Pasquale Spezzano UNIDO Consultant BAT and provisional guidance on BEP relevant to Article 5 and Annex C of the Stockholm Convention on POPs Seminar on Metallurgy and Integrated Permit 8 December 2011 Faculty of Technology and Metallurgy Belgrade, Serbia

A production process Energy Raw materials Workforce Profit Product By-products/ residues Pollutants (CO 2, NOx, SOx, PM… U-POPs) Investment

Persistent Organic Pollutants nPesticides (for instance DDT) nIndustrial chemicals (for instance PCB) nUnintended by-products (chemicals generated unintentionally as a result of incomplete combustion and/or chemical reactions)

Persistent Organic Pollutants Toxicity Persistence Long-range transport Bio-magnification No tolerance Why should we worry about POPs?

Stockholm Convention on Persistent Organic Pollutants The Stockholm Convention on Persistent Organic Pollutants is a global treaty to protect human health and the environment. The Stockholm Convention was adopted on 22 May 2001 and entered into force on 17 May It initially listed twelve chemicals. In 2009, nine more substances were added to the Convention. Probably, more substances will be added in the future.

Stockholm Convention on Persistent Organic Pollutants Status of ratification as of 24 November 2011: 176 Parties

Unintentionally produced Persistent Organic Pollutants ………… Take measures to reduce the total releases derived from anthropogenic sources of each of the chemicals listed in Part I of Annex C… Parties shall promote in some cases and require in others the use of Best Available Techniques (BAT), and promote the application of Best Environmental Practices (BEP) for source categories listed in Parts II and III of Annex C. ……….. Article 5

n Polychlorinated dibenzo-p-dioxins (PCDDs) n Polychlorinated dibenzofurans (PCDFs) n Polychlorinated biphenyls (PCBs) n Hexachlorobenzene (HCB) n Pentachlorobenzene (PeCB) Annex C, Part I Unintentionally produced Persistent Organic Pollutants

Best Available Techniques (BAT) "Best" means the most effective and advanced stage in the development of activities and their methods of operation... to prevent and … generally to reduce releases of chemicals listed in Part I of Annex C. Available means those techniques that are accessible to the operator and that are developed on a scale that allows implementation in the relevant industrial sector, under economically and technically viable conditions, taking into consideration the costs and advantages; Techniques includes both the technology used and the way in which the installation is designed, built, maintained, operated and decommissioned;

Best Environmental Practices (BEP) Definition under the Stockholm Convention: BEP means the application of the most appropriate combination of environmental control measures and strategies. A more detailed description of BEP could not be reached during the negotiation of the Convention. We can think BEP as the infrastructural measures, which in part extend beyond the level of individual installations and which, in combination with BAT, take them towards a reduction strategy which must be implemented comprehensively.

Guidelines/Guidance on best available techniques and best environmental practices

Primary and secondary measures Measures to reduce emissions to the environment generally fall into two categories: nprimary or process-integrated measures that attempt to prevent or minimize the pollutant being formed and emitted from the main process; nsecondary or end-of-pipe measures that attempt to destroy or recapture emissions after they have been formed and emitted from the main process.

Primary and secondary measures To reduce the total releases derived from anthropogenic sources of each of the chemicals listed in Annex C, releases of U-POPs into the general five compartments and/or media into which U-POPs can be released or transferred (air, water, land, residues, and products) must be considered. End-of pipe measures such as fabric filters or scrubbers simply transfer pollutants from one medium to another (i.e. from air to filter dust or sludge).

Primary and secondary measures Substitution is an important requirement of the Stockholm Convention: n Parties shall, at a minimum, Promote the development and, where it deems appropriate, require the use of substitute or modified materials, products and processes to prevent the formation and release of the chemicals listed in Annex C (Article 5, paragraph c). n When considering proposals to construct new facilities or significantly modify existing facilities using processes that release chemicals listed in [Annex C], priority consideration should be given to alternative processes, techniques or practices that have similar usefulness but which avoid the formation and release of such chemicals (Annex C, Part V).

Dioxin formation There are three main mechanisms that generate and release dioxins: n Releases of dioxins present in the material being burned/ processed that are not destroyed by the combustion process; n Formation from precursors; n De novo synthesis from carbon, hydrogen, oxygen, and chlorine, the building blocks of dioxins. It occurs in the temperature window between 250°C and 500°C

Major factors influencing dioxin formation n The process feed (raw materials); n The process operating conditions (combustion quality); n The off-gas cooling conditions (residence time, critical temperature for de novo synthesis); n Memory effects (i.e. dust cumulated inside the ducts).

General primary measures Primary measures identified to prevent or minimize the formation of PCDD/F: n Feed material selection (sorting); n Feed material preparation (i.e. de-coating and de-oiling processes, stripping cable insulation, mixing, etc); n Stable and consistent process operations; n Effective process control to establish optimum operating conditions that minimize PCDD/F generation; n Continuous parameter monitoring to maintain optimum operating conditions.

General secondary measures Secondary measures capable to reduce PCDD/F releases n Efficient fume and gas collection; n High-efficiency dust removal equipment; n Post-combustion of the waste gas at a temperature above 850°C followed by a rapid quenching of the hot gases to temperatures of less than 250°C to avoid de novo synthesis; n Adsorption/absorption onto materials such as activated carbon in a fixed bed or moving bed reactor or by injection into the gas stream, and subsequent removal as filter dust.

