the Canadian Council of
15
1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram); Nm3 = normal cubic metre, dry gas volume measured at 0 C and 101.3 kPa. For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines. The operating oxygen concentration conditions of exhaust gases are used for metallurgical sources. Guidelines on BAT and Guidance on BEP Environment Canada Revision April 28, 2006
SECTION VI. Guidance/guidelines by source category: Part III of Annex C Ministers of the Environment (CCME), Contract No. 283-2003. www.ccme.ca/assets/pdf/df_eaf_p2_ctxt_p2_strtgy_e.pdf .
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UNEP (United Nations Environment Programme). 2001. Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. Draft.
http://www.chem.unep.ch/pops/pdf/toolkit/toolkit.pdf
UNEP (United Nations Environment Programme). 2003. Formation of PCCD/PCDF An Overview. Draft. UNEP/POPS/EGB.1/INF/5. UNEP Chemicals, Geneva. www.pops.int/documents/meetings/bat_bep/1st_session/meetdocen.htm/. UNEP, Compilation of comments received from Parties and others on the draft Guidelines on Best Available Techniques and provisional Guidance on Best Environmental Practices, October 14, 2005
http://www.pops.int/documents/meetings/bat_bep/EGBATBEP1/meetingdocs/EGBATBE P_1_inf5.pdf
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(v)
Primary base metals smelting
Summary
Primary base metals smelting involves the extraction and refining of nickel, lead, copper, zinc and cobalt. Generally, primary base metals smelting facilities process ore concentrates. Most primary smelters have the technical capability to supplement primary concentrate feed with secondary materials (for example, recyclables). Production techniques may include pyrometallurgical or hydrometallurgical processes. Chemicals listed in Annex C of the Stockholm Convention are thought to originate through high-temperature thermal metallurgical processes; hydrometallurgical processes are therefore not considered in this section on best available techniques for primary base metals smelting. Available information on emissions of PCDD and PCDF from a variety of source sectors (for example, incinerators, steel electric arc furnaces, iron sintering plants) suggests that process technologies and techniques, and associated off-gas conditioning, can influence the formation and subsequent release of PCDD/PCDF. Consideration should be given to hydrometallurgical processes, where technically and economically feasible, as alternatives to pyrometallurgical processes when considering proposals for the construction and commissioning of new base metals smelting facilities or processes. Primary measures include the use of hydrometallurgical processes, quality control of feed materials and scrap to minimize contaminants leading to PCDD/PCDF formation, effective process control to avoid conditions leading to PCDD/PCDF formation, and use of flash smelting technology. Identified secondary measures include high-efficiency gas cleaning and conversion of sulphur dioxide to sulphuric acid, effective fume and gas collection and highefficiency dust removal. The achievable performance level using best available techniques for base metals smelters is < 0.1 ng TEQ/Nm3.
1.
Process description
The technical processes involved in the extraction and refining of base metals (nickel, lead, copper, zinc and cobalt) generally proceed as shown in Figure 1. Key metal recovery technologies that are used to produce refined metals can be categorized as follows: Pyrometallurgical technologies use heat to separate desired metals from unwanted materials. These processes exploit the differences between constituent oxidation potential, melting point, vapour pressure, density and miscibility when melted; Hydrometallurgical technologies use differences between constituents solubility and electrochemical properties while in aqueous acid solutions to separate desired metals from unwanted materials; Vapometallurgical technologies apply to the Inco carbonyl process whereby nickel alloys are treated with carbon monoxide gas to form nickel carbonyl. Generally, primary base metals smelting facilities process ore concentrates. Most primary smelters have the technical capability to supplement primary concentrate feed with secondary materials (for example, recyclables). Figure 1 provides a generic flowsheet showing the main production processes associated with primary smelting and refining.
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Chemicals listed in Annex C of the Stockholm Convention are thought to originate through hightemperature thermal metallurgical processes; hydrometallurgical processes are therefore not considered in this section on best available techniques for primary base metals smelting. Figure 1. Generic flowsheet for primary base metals smelting and refining
Consumed Scrap
New Scrap
Ore
Mining Pre-treatment Minerals Concentrating
Sintering/ Smelting
Smelting
Roasting/ Smelting/ Converting
Smelting/ Converting
Roasting and Leaching
Leaching
Distillation
Electro-refining
Drossing/ Refining
Purification/ Electrolysis
Solvent Extraction/ Electrowinning
Refined Metal
Air Pollution and Abatement Systems
Melting/ Casting/ Manufacturing
New Scrap
Manufacturing/ Applications and Use
Consumed Scrap
Artisinal and small enterprise metal recovery activities are sometimes used in developing countries and countires with economies in transition. These artisinal processes may be significant sources of pollution and of adverse human health impacts. Metals that are known to be produced by artisinal
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and small enterprise metal recovery activities include aluminium, antimony, copper, gold, iron, lead, manganese, mercury, tin, tungsten, silver, and zinc. These activities usually do not have any pollution controls and may be sources of unintentionally produced persistent organic pollutants. While artisinal metal recovery activities are not consider best available techniques or best environmental practices, it is recommended that, as a minimum, appropriate ventilation and material handling should be carried out to minimize human exposure to pollutants from these activities.
2.
Primary base metals smelters can be sources of chemicals listed in Annex C. The formation and release of such chemicals from primary smelters are not well understood, and it has been shown that emissions of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) can range significantly between operations using similar processes.
2.1.
Releases to air
2.1.1.General information on emissions from base metals smelting The main environmental issues for the production of most non-ferrous metals from primary raw materials are the potential emission to air of dust and metals/metal compounds and of sulphur dioxide if roasting and smelting sulphide concentrates or using sulphur containing fuels or other materials. The capture of sulphur and its conversion or removal is therefore an important factor in the production of non-ferrous metals. The pyrometallurgical processes are potential sources of dust and metals from furnaces, reactors and the transfer of molten metal (European Commission 2001). 2.1.2.Emissions of PCDD and PCDF There is limited published information on dioxin/furan mechanisms of formation for the base metals smelting sector, most of which is based on European experience for secondary base metal smelters. There are a few general statements that dioxins and furans might be present in some of the raw materials for secondary base metals smelting and that oils and organic materials are present in many of these raw materials. The presence of oils and other organic materials in scrap or other sources of carbon (partially burnt fuels and reductants such as coke) can produce fine carbon particles which react with inorganic chlorides or organically bound chlorine in the temperature range of 250 to 500C to produce dioxins and furans. This process is known as de novo synthesis which is dependent on catalysts such as copper and iron. Although dioxins and furans are destroyed at high temperature (above 850C) in the presence of oxygen, the process of de novo synthesis is still possible as the gases are cooled (Charles E. Napier Co. Ltd. 2002).
Available information on emissions of PCDD and PCDF from a variety of source sectors (for example, incinerators, steel electric arc furnaces, iron sintering plants) suggests that process technologies and techniques, and associated off-gas conditioning, can influence the formation and subsequent release of PCDD/PCDF. Canadian base metals smelting and refining facilities undertook emissions testing for PCDD and PCDF, and results from their work showed that concentration levels varied with the type of off-gas conditioning system. Smelting facilities in Canada generally process sulphide concentrates, and, at some facilities, also process some secondary materials. Off-gas conditioning varies from extensive cleaning (for example, high efficiency dedusting) and conversion to sulphuric acid, to dedusting by fabric filters, to dedusting by electrostatic precipitator. These facilities produce nickel, copper, lead, zinc and coproduct metals. There were 11 participating facilities in the Canadian test programme, conducting approximately 20 emission tests on 16 different sources. No two facilities had the same
109
combination and configuration of production processes and off-gas conditioning systems, further complicating any possible analysis. As such, the observations noted below are general in nature. Where off-gases were cleaned (i.e., dedusted, scrubbed) and processed through an acid plant for conversion of off-gases rich in sulphur dioxide (SO 2) to sulphuric acid, emission test results showed concentrations below 5 pg (0.005 ng) TEQ/m3.16 Where off-gases were dedusted by baghouse, concentration levels typically ranged from a few pg TEQ/m3 to < 30 pg TEQ/m3. Where off-gases were dedusted by electrostatic precipitator, concentration levels ranged from approximately 30 pg TEQ/m3 to approximately 500 pg TEQ/m3.
2.2.
No information was found on releases of chemicals listed in Annex C from primary base metals smelters to media other than air.
3.
Alternative processes for base metals smelting
In accordance with the Stockholm Convention, when consideration is being given to proposals for construction of a new base metals smelting facility, priority consideration should be given to alternative processes, techniques or practices that have similar usefulness but which avoid the formation and release of the identified substances. As indicated in Figure 1, there is a wide range of processes used in the primary production of base metals smelting. The processes used to produce crude or refined base metals from primary sources will depend to a large extent on the available ore or concentrate (i.e., laterite ore or sulphide ore), and other considerations (for example, properties of the desired metal(s), properties of the feed materials, available fuel and energy sources, capacity and economic considerations). The formation and release of chemicals listed in Annex C is considered to be a result of hightemperature thermal metallurgical operations. Consideration should be given to hydrometallurgical processes (for example, leaching, electrowinning), where technically feasible, as alternatives to pyrometallurgical processes (for example, roasting, smelting, converting, fire refining) when considering proposals for the construction and commissioning of new base metals smelting facilities or processes.
