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Page 1 21/06/2016
Monitoreo y Redución de Emisiones de Mercurio “Capacitación para mejorar la calidad del aire”
Lima, Peru 21 de Junio 2016
Recycling and/or Alternatives
for Mercury
Prof. Dr. Florian Schindler Consultor GIZ, Universidad de Ciencias Aplicadas, Berlín
Dr. Sandra Bräutigam Consultora GIZ, Universidad de Ciencias Aplicadas, Berlín
Julika Tribukait (GIZ) Sector Project Environmental Policy and Sustainable Development Bonn, Germany
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Reciclaje y Alternativas para el uso de Mercurio
Procesos y productos usando grandes cantidades de Mercurio
Technologías de reciclaje y ejemplos prácticos de los EE.UU. y de Europa
Guias para a el Convenio de Minamata sobre Mercurio
Perspectivas Futuras
Agenda
Das Bild kann zurzeit nicht angezeigt werden.
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Figure 1: Global mercury events timeline A [1]
[1] http://www.unep.org/PDF/PressReleases/Mercury_TimeToAct_hires.pdf , on 17.03.2015
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Products containing Mercury Governments have agreed on a range of mercury containing products whose production, export and import will be phase-out by 2020. 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
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Figure 2: In- and Output of Mercury in industrial processes from GRID-Arendal [1]
[1] http://www.grida.no/graphicslib/detail/industrial-processes-input-and-output-of-mercury_84ee
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Processes involing Mercury
Figure 3 Mercury emissions in 2010 [1]
[1] http://mercurypolicy.scripts.mit.edu/blog/wp-content/uploads/2013/01/2013UNEPemissions.jpg on 28.03.2015
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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 (Hg2Cl2/ 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: chemical- pharmaceutical processes, paints, pigments
Catalysts for polyurethane production, fungicide in water-based latex paints, Vermilion (brilliant red) pigment, and other polymer production
Less than 100 tonnes per year
Rare earth metal catalysts, pigments
Table 1: Top ten usages/applications involving mercury
*World Estimate of Mercury Use in Artisanal and Small - Scale Gold Mining for 2011, Kevin Telmer, Artisanal Gold Council,October 2011, INC3, Nairobi Ref. http://www.unep.org/chemicalsandwaste/Portals/9/Mercury/Documents/INC3/Tech%20session/4.%20Telmer%20INC3%20Nairobi%20ASGM%20Hg%20use%20and%20trends_oct30.pdf
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Artisanal Gold-Mining (ASGM)
Figure 4: Child labour in ASGM in Africa[1] [1] Pulitzer Centre: http://pulitzercenter.org/reporting/burkina-faso-gold-mines-child-labor-exploitation-poverty-migration-larry-price-gold-rush-ILO
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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
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Figure 9: Small Scale Jewellery on Lombok island
Figure Indonesia 8: Top 10 Worst Pollution Problems (Blacksmith Institute)[1]
[1] http://www.worstpolluted.org/projects_reports/display/56 on 11.04.2015
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Alternative Techniques in mercury-free ASGM Available alternative methods are demonstrated in the following Guide:
Figure 10: UNEP - ASGM Guide [1] [1] Ref. UNEP - http://www.unep.org/hazardoussubstances/Portals/9/Mercury/Documents/ASGM/Techdoc/UNEP%20Tech%20Doc%20APRIL%202012_120608b_web.pdf
Last visited on 29.09.2015
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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:
http://www.matthey.com/innovation/innovation_in_action/vcm-catalyst on 10.10.2015
http://www.datenna.com/2014/05/08/mercury-free-nano-carbon-catalyst-for-pvc-production/ on 10.10.2015
http://chemchina.com.cn/en/xwymt/jtxw/webinfo/2013/11/1387235727080514.htm on 10.10.2015
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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. http://ludens.cl/Electron/mercreg/mercreg.html on 01.10.2015
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Chlor-Alkali Industry and Recycling of Mercury Mercury is applied in the chlor-alkali industry where mercury-containing electrolytic cells are used in the production of chlorine and caustic soda.
[1] Source: Mercury Flows and safe storage of surplus mercury, EU-Directorate General for Environment, http://ec.europa.eu/environment/chemicals/mercury/pdf/hg_flows_safe_storage.pdf
Table 2: Global Recycling of mercury by the Chlor-Alkali Industry[1]
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Fig. 11 Chlor-Alkali Hg –Electrolysis with Mercury Electrode
Fig. 12 Chlor Alkali Membrane Electrolysis
Ref. www.uhdenora.com web-page
Ref. www.ec.gc.ca 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.
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Alternatives to Mercury in Industry
Figure 14 : EU –BREF Publication on Mercury and Industry[2]
Figure 13: UNEP, Publication on Mercury and Industry[1]
[1] http://www.unep.org/chemicalsandwaste/Portals/9/Mercury/AwarenessPack/English/UNEP_Mod2_UK_Web.pdf [2] http://eippcb.jrc.ec.europa.eu/reference/BREF/CAK_BREF_102014.pdf
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Dental Amalgam
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. https://youtu.be/vsT5xSBa4Jc?t=200 on 10.10.2015
Fig. 15 Mercury based fillings
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Cremation of Dead Bodies Another source of air pollution can be the cremation (burning) of dead bodies. Either the mercury has to be removed prior to the cremation or the cremator exhaust should be fitted with air filter equipment that removes mercury.
Zero-mercury campaign [1]
Most crematoria around the world still have no controls on emissions, In the Netherlands, the number of fillings is expected to increase from 3.2 to 5.1 during the period 1995-2020.
In the UK it has been calculated that by 2020 crematoria will be by far the largest single contributor to mercury emissions (just over 25% of the UK mercury emissions to air) unless action is taken.
[1] Ref. http://www.zeromercury.org/index.php?option=com_content&view=article&id=211&Itemid=99 on 10.11.2015
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Alternatives to Mercury Measuring Devices
Ref. http://www.newmoa.org/prevention/mercury/imerc/FactSheets/measuring_devices.cfm on 10.10.2015
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 Non-Mercury Alternative(s) Barometer Aneroid, digital, eco-celli liquid-gas silicon Flow Meter Digital, ball-actuated Hydrometer Lead ballast hydrometers Hygrometer Spirit-filled glass bulb, digital, aneroid
Manometer U-shaped tubes using any colored liquid, digital
Pyrometer Optical, digital Psychrometer Spirit-filled glass bulb, digital Sphygmomanometer Aneroid, digital
Thermometer Alcohol or mineral spirit-filled glass bulb, digital
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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), 2014 http://www.newmoa.org/prevention/mercury/imerc/factsheets/switches_relays_2014.pdf on 17.11.2015
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Mercury Tilt Switches
The characteristics of mercury tilt switch thermostats and potential mercury-free alternatives are summarized in the following table:
Table 4: Mercury switches and its alternatives[1]
Ref. [1] US EPA, May 1994, Study, Risk Reduction Engineering Laboratory, Cincinnati
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Alternatives to Mercury
Table 5: Alternatives to Mercury – Added Switches & Relays
For more information on non-mercury alternatives for switches and relays, see a source from 2003: http://sustainableproduction.org/downloads/An%20Investigation%20Hg.pdf
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Figure 17: Lamp recycling plant [1] [1] Source: http://www.illuminate-project.com/methodology on 28.02.2015
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Compact Fluorescent Lamps (CFL) Recycling
Figure 18: CFL Compact Fluorescent Lamps[1]
[1] Deutsche Welle (DW), Germany’s international broadcaster, http://www.dw.de/popups/popup_gallery/de_quecksilber.html
cleaned glass will be sold back to manufacturers
Figure 20: Glass residue, [1]
Figure 19: