S³C 2nd Summer School on Sustainable Chemistry for Sustainable Development Value chains and the example of textiles

Transcription

1 S³C 2nd Summer School on Sustainable Chemistry for Sustainable Development Value chains and the example of textiles 12th September 16th September 2016 at Leuphana University, Lüneburg Phasing out the usage of mercury, the international Convention on Mercury (Minamata) and alternatives for a sustainable replacement of mercury Prof. Dr. Florian Schindler Consultant GIZ, University of Applied Sciences, Berlin Julika Tribukait (GIZ) Sector Project Environmental Policy and Sustainable Development Bonn, Germany 20/06/2016 Page 1

2 Agenda Minamata convention Important Facts about Mercury Mercury Emissions and Mercury in the Food Chain Production of Mercury and Gobal Mercury Flows Recycling / Alternatives for Mercury Processes and products involving larger quanities of Mercury Recycling technologies and examples in Europe and the US Future perspectives / Further reading / Literature 20/06/2016 Page 2

3 Contenido The treaty was agreed at the fifth session of the Intergovernmental Negotiating Committee (INC) in Geneva, Switzerland 19 January Figure 1: International- MINAMATA Convention The text was adopted and opened for signature at the Conference of Plenipotentiaries held in Minamata and Kumamoto, Japan, from 9 to 11 October [1] Latest ratifications: Ecuador in July 2016 and China in August as No. 30 [1] last visited on /06/2016 Page 3

4 Minamata Convention The Convention entered into force following the ratification by more than 50 countries. Figure 2: Overview of Countries that have signed or ratified the Minamata convention [2] [2] on /06/2016 Page 4

5 Facts about Mercury Mercury is a silver-white coloured (shining) transition metal. What makes mercury unique is the fact that it is liquid at room temperature. It has a shiny appearance on its surface and in combination with its colour it is commonly known as quicksilver: Figure 4: Liquid Mercury flow at room temperature [1]. Name: Hydrargyrum [2] Hg Mw = g/mol [1] and [2] Source: 1 Fotolia or pls. see also under Deutsche Welle (DW), Germany s international broadcaster, on /06/2016 Page 5

6 Figure 3: Periodic Table of Elements with mercury (marked in blue) Source: on /06/2016 Page 6

7 The melting point of Mercury at C and boiling point of C are exceptionally low for a metal. 20/06/2016 Misión de Evaluación del Programa 4E Page 7

8 Toxicity of Mercury In spite of its beautiful appearance mercury is a toxic metal. Elemental mercury evaporates at room temperature and the vapours highly toxic and can cause both chronic and acute poisoning. Figure 5: Mucous membranes in the lung [1] [1] Source: on /06/2016 Page 8

9 Mercury compounds are often accumulated in the food chain an effect which is called bio-accumulation or bio-magnification. Figure 6: Mercury in the food chain [1] [1] Source: on /06/2016 Page 9

10 Minamata, Japan was the place where the production of acetaldehyde using a mercury catalyst started in May The discharged wastewater went into the bay. Minamata Disease - discovered in Minamata Japan, Cause: release of CH 3 Hg in industrial wastewater by chemical factory - Highly toxic methyl-mercury bioaccumulated in fish and shellfish Figure 7: Crippled hand of a Minamata disease victim - The fish eaten by the local populace, resulted in mercury poisoning. Film under : eo/tabid/3455/default.aspx [1] Source: W. Eugene Smith in Wikipedia - on /06/2016 Page 10

11 The atmosphere in industrialised countries is often contaminated with mercury vapours: Figure 8: Anthropogenic Mercury Emissions [1] [1] Source: 2013, January, UNEP, Global Mercury Assessment, Sources, Emissions, Re leases, and Environmental Transport, Division of Technology, Industry and Economics (DTIE), Chemicals Branch, p /06/2016 Page 11

12 Figure 9: Mercury Emissions worldwide visualised [1] [1] Source: Artic Monitoring and Assessment Programme (AMAP) website last visited on /06/2016 Page 12

13 In nature mercury is found soft, red to reddish brown ores known as cinnabar : Cinnabar is composed of mercury and sulphur represented by the chemical formula of mercury sulphide HgS All chemical compounds of HgS and they are insoluble in water. Other mercury ores / minerals include corderoite (Hg 3 S 2 Cl 2 ), livingstonite (HgSb 4 S 8 ), montroydite (HgO), and calomel (HgCl). Figure 10: Mercury ore = Cinnabar [1] [1] Source: Natural Pigments website on /06/2016 Page 13