4.
There is a paucity of information on the release of chemicals listed in Annex C from primary base metals smelting operations. No techniques were identified specifically for the primary base metals smelting sector to prevent or control the unintentional formation and release of PCDD/PCDF and other chemicals listed in Annex C. The following measures constitute general measures which may result in lower pollutant emissions at primary base metals smelters, including releases of PCDD/PCDF. The extent of emission reduction possible with implementation of primary measures only is not readily known. It is therefore recommended that consideration be given to implementation of both primary and secondary measures.
4.1.
Primary measures
Primary measures are regarded as pollution prevention measures that will prevent or minimize the formation and release of the identified substances, namely PCDD, PCDF, hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB). These are sometimes referred to as process optimization or integration measures. Pollution prevention is defined as: The use of processes, practices, materials, products or energy that avoid or minimize the creation of pollutants and
16
1 pg (picogram) = 1 x 10-15 kilogram (1 x 10-12 gram); 1 ng (nanogram) = 1 10-12 kilogram (1 10-9 gram). For information on toxicity measurement see section I.C, paragraph 3 of the present guidelines.
110
waste, and reduce overall risk to human health or the environment. (See section III.B of the present guidelines.) Primary measures that may assist in reducing the formation and release of pollutant emissions include: 4.1.1.Use of hydrometallurgical processes Use of hydrometallurgical processes rather than pyrometallurgical processes where possible is a significant means of preventing emissions. Closed-loop electrolysis plants will contribute to prevention of pollution. 4.1.2.Quality control of (scrap) feed material The presence of oils, plastics and chlorine compounds in scrap feed materials should be avoided to reduce the generation of PCDD/PCDF during incomplete combustion or by de novo synthesis. Feed material should be classified according to composition and possible contaminants. Selection and sorting to prevent the addition of material that is contaminated with organic matter or precursors can reduce the potential for PCDD/PCDF formation. Storage, handling and pretreatment techniques will be determined by feed size distribution and contamination. Methods to be considered are (European Commission 2001, p.232): Oil removal from feed (for example, thermal decoating and de-oiling processes followed by afterburning to destroy any organic material in the off-gas); Use of milling and grinding techniques with good dust extraction and abatement. The resulting particles can be treated to recover valuable metals using density or pneumatic separation; Elimination of plastic by stripping cable insulation (for example, possible cryogenic techniques to make plastics friable and easily separable); Sufficient blending of material to provide a homogeneous feed in order to promote steady-state conditions. 4.1.3.Effective process control Process control systems should be utilized to maintain process stability and ensure operation at parameter levels that will contribute to the minimization of PCDD/PCDF generation, such as maintaining furnace temperature above 850 C to destroy PCDD/PCDF. Ideally, PCDD/PCDF emissions would be monitored continuously to ensure reduced releases. Continuous emissions sampling of PCDD/PCDF has been demonstrated for some sectors (for example, waste incineration), but research is still developing in this field. In the absence of continuous PCDD/PCDF monitoring, other variables such as temperature, residence time, gas components and fume collection damper controls should be continuously monitored and maintained to establish optimum operating conditions for the reduction of PCDD/PCDF. 4.1.4.Use of flash smelting technology The most effective pollution prevention option is to choose a process that entails lower energy usage and lower emissions. Where pyrometallurgical techniques are used, use of flash smelting technology rather than older technologies (for example, roasters, blast furnace) is a significant means of reducing energy use and reducing emissions. Flash smelting will also result in high concentration of sulphur dioxide in the off-gas stream, which would permit the efficient fixation or recovery of sulphur dioxide prior to off-gas venting. 4.1.5.Maximization of SO2 content for sulphur fixation A general measure involves operation of processes in a manner that maximizes the concentration of the SO2 in the off-gas (when processing sulphide ores or concentrates). It is important, therefore, that a process be selected that uses oxygen-enriched air (or pure oxygen) to raise the SO 2 content of
111
the process gas stream and reduce the total volume of the stream, thus permitting efficient fixation of SO2.
4.2.
Secondary measures
Secondary measures are understood to be pollution control technologies or techniques, sometimes described as end-of-pipe treatments. Secondary measures that may assist in reducing the formation and release of pollutant emissions include: 4.2.1.High-efficiency gas cleaning and conversion of SO2 to sulphuric acid For SO2-rich off-gases (typically 5% or greater) generated by pyrometallurgical processing of sulphide ores or concentrates, high-efficiency precleaning of off-gases followed by conversion of SO2 to sulphuric acid are together considered best available techniques for this type of source. Emission concentrations of PCDD/PCDF with use of this combination of techniques are < 0.005 ng TEQ/m3. For conversion to sulphuric acid, a double-contact, double-absorption process is considered a best available technique. A double-contact, double-absorption plant should emit no more than 0.2 kg of SO2 per ton of sulphuric acid produced (based on a conversion efficiency of 99.7%) (World Bank 1998). SO2-rich off-gases from smelting facilities pass through a gas-cleaning train, which typically includes high-efficiency dedusting, prior to the sulphuric acid plant. This combination of techniques has the co-benefit of controlling dust and SO 2 emissions, in addition to PCDD/PCDF. Other techniques for sulphur fixation, which may require precleaning of off-gases prior to conversion or recovery, may potentially contribute to the minimization of PCDD/PCDF emissions (World Bank 1998). These techniques include (World Bank 1998): Recovery as liquid sulphur dioxide (absorption of clean, dry off-gas in water or chemical absorption by ammonium bisulphite or dimethyl aniline); Recovery as elemental sulphur, using reductants such as hydrocarbons, carbon or hydrogen sulphide. Normally the sulfur content in the gas is still higher than acceptable when using this technique. The reduction conditions are also favourable for dioxins formation. Thus, after the recovery, the gas should be post combusted and cleaned using techniques such as scrubbing. 4.2.2.Fume and gas collection Air emissions should be controlled at all stages of the process, from material handling, smelting and material transfer points, to control of the emission of PCDD/PCDF. Sealed furnaces are essential to contain fugitive emissions while permitting heat recovery and collecting off-gases for process recycling. Proper design of hooding and ductwork is essential to trap fumes. Furnace or reactor enclosures may be necessary. If primary extraction and enclosure of fumes is not possible, the furnace should be enclosed so that ventilation air can be extracted, treated and discharged. Roofline collection of fume should be avoided due to high energy requirements. The use of intelligent damper controls can improve fume capture and reduce fan sizes and hence costs. Sealed charging cars or skips used with a reverberatory furnace can significantly reduce fugitive emissions to air by containing emissions during charging (European Commission 2001, p. 187188). Fortunately the number of reverberatory furnaces is steadily decreasing in the world because of the difficulty to control the emissions and the high costs involved. It is difficult to imagine that new reverberatory furnaces would be built today. (Personal Communication, February 2006) 4.2.3.High-efficiency dust removal
112
The smelting process generates high volumes of particulate matter with large surface area on which PCDD/PCDF can adsorb. These dusts and metal compounds should be removed to reduce PCDD/PCDF emissions. Very high-efficiency dust removal techniques should be employed, for example, ceramic filters, high-efficiency fabric filters or the gas-cleaning train prior to a sulphuric acid plant. Preference should be given to fabric filters over wet scrubbers, wet electrostatic precipitators, or hot electrostatic precipitators for dust control. Dust from dust control equipment should be returned to the process. Returned or collected dust should be treated in high-temperature furnaces to destroy PCDD/PCDF and recover metals preferably by recycling the dust back into the smelting process. Dust that is captured but not recycled will need to be disposed of in a secure landfill or other acceptable manner. Fabric filter operations should be constantly monitored by devices to detect bag failure.
5.
5.1.
Emerging research
Catalytic oxidation
Selective catalytic reduction has been used for controlling emissions of nitrogen oxides (NO x) from a number of industrial processes. Modified selective catalytic reduction technology (i.e., increased reactive area) and select catalytic processes have been shown to decompose PCDD and PCDF contained in off-gases, probably through catalytic oxidation reactions. This may be considered as an evolving technique with potential for effectively reducing emissions of persistent organic pollutants from base metals smelting operations and other applications. However, catalytic oxidation can, subject to catalyst selection, be subject to poisoning from trace metals and other exhaust gas contaminants. Validation work would be necessary before use of this process.
6.
Summary of measures
Tables 1 and 2 present a summary of the measures discussed in previous sections. Table 1. Measures for new primary base metals smelting operations
Measure Alternative processes Description Priority consideration should be given to alternative processes with potentially less environmental impacts than pyrometallurgical base metals smelting Considerations Hydrometallurgical processes are a significant means of preventing emissions. It has been commented that direct atmospheric leaching of sulfide concentrations (Fex to Zn concentrates) should be considered. (Finnish representative, 2006) Closed-loop electrolysis plants will contribute to prevention of pollution Consideration should be given to the primary and secondary measures listed Performance requirements for achievement should take into consideration Other comments
New primary base metals smelting operations should be permitted to achieve

