prop · GM03141 · 1999-01-01 00:00:00 — This annex takes into account the emissions of cadmium, lead and mercury and their compounds, in solid (particle-bound) and/or gaseous form. Speciation of these compounds is, in general, not considered here. Nevertheless, the efficiency of emission control devices with regard to the physical properties of the heavy metal, especially in the case of mercury, has been taken into account. Emission values expressed as mg/m3 refer to standard conditions (volume at 273.15 K, 101.3 kPa, dry gas) not corrected for oxygen content unless otherwise specified, and are calculated in accordance with draft (Comité européen de normalisation) and, in some cases, national sampling and monitoring techniques. GENERAL OPTIONS FOR REDUCING EMISSIONS OF HEAVY METALS AND THEIR COMPOUNDS There are several possibilities for controlling or preventing heavy metal emissions. Emission reduction measures focus on add-on technologies and process modifications (including maintenance and operating control). The following measures, which may be implemented depending on the wider technical and/or economic conditions, are available: (a) Application of low-emission process technologies, in particular in new installations; (b) Off-gas cleaning (secondary reduction measures) with filters, scrubbers, absorbers, etc.; (c) Change or preparation of raw materials, fuels and/or other feed materials (e.g. use of raw materials with low heavy metal content); (d) Best management practices such as good housekeeping, preventive maintenance programmes, or primary measures such as the enclosure of dust-creating units; (e) Appropriate environmental management techniques for the use and disposal of certain products containing Cd, Pb, and/or Hg. It is necessary to monitor abatement procedures to ensure that appropriate control measures and practices are properly implemented and achieve an effective emission reduction. Monitoring abatement procedures will include: (a) Developing an inventory of those reduction measures identified above that have already been implemented; (b) Comparing actual reductions in Cd, Pb and Hg emissions with the objectives of the Protocol; (c) Characterizing quantified emissions of Cd, Pb and Hg from relevant sources with appropriate techniques; (d) Regulatory authorities periodically auditing abatement measures to ensure their continued efficient operation. Emission reduction measures should be cost-efficient. Cost-efficient strategy considerations should be based on total costs per year per unit abated (including capital and operating costs). Emission reduction costs should also be considered with respect to the overall process. The major categories of available control techniques for Cd, Pb and Hg emission abatement are primary measures such as raw material and/or fuel substitution and low- emission process technologies, and secondary measures such as fugitive emission control and off-gas cleaning. Sector-specific techniques are specified in chapter IV. The data on efficiency are derived from operating experience and are considered to reflect the capabilities of current installations. The overall efficiency of flue gas and fugitive emission reductions depends to a great extent on the evacuation performance of the gas and dust collectors (e.g. suction hoods). Capture/collection efficiencies of over have been demonstrated. In particular cases experience has shown that control measures are able to reduce overall emissions by or more. In the case of particle-bound emissions of Cd, Pb and Hg, the metals can be captured by dust-cleaning devices. Typical dust concentrations after gas cleaning with selected techniques are given in table 1. Most of these measures have generally been applied across sectors. The minimum expected performance of selected techniques for capturing gaseous mercury is outlined in table 2. The application of these measures depends on the specific processes and is most relevant if concentrations of mercury in the flue gas are high. Table 1: Performance of dust-cleaning devices expressed as hourly average dust concentrations Dust concentrations after cleaning (mg/m3) Fabric filters Fabric filters, membrane type Dry electrostatic precipitators electrostatic precipitators High-efficiency scrubbers < 10 < 1 < 50 < 50 < 50 Note: Medium- and low-pressure scrubbers and cyclones generally show lower dust removal efficiencies. Table 2: Minimum expected performance of mercury separators expressed as hourly average mercury concentrations Mercury content after cleaning (mg/m3) Selenium filter Selenium scrubber Carbon filter Carbon injection + dust separator chloride process Lead sulphide process Bolkem (Thiosulphate) process < 0.01 < 0.2 < 0.01 < 0.05 < 0.1 < 0.05 < 0.1 Care should be taken