Primary measures in the iron ore sintering process Specific primary measures identified to prevent or minimize the formation of PCDD/F during iron ore sintering: n Urea addition to suppress formation of PCDD/F; n Recirculation of off-gases.

Specific secondary measures capable to reduce PCDD/F releases from sinter plants: n Regenerative activated carbon (RAC) technology; n Fine wet scrubbing technology; n Selective catalytic oxidation. Secondary measures in the iron ore sintering process

Scrap processed in secondary steel facilities comes mainly from construction and demolition, automobiles, other vehicles, machinery and appliances. The process combusts impurities in scrap and can results in dioxin emission, especially when scrap is contaminated with paints, plastics, lubricants, and other organics including phenols, chlorinated plastics such as PVC and PCBs (e.g. from small capacitors in old appliances). Electric arc furnace steel-making process

Prevent the entry of contaminants into EAFs by changing material specifications and types of raw materials accepted (such as avoidance of oily scrap); Metal shredders should remove any small capacitors (that may contain PCBs) from electrical and electronic equipment prior to shredding; Certain measures that improve operational and energy efficiency appear also to reduce dioxin emissions; Avoid scrap pre-heating if post-combustion is not performed. Primary measures in the electric arc furnace steel-making process

Primary measures in secondary aluminum production Specific primary measures identified to prevent or minimize the formation of PCDD/F: n avoid hexachloroethane for the removal of magnesium from the melt. Hexachloroethane produces hexachlorobenzene (HCB). n Use of argon or nitrogen bubbling as degassing agents instead that chlorine is capable to attain similar or even superior technical efficiency and performance.

Considerable quantities of lead are recovered from scrap, in particular vehicle batteries. PCDD/F emissions may be linked to the use of PVC separators in vehicle batteries. Replacing PVC separators with non-chlorinated materials could aid in the reduction of PCDD/F emissions from secondary lead production, given that PVC is one of the main sources of chlorine in scrap. Secondary lead production

Implemented modifications: n chlorine input was reduced; n oily mill scale was not recycled; n inhibitors (urea) were added; n the process parameters were changed (the porosity of the sinter layer was increased); n activated carbon was injected in the gas stream. Yearly average emission concentrations: 1998 = 7.7 ng TEQ/Nm = 2.0 ng TEQ/Nm = 0.58 ng TEQ/Nm = 0.48 ng TEQ/Nm 3 Sidmar sinter plant, Belgium

Ilva sinter plant, Italy Yearly average emission concentrations: = 600 – 900 g TEQ/year (estimated) = ng TEQ/Nm 3 (150 g TEQ/year) 2009 = 2.5 ng TEQ/Nm 3 (50 g TEQ/year) 2010 = 0.4 ng TEQ/Nm 3 (50 g TEQ/year) Emission limit value: 0.4 ng TEQ/Nm 3 (1 January 2011)

Ilva sinter plant, Italy Addition of urea Injection of activated carbon

Badische Stahlwerke (BSW) in Germany Two electric arc furnaces, 1.8 million tons of steel per year Limiting values for permits 1991: 0.5 ng TEQ/Nm : 0.3 ng TEQ/Nm : 0.2 ng TEQ/Nm : 0.1 ng TEQ/Nm 3 These performance were obtained with: z stopping scrap preheating; z doing extensive development works on de-dusting system (succeeding to comply with a value of 1 mg/Nm 3 at 1.8 million Nm 3 /h); z installing a quenching system Yearly average emission concentrations 1986 ~ 2 ng TEQ/Nm < 0.1 ng TEQ/Nm 3

Global Forums are already established or will be established on all aspects of UNIDO's POPs related activities. The CEECCA Regional Forum on BAT/BEP is a voluntary regional collaboration and cooperation platform on BAT and BEP and is open to all countries of the CEECCA region - developed, developing and countries with economies in transition. The Forum objective is to serve as a platform for information dissemination and exchange of experiences among countries on different aspects of implementation of BAT and BEP and to promote strategies to reduce or eliminate unintentionally produced persistent organic pollutants (POPs) from industry. Central and Eastern Europe, Caucasus, and Central Asia (CEECCA) Regional Forum on BAT/BEP

Introduction of BAT and BEP methodologies to reduce or eliminate unintentionally produced POPs released from thermal processes in the metallurgical industry of the CEECCA Region. Armenia Czech Republic* Macedonia Romania* Serbia Tajikistan Turkey *Cooperating Countries (non-GEF eligible). Central and Eastern Europe, Caucasus, and Central Asia (CEECCA) Regional Forum on BAT/BEP UNIDO-GEF-CEECCA Countries Project:

Introduction of BAT and BEP methodologies to reduce or eliminate unintentionally produced POPs released from thermal processes in the metallurgical industry of the CEECCA Region The project will be based on five main components targeted to thermal processes in the metallurgical industry: Formulation of regional guidelines and guidance on BAT/BEP; Introduction of Pollution Prevention/Cleaner Production (PP/CP) strategies and BAT/BEP measures; Development of updated inventory reports of U-POPs releases; Development of human resources skilled on BAT and BEP; Strengthening the monitoring (sampling and analysis) capacity of national laboratories.

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