Measure Description stringent performance and reporting requirements associated with best available techniques Considerations in table 2 Other comments
113
achievable emission levels of PCDD/PCDF identified in subsection 7
Table 2. Summary of primary and secondary measures for primary base metals smelting operations
Measure Primary measures Use of hydrometallurgical processes Use of hydrometallurgical processes rather than pyrometallurgical processes where possible, as a significant means of preventing emissions. Closed-loop electrolysis plants will contribute to prevention of pollution Use of hydrometallurgical processes will depend in large part on the ore and concentrate to be processed (e.g. laterite or sulphide) It has been commented that the combination of hydro and pyro metallurgy for Zn, emerging for other metals like Ni and Cu, should be considered. (Finnish representative, 2006) Methods to be considered are: Oil removal from feed (e.g. thermal decoating and deoiling processes followed by afterburning to destroy any organic material in the off-gas) Use of milling and grinding techniques with good dust extraction and abatement. The resulting particles can be treated to recover valuable metals using density or pneumatic separation Elimination of plastic by stripping cable insulation (e.g. possible cryogenic techniques to make plastics friable and easily separable) Sufficient blending of material to provide a homogeneous feed in order to promote steady-state Description Considerations Other comments
Quality control of (scrap) feed material
Selection and sorting to prevent the addition of material that is contaminated with organic matter or precursors can reduce the potential for PCDD/PCDF formation
114
Measure

Description Considerations conditions. It has been commented that this should be the first priority. (Finnish representative, 2006) Other comments
Process control systems should be utilized to maintain process stability and operate at parameter levels that will contribute to the minimization of PCDD/PCDF generation. In the absence of continuous PCDD/PCDF monitoring, other variables such as temperature, residence time, gas components and fume collection damper controls should be continuously monitored and maintained to establish optimum operating conditions for the reduction of PCDD/PCDF Where pyrometallurgical techniques are used, use of flash smelting technology rather than older technologies (e.g. roasters, blast furnace) is a significant means of reducing energy use and reducing emissions This general measure involves operation of processes in a manner that maximizes the concentration of the SO2 in the off-gas (where processing sulphide ores or concentrates), to enable recovery or fixation of the sulphur. Preference should be given to processes that use oxygenenriched air (or pure oxygen) to raise the SO2 content of the process gas stream and reduce the total volume of the stream
For example, furnace temperatures should be maintained above 850 C to destroy PCDD/PCDF
Use flash smelting technology
Flash smelting will also result in high concentration of SO2 in the off-gas stream, which would permit the efficient fixation or recovery of SO2 prior to off-gas venting
Maximize SO2 content for sulphur fixation
Secondary measures The following secondary measures can effectively reduce emissions of PCDD/PCDF and should be considered as examples of best available techniques High-efficiency gas cleaning and conversion of SO2 to sulphuric acid SO2-rich off-gases, high-efficiency precleaning of off-gases followed by conversion of SO2 to sulphuric acid should be employed, and are together considered best available techniques This combination of techniques has the cobenefit of controlling dust and SO2 emissions, in addition to PCDD/PCDF Emission concentrations of PCDD/PCDF with use of high-efficiency gas cleaning

Measure Description Considerations
115
Other comments and conversion of SO2 to sulphuric acid are < 0.005 ng TEQ/m3
Fume and gas collection
Air emissions should be controlled at all stages of the process, from material handling, smelting and material transfer points, to control the emission of PCDD/PCDF Dusts and metal compounds should be removed to reduce PCDD/PCDF emissions. Very high-efficiency dust removal techniques should be employed, for example, ceramic filters, highefficiency fabric filters or the gascleaning train prior to a sulphuric acid plant. Dust from dust control equipment should be returned to the process. Returned/collected dust should be treated in high-temperature furnaces to destroy PCDD/PCDF and recover metals. Fabric filter operations should be constantly monitored by devices to detect bag failure Preference should be given to fabric filters over wet scrubbers, wet electrostatic precipitators, or hot electrostatic precipitators for dust control. Dust that is captured but not recycled will need to be disposed of in a secure landfill or other acceptable manner
7.
Emission levels achieved at primary base metals smelting operations are noted in Table 3. Table 3. Performance levels achieved at primary base metals smelting operations 17
Primary base metals smelting source type New primary smelters Acid plant tail gas (recovery of sulphur dioxide in off-gas from pyrometallurgical sources) Off-gas dedusted by baghouse Off-gas dedusted by electrostatic precipitator Achievable performance < 0.1 ng TEQ/Nm3 < 0.005 pg TEQ/m3 < 0.005 ng TEQ/m3 to < 0.03 ng TEQ/m3 0.03 ng TEQ/m3 to < 0.5 ng TEQ/m3
References
17
116
A.J. Gunson, Yue Jian, Artisanal Mining in The People's Republic of China, Mining, Minerals and Sustainable Development (MMSD), International Institute for Environment and Development (IIED), September 2001 Charles E. Napier Co. Ltd. 2002. Generic Dioxin/Furan Emission Testing Protocol for the Base Metals Smelting Sector. Prepared for Environment Canada. European Commission. 2001. Reference Document on Best Available Techniques in the NonFerrous Metals Industries. BAT Reference Document (BREF). European IPPC Bureau, Seville, Spain. eippcb.jrc.es. Feng Xinbin, Qui Guangle, Li Guanghui, Li Ping, Wang Shaofeng, Mercury Emissions from Artisanal Zinc and Mercury Smelting in Guizhou, PR China, Goldschmidt Conference Abstracts 2005, The Geochemistry of Mercury, page A705 Personal communication from Expert Group Best Available Techniques Best Environmental Practices, Finland Member, February 2006 World Bank. 1998. Pollution Prevention and Abatement Handbook. Chapters on copper, nickel, lead and zinc smelting. www.worldbank.org. UNEP Environment Program News Centre,
http://www.unep.org/Documents.Multilingual/Default.asp? DocumentID=284&ArticleID=3204&l=en, as read on January 20, 2006

Xinbin Feng, Xianwu Bi, Guangle Qiu, Guanghui Li, Shunlin Tang, Mercury Pollution in Guizhou, China - A status Report, http://pbc.eastwestcenter.org/abstracts2005/abstract2005fengxinbin.htm, as read on December 29th, 2005

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Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

(ii) Sinter plants in the iron and steel industry

(iii) Secondary aluminium production

(iv) Secondary zinc production

Summaries by source categories Part III of Annex C

(ii) Primary aluminium production

(iii) Magnesium production

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

(iv) Secondary steel production

(v) Primary base metals smelting

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Section V Guidance/guidelines by source category: Source categories in Part II of Annex C

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Figure 1. Secondary copper smelting

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Flux, scrap, air, oxygen

Clean scrap, reductant, air

Air emissions:, SO2, metals, dust

Potential output Smelting reduction

Flux, scrap, air, oxygen

Clean scrap, reductant, air

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Source: European Commission 2001, p. 217

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Sources of chemicals listed in Annex C of the Stockholm Convention

General information on emissions from secondary copper smelters

Emissions of PCDD/PCDF to air

Releases to other media

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Primary and secondary measures

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006

SECTION V. Guidelines/guidance by source category: Part II of Annex C

Afterburners and quenching

Adsorption on activated carbon

Lime/carbon mixtures can also be used

Guidelines on BAT and Guidance on BEP

Environment Canada Revision, April 28, 2006