to ensure that these control techniques do not create other environmental problems. The choice of a specific process because of its low emission into the air should be avoided if it worsens the total environmental impact of the heavy metals'''' discharge, e.g. due to more water pollution from liquid effluents. The fate of captured dust resulting from improved gas cleaning must also be taken into consideration. A negative environmental impact from the handling of such wastes will reduce the gain from lower process dust and fume emissions into the air. Emission reduction measures can focus on process techniques as well as on off-gas cleaning. The two are not independent of each other; the choice of a specific process might exclude some gas-cleaning methods. The choice of a control technique will depend on such parameters as the pollutant concentration and/or speciation in the raw gas, the gas volume flow, the gas temperature, and others. Therefore, the fields of application may overlap; in that case, the most appropriate technique must be selected according to case-specific conditions. Adequate measures to reduce stack gas emissions in various sectors are described below. Fugitive emissions have to be taken into account. Dust emission control associated with the discharging, handling, and stockpiling of raw materials or by-products, although not relevant to long-range transport, may be important for the local environment. The emissions can be reduced by moving these activities to completely enclosed , which may be equipped with ventilation and dedusting facilities, spray systems or other suitable controls. When stockpiling in unroofed areas, the material surface should be otherwise protected against wind entrainment. Stockpiling areas and roads should be kept clean. The investment/cost figures listed in the tables have been collected from various sources and are highly case-specific. They are expressed in 1990 US$ (US$ 1 (1990) = ECU 0.8 (1990)). They depend on such factors as plant capacity, removal efficiency and raw gas concentration, type of technology, and the choice of new installations as opposed to retrofitting. This chapter contains a table per relevant sector with the main emission sources, control measures based on the best available techniques, their specific reduction efficiency and the related costs, where available. Unless stated otherwise, the reduction efficiencies in the tables refer to direct stack gas emissions. Combustion of fossil fuels in utility and industrial boilers (annex II, category 1) The combustion of coal in utility and industrial boilers is a major source of anthropogenic mercury emissions. The heavy metal content is normally several orders of magnitude higher in coal than in oil or natural gas. Improved energy conversion efficiency and energy conservation measures will result in a decline in the emissions of heavy metals because of reduced fuel requirements. Combusting natural gas or alternative fuels with a low heavy metal content instead of coal would also result in a significant reduction in heavy metal emissions such as mercury. Integrated gasification combined-cycle (IGCC) power plant technology is a new plant technology with a low-emission potential. With the exception of mercury, heavy metals are emitted in solid form in association with fly-ash particles. Different coal combustion technologies show different magnitudes of fly-ash generation: grate-firing boilers ; fluidized-bed combustion ; dry bottom boilers (pulverized coal combustion) of total ash. The heavy metal content in the small particle size fraction of the fly-ash has been found to be higher. Beneficiation, e.g. "washing" or "bio-treatment", of coal reduces the heavy metal content associated with the inorganic matter in the coal. However, the degree of heavy metal removal with this technology varies widely. A total dust removal of more than can be obtained with electrostatic precipitators (ESP) or fabric filters (FF), achieving dust concentrations of about /m3 in many cases. With the exception of mercury, heavy metal emissions can be reduced by at least , the lower figure for the more easily volatilized elements. Low filter temperature helps to reduce the gaseous mercury off-gas content. The application of techniques to reduce emissions of nitrogen oxides, sulphur dioxide and particulates from the flue gas can also remove heavy metals. Possible cross media impact should be avoided by appropriate waste water treatment. Using the techniques mentioned above, mercury removal efficiencies vary extensively from plant to plant, as seen in table 3. Research is ongoing to develop mercury removal techniques, but until such techniques are available on an industrial scale, no best available technique is identified for the specific purpose of removing mercury. Table 3: Control measures, reduction efficiencies and costs for fossil-fuel combustion emissions Emission source Control measure(s) Reduction efficiency (%) Abatement costs (total costs US$) Combustion of fuel oil Switch fuel oil to gas Cd, Pd: 100; Hg: 70- 80 Highly case- specific Combustion of coal Switch from coal to fuels with lower heavy metals emissions Dust 70-100 Highly case- specific ESP (cold-side) Cd, Pb: > 90; Hg: 10-40 Specific investment US$8- 15/m3 waste gas per hour (> /h) fuel-gas desulphurization (FGD) a/ Cd, Pb: > 90; Hg: 10-90 b/ 15-30/Mg waste Fabric filters (FF) Cd: >95; Pb: > 99; Hg: 10-60 Specific investment US$8- 15/m3 waste gas per hour (> /h) a/ Hg removal efficiencies increase with the proportion of ionic mercury. High-dust selective catalytic reduction (SCR) installations facilitate Hg(II) formation. b/ This is primarily for SO2 reduction. Reduction in heavy metal emissions is a side benefit. (Specific investment US$ 60-250/kWel.) Primary iron and steel industry (annex II, category 2) This section deals with emissions from sinter plants, pellet plants, blast furnaces, and steelworks with a basic oxygen furnace (BOF). Emissions of Cd, Pb and Hg occur in association with particulates. The content of the heavy metals of concern in the emitted dust depends on the composition of the raw materials and the types of alloying metals added in steel-making. The most relevant emission reduction measures are outlined in table 4. Fabric filters should be used whenever possible; if conditions make this impossible, electrostatic precipitators and/or high-efficiency scrubbers may be used. When using BAT in the primary iron and steel industry, the total specific emission of dust directly related to the process can be reduced to the following levels: Sinter plants 40 - /Mg Pellet plants /Mg Blast furnace 35 - /Mg BOF 35 - /Mg. Purification of gases using fabric filters will reduce the dust content to less than /m3, whereas electrostatic precipitators and scrubbers will reduce the dust content to /m3 (as an hourly average). However, there are many applications of fabric filters in the primary iron and steel industry that can achieve much lower values. Table 4: Emission sources, control measures, dust reduction efficiencies and costs for the primary iron and steel industry Emission source Control measure(s) Dust reduction efficiency (%) Abatement costs (total costs US$) Sinter plants Emission optimized sintering ca. Scrubbers and ESP > 90 .. Fabric filters > 99 .. Pellet plants ESP + lime reactor + fabric filters > 99 .. Scrubbers > 95 .. Blast furnaces Blast furnace gas cleaning FF / ESP > 99 ESP: 0.24-1/Mg pig- iron scrubbers > 99 .. 99 .. BOF Primary dedusting: wet separator/ESP/99 Dry ESP: 2.25/Mg steel Secondary dedusting: dry ESP/97 FF: 0.26/Mg steel Fugitive emissions Closed conveyor belts, enclosure, wetting stored feedstock, cleaning of reads 80 - 99 .. Direct reduction and direct smelting are under development and may reduce the need for sinter plants and blast furnaces in the future. The application of these technologies depends on the ore characteristics and requires the resulting product to be processed in an electric arc furnace, which should be equipped with appropriate controls. Secondary iron and steel industry (annex II, category 3) It is very important to capture all the emissions efficiently. That is possible by installing doghouses or movable hoods or by total evacuation. The captured emissions must be cleaned. For all dust-emitting processes in the secondary iron and steel industry, dedusting in fabric filters, which reduces the dust content to less than /m3, shall be considered as BAT. When BAT is used also for minimizing fugitive emissions, the specific dust emission (including fugitive emission directly related to the process) will not exceed the range of 0.1 to /Mg steel. There are many examples of clean gas dust content below /m3 when fabric filters are used. The specific dust emission in such cases is normally below /Mg. For the melting of scrap, two different types of furnace are in use: open-hearth furnaces and electric arc furnaces (EAF) where open-hearth furnaces are about to be phased out. The content of the heavy metals of concern in the emitted dust depends on the composition of the iron and steel scrap and the types of alloying metals added in steel- making. Measurements at EAF have shown that of emitted mercury and of cadmium emissions occur as vapour. The most relevant dust emission reduction measures are outlined in table 5. Table 5: Emission sources, control measures, dust reduction efficiencies and costs for the secondary iron and steel industry Emission source Control measure(s) Dust reduction efficiency (%) Abatement costs (total costs US$) > 99 > 99.5 .. FF: 24/Mg steel foundaries (annex II, category 4) It is very important to capture all the emissions efficiently. That is possible by installing doghouses or movable hoods or by total evacuation. The captured emissions must be cleaned. In iron foundries, cupola furnaces, electric arc furnaces and induction furnaces are operated. Direct particulate and gaseous heavy metal emissions are especially associated with melting and sometimes, to a small extent, with pouring. Fugitive emissions arise from raw material handling, melting, pouring and fettling. The most relevant emission reduction measures are outlined in table 6 with their achievable reduction efficiencies and costs, where available. These measures can reduce dust concentrations to /m3, or less. The iron foundry industry comprises a very wide range of process sites. For existing smaller installations, the measures listed may not be BAT if they are not economically viable. Table 6: Emission sources, control measures, dust reduction efficiencies and costs for iron foundries Emission source Control measure(s) Dust reduction efficiency (%) Abatement costs (total costs US$) EAF ESP > 99 .. 99.5 FF: 24/Mg iron Induction furnace FF/dry absorption + 99 .. Cold blast cupola Below-the-door take- off: 98 .. Above-the-door take- off: FF + pre-dedusting > 97 8-12/Mg iron FF + chemisorption > 99 45/Mg iron Hot blast cupola FF + pre-dedusting > 99 23/Mg iron Disintegrator/venturi scrubber > 97 .. Primary and secondary non-ferrous metal industry (annex II, categories 5 and 6) This section deals with emissions and emission control of Cd, Pb and Hg in the primary and secondary production of non-ferrous metals like lead, copper, zinc, tin and nickel. to the large number of different raw materials used and the various processes applied, nearly all kinds of heavy metals and heavy metal compounds might be emitted from this sector. Given the heavy metals of concern in this annex, the production of copper, lead and zinc are particularly relevant. Mercury ores and concentrates are initially processed by crushing, and sometimes screening. Ore beneficiation techniques are not used extensively, although flotation has been used at some facilities processing low-grade ore. The crushed ore is then heated in either retorts, at small operations, or furnaces, at large operations, to the temperatures at which mercuric sulphide sublimates. The resulting mercury vapour is condensed in a cooling system and collected as mercury metal. Soot from the condensers and settling tanks should be removed, treated with lime and returned to the retort or furnace. For efficient recovery of mercury the following techniques can be used: - Measures to reduce dust generation during mining and stockpiling, including minimizing the size of stockpiles; - Indirect heating of the furnace; - the ore as dry as possible; - Bringing the gas temperature entering the condenser to only 10 to 20 C above the dew point; - the outlet temperature as low as possible; and - Passing reaction gases through a post-condensation scrubber and/or a selenium filter. Dust formation can be kept down by indirect heating, separate processing of fine grain of ore, and control of ore water content. Dust should be removed from the hot reaction gas before it enters the mercury condensation unit with cyclones and/or For gold production by amalgamation, similar strategies as for mercury can be applied. Gold is also produced using techniques other than amalgamation, and these are considered to be the preferred option for new plants. Non-ferrous metals are mainly produced from sulphitic ores. For technical and product quality reasons, the off-gas must go through a thorough dedusting (< /m3) and could also require additional mercury removal before being fed to an SO3 contact plant, thereby also minimizing heavy metal emissions. Fabric filters should be used when appropriate. A dust content of less than /m3 can be obtained. The dust of all pyrometallurgical production should be recycled in-plant or off-site, while protecting occupational health. For primary lead production, first experiences indicate that there are interesting new direct smelting reduction technologies without sintering of the concentrates. These processes are examples of a new generation of direct autogenous lead smelting technologies which pollute less and consume less energy. Secondary lead is mainly produced from used car and truck , which are dismantled before being charged to the smelting furnace. This BAT should include one melting operation in a short furnace or shaft furnace. Oxy-fuel can reduce waste gas volume and flue dust production by . Cleaning the flue-gas with fabric filters makes it possible to achieve