14 Supply and Trade of Mercury worldwide Figure 12: Schematic Mercury Trade Flow Map [1] The Data collection is from 2007, prior to the export bans in the European Union (2011) and the USA (2013). [1] Ref. on /06/2016 Page 14

15 Products containing Mercury Governments have agreed on a range of mercury containing products whose production, export and import will be phase-out by These include: Batteries, except for 'button cell' batteries Medical measurement devices (thermometers and blood pressure devices) Switches and relays Energy saving lamps such as compact fluorescent lamps (CFLs) Mercury in cold cathode fluorescent lamps and external electrode fluorescent lamps Dental Fillings Soaps and cosmetics Page 15

16 Processes involving Mercury Figure 3 Mercury emissions in 2010 [1] [1] on Page 16

17 Figure 2: In- and Output of Mercury in industrial processes from GRID-Arendal [1] [1] Page 17

18 Convención de Minamata Page 18

19 Table 1: Top ten usages/applications involving mercury Rank Application field Mercury containing Product (form of mercury) To / worldwide Alternative 1 Gold processing in Artisanal Small Scale Gold Mining (ASGM) Amalgamation (binding) of gold (elemental Hg liquid mercury) 1,465 tonnes/year (2011) * Hg- free technologies such as panning centrifuging, sluicing, shaking tables, spiral concentrators 2 Chemical industry plastic/polymer PVC Vinyl-chloride monomer (VCM) production using catalysts (Hg 2 Cl 2 / C catalyst) and hydrochloric acid (HCl), coal based process using acetylene 875 tons per year (2005) Manufacturing VCM from ethylene by direct chlorination and oxy-chlorination method or new (gold) catalysts 3 Chlor-alkali electrolysis in the Chemical Industry Mercury used as electrolysis cathode, (elemental liquid, conductive Hg mercury) 625 tonnes per year (2005) Polymer - Membrane Electrolysers i.e. membrane based (mercury- free) electrolysis 4 Batteries, primary / button cells Non rechargeable electrochemical DC battery, (mercuric oxide HgO) 542 tonnes per year (2005) Silveroxide, zinc-air or carbon or alkaline based batteries as well as lithium based ones 5 Dental amalgam to fill cavities in teeth Dental amalgam filling material composed of often more than 50 % elemental Hg (liquid mercury) mixed with silver, tin and copper 333 tons per year (2005) Prevention of fillings, ceramic or resin based / polymer fillings 6 Electrical and electronic Industry, automotive Electrical (tilt) switches, relays, acceleration, fire/flame sensors, thermostats, float switches (elemental liquid, conductive Hg mercury) 292 tons per year (2005) Electronic switches, air-controlled, reed switch, vapour-filled diaphragm, snap-switch, digital thermostats 7 Pressure and temperature measurement devices; other measuring instrumentation Thermometers, barometers (blood pressure) medical devices hospital equipment such as sphygmomanometers (elemental liquid, Hg) 292 tonnes per year (2005) Electronic devices, aneroid sphygmomanometers, oscillometric devices, infrared-thermo- and digital hygrometers 8 Lighting devices high intensity discharge (HID) mercury vapour lamps Mercury vapour lamps (mercury vapour), compact (CFK) fluorescent lamps, (Hg vapour), compact fluorescent lamps (CFLs) 166 tonnes per year (2005) Metal Halide (metallic zinc), high pressure sodium vapour as well as xenon (HID) lamps or light emitting diodes (LEDs) 9 Liquid crystal displays (LCDs), scanners cold cathode fluorescent lamps (CCFLs) in back-light screens Less than 100 tonnes per year Light emitting diodes (LED) based screens or in future organic light emitting diodes (OLEDs) 10 Other applications: chemicalpharmaceutical processes, paints, pigments Catalysts for polyurethane production, fungicide in waterbased latex paints, Vermilion (brilliant red) pigment, and other polymer production Less than 100 tonnes per year Rare earth metal catalysts, pigments *World Estimate of Mercury Use in Artisanal and Small - Scale Gold Mining for 2011, Kevin Telmer, Artisanal Gold Council,October 2011, INC3, Nairobi Ref. Page 19

20 No Application field Mercury containing Product To / worldwide Alternative 1 Gold processing in Artisanal Small Scale Gold Mining (ASGM) Amalgamation (binding) of gold (elemental Hg liquid mercury) 1,465 tonnes/year (2011) Hg- free technologies such as panning centrifuging, sluicing, shaking tables, spiral concentrators 2 Chemical industry plastic/polymer PVC 3 Chlor-alkali electrolysis in the Chemical Industry 4 Batteries, primary / button cells 5 Dental amalgam to fill cavities in teeth 6 Electrical and electronic Industry, automotive 7 Pressure and temperature measurement devices; other measuring instrumentation Vinyl-chloride monomer (VCM) production using catalysts (Hg 2 Cl 2 / C catalyst) and hydrochloric acid (HCl), coal based process using acetylene Mercury used as electrolysis cathode, (elemental liquid, conductive Hg mercury) Non rechargeable electrochemical DC battery, (mercuric oxide HgO) Dental amalgam filling material composed of often more than 50 % elemental Hg (liquid mercury) mixed with silver, tin and copper Electrical (tilt) switches, relays, acceleration, fire/flame sensors, thermostats, float switches (elemental liquid, conductive Hg mercury) Thermometers, barometers (blood pressure) medical devices hospital equipment such as sphygmomanometers (elemental liquid, Hg) 875 tons per year (2005) 625 tonnes per year (2005) 542 tonnes per year (2005) 333 tons per year (2005) 292 tons per year (2005) 292 tonnes per year (2005) Manufacturing VCM from ethylene by direct chlorination and oxy-chlorination method or new (gold) catalysts Polymer - Membrane Electrolysers i.e. membrane based (mercury- free) electrolysis Silveroxide, zinc-air or carbon or alkaline based batteries as well as lithium based ones Prevention of fillings, ceramic or resin based / polymer fillings Electronic switches, air-controlled, reed switch, vapour-filled diaphragm, snapswitch, digital thermostats Electronic devices, aneroid sphygmomanometers, oscillometric devices, infrared-thermo- and digital hygrometers 8 Lighting devices high intensity discharge (HID) mercury vapour lamps Mercury vapour lamps (mercury vapour), compact (CFK) fluorescent lamps, (Hg vapour), compact fluorescent lamps (CFLs) 166 tonnes per year (2005) Metal Halide (metallic zinc), high pressure sodium vapour as well as xenon (HID) lamps or light emitting diodes (LEDs) 9 Liquid crystal displays (LCDs), scanners 10 Other applications: chemical- pharmaceutical processes, paints, pigments cold cathode fluorescent lamps (CCFLs) in back-light screens Catalysts for polyurethane production, fungicide in water-based latex paints, Vermilion (brilliant red) pigment, and other polymer production Less than 100 tonnes per year Less than 100 tonnes per year Light emitting diodes (LED) based screens or in future organic light emitting diodes (OLEDs) Rare earth metal catalysts, pigments Table 5 (1a) Page 20

21 Artisanal Gold-Mining (ASGM) Figure 4: Child labour in ASGM in Africa [1] [1] Pulitzer Centre: Page 21

22 The Amalgamation Method Figures 5,6,7: Gold extraction from mercury amalgam [1] [1] Schindler Florian, 2012, Gold extraction with mercury, GIZ-Green Economy Mission Lombok Island, Indonesia Page 22

23 Figure 9: Small Scale Jewellery on Lombok island Figure 8: Indonesia -Top 10 Worst Pollution Problems (Blacksmith Institute) [1] [1] on Page 23

24 Vinyl Chloride Monomer (VCM) production The alternatives address the need for the implementation of mercury free catalyst in the VCM industry. After 2017 new VCM plants will not be allowed to use a mercury catalyst and after 2022 all VCM plants have to use mercury-free catalysts providing there is an economically available alternative. Economically viable solutions for China and other countries still applying the mercury based catalyst are on the verge and some chemical companies and/or research organisations: on on on Page 24

25 Mercury batteries and their replacement Mercury oxide, silver oxide, and button cell batteries are the most common batteries containing mercury. They were commonly used in small electrical devices such as watches, photo-cameras, calculators or in hearing aids. Batteries generally contain between 5 and 25 milligrams of mercury Alternatives for the mercury containing batteries are: zinc-air batteries (high capacity, but need to be activated before) + short life time rechargeable batteries (high initial costs but good cost recovery) silver-oxide batteries (flat voltage of 1.58 volts and long lifetime) alternative batteries may contain silver, nickel, cadmium, lithium, lead, zinc, manganese, potassium and alkalines. Manufactures offer replacements based on alkaline cells for the mercury batteries, but one must be careful with the applications since the voltage often varies. Ref. on Page 25

26 Convención de Minamata Page 26

27 Fig. 11 Chlor-Alkali Hg Electrolysis with Mercury Electrode Fig. 12 Chlor Alkali Membrane Electrolysis Ref. Web-page Alternatives for the electrolysis using mercury as a cathode is the membrane electrolysis technology. Mercury-processing technology is being phased out in the Chlor-Alkali industry all over the world. Ref. web-page Page 27

28 Dental Amalgam Fig. 15 Mercury based fillings Mercury based fillings are very cost effective and easy to apply. In any case amalgam traps in order to prevent mercury releases with the waste streams have to be used. Alternative plastic and/or ceramic fillings should be used in dental practice centres. Ref. on Page 28

29 Alternatives to Mercury Measuring Devices There are non-mercury alternatives hat may be suitable for replacing the traditional mercury-added measuring devices. Table 3: Alternatives to Mercury Measuring Devices Component or Product Barometer Flow Meter Hydrometer Hygrometer Manometer Pyrometer Psychrometer Sphygmomanometer Thermometer Non-Mercury Alternative(s) Aneroid, digital, eco-celli liquid-gas silicon Digital, ball-actuated Lead ballast hydrometers Spirit-filled glass bulb, digital, aneroid U-shaped tubes using any colored liquid, digital Optical, digital Spirit-filled glass bulb, digital Aneroid, digital Alcohol or mineral spirit-filled glass bulb, digital Ref. on Page 29

30 Mercury use in switches and relays Mercury switches and relays sold in the U.S. during 2001 till 2010 The data also indicates that the largest amount of mercury reported was used in tilt switches, followed by float switches (used in pumps and pump systems).[1] Figure 16: Switches and relays containing mercury Ref. [1] NEWMOA (an US interstate association), on Page 30

31 Convención de Minamata Page 31

32 Figure 17: Lamp recycling plant [1] [1] Source: on Page 32

33 Compact Fluorescent Lamps (CFL) Recycling The remaining white sludge contains mercury, fine glass practices and precious rare earth elements such as Ytrium and Europium. Figure 18: CFL Compact Fluorescent Lamps [1] Figure 19: Lamp coating material [1] Figure 20: Glass residue, [1] cleaned glass will be sold back to manufacturers [1] Deutsche Welle (DW), Germany s international broadcaster, Page 33

34 Mercury Recycling plant in Germany Figure 21: Mercury sulphide containing sludge [1] Figure 22: Rotary kiln for sludge treatment [2] [1] Source: DW F. Schmidt in Deutsch Welle, DW German broadcast, on [2] DELA company in Dorsten, Germany Foto: DW F. Schmidt, Deutsch Welle, DW German broadcast, on Page 34

35 Recovery of Mercury For the recovery of mercury some more case studies can be found in the Practical Sourcebook on Mercury Waste Storage and Disposal 2015 [1] Chapter 4 Recovery Options for Mercury Wastes p.51 ff Figure 23: Recovery of Mercury Ref. [1] Convención de Minamata Page 35

36 Recent Developments / Projects: The Special Programme is calling developing countries and countries with economies in transition to submit projects proposals for funding between USD $50,000 to $250,000. The deadline for applications is 4 July The Special Programme aims to strengthen national institutions and to promote the mainstreaming of the sound management of chemicals and waste. Key activities supported by the programme provide countries to advance institutional capacity for the implementation of the Basel, Rotterdam and Stockholm Conventions, the Minamata Convention and SAICM. Figure 26: Projects for Hg [1] Ref: [1] on Page 36

37 More Information: Ref. ebooks/mercury- Acting-Now#1 To learn more from UNEP, please visit Ref. l ast visited on /06/2016 Convención de Minamata Page 37

38 Guides for the Mercury Treaty issued by the heavy metals working group of the International POPs Elimination Network (IPEN) published two interesting guides which can be referred to: Figure 24: IPEN Guides [1] Guide to the new Mercury Treaty (4/2013) & An NGO Introduction to Mercury Pollution and the Minamata Convention on Mercury (4/2014) [2] Ref. [1] on [2] on Page 38

39 Contact: Prof. Dr. F. Schindler (PhD) Letzkauer Steig 14, Berlin Germany Tel. +49 (0) Fax +49 (0) Movil +49 (0) web: Get a personal impression from us! Page 39