dust concentration levels of /m3. Primary zinc production is carried out by means of roast-leach electrowin technology. Pressure leaching may be an alternative to roasting and may be considered as a BAT for new plants depending on the concentrate characteristics. Emissions from pyrometallurgical zinc production in Smelting (IS) furnaces can be minimized by using a double bell furnace top and cleaning with high-efficiency scrubbers, efficient evacuation and cleaning of gases from slag and lead casting, and thorough cleaning (< /m3) of the CO-rich furnace off-gases. To recover zinc from oxidized residues these are processed in an IS furnace. low- grade residues and flue dust (e.g. from the steel industry) are first treated in furnaces (Waelz-furnaces) in which a high-content zinc oxide is manufactured. Metallic materials are recycled through melting in either induction furnaces or furnaces with direct or indirect heating by natural gas or liquid fuels or in vertical retorts, in which a large variety of oxidic and metallic secondary material can be recycled. Zinc can also be recovered from lead furnace slags by a slag fuming process. Table 7 (a): Emission sources, control measures, dust reduction efficiencies and costs for the primary non-ferrous metal industry Emission source Control measure(s) Dust reduction efficiency (%) Abatement costs (total costs US$) Fugitive emissions Suction hoods, enclosure, etc. off-gas cleaning by 99 .. Roasting/sintering Updraught sintering: ESP + scrubbers (prior to double contact sulphuric acid plant) + FF for tail gases .. 7 - 10/Mg H2SO4 Conventional smelting (blast furnace reduction) Shaft furnace: closed top/efficient evacuation of tap holes + FF, covered launders, double bell furnace top .. .. smelting High-efficiency scrubbing > 95 .. Venturi scrubbers .. .. Double bell furnace top .. 4/Mg metal produced Pressure leaching Application depends on leaching characteristics of concentrates > 99 site-specific Direct smelting reduction processes Flash smelting, e.g. kivcet, Outokumpu and process .. .. Bath smelting, e.g. top blown converter, Ausmelt, Isasmelt, QSL and processes Ausmelt: Pb 77, Cd 97; QSL: Pb 92, Cd 93 QSL: operating costs 60/Mg Pb Table 7 (b): Emission sources, control measures, dust reduction efficiencies and costs for the secondary non-ferrous metal industry Emission source Control measure(s) Dust reduction efficicency (%) Abatement costs (total costs, US$) Lead production Short furnace: suction hoods for tap holes + FF; tube condenser, oxy-fuel 99.9 45/Mg Pb Zinc production smelting > 95 14/Mg Zn In general, processes should be combined with an effective dust collecting device for both primary gases and fugitive emissions. The most relevant emission reduction measures are outlined in tables 7 (a) and (b). Dust concentrations below /m3 have been achieved in some cases using fabric filters. Cement industry (annex II, category 7) Cement kilns may use secondary fuels such as waste oil or waste tyres. Where waste is used, emission requirements for waste incineration processes may apply, and where hazardous waste is used, depending on the amount used in the plant, emission requirements for hazardous waste incineration processes may apply. However, this section refers to fossil fuel fired kilns. Particulates are emitted at all stages of the cement production process, consisting of material handling, raw material preparation (crushers, dryers), clinker production and cement preparation. Heavy metals are brought into the cement kiln with the raw materials, fossil and waste fuels. For clinker production the following kiln types are available: long wet kiln, long dry kiln, kiln with cyclone preheater, kiln with grate preheater, shaft furnace. In terms of energy demand and emission control opportunities, kilns with cyclone preheaters are preferable. For heat recovery purposes, kiln off-gases are conducted through the preheating system and the mill dryers (where installed) before being dedusted. The collected dust is returned to the feed material. Less than of lead and cadmium entering the kiln is released in exhaust gases. The high alkali content and the scrubbing action in the kiln favour metal retention in the clinker or kiln dust. The emissions of heavy metals into the air can be reduced by, for instance, taking off a bleed stream and stockpiling the collected dust instead of returning it to the raw feed. However, in each case these considerations should be weighed against the consequences of releasing the heavy metals into the waste stockpile. Another possibility is the hot-meal bypass, where calcined hot-meal is in part discharged right in front of the kiln entrance and fed to the cement preparation plant. Alternatively, the dust can be added to the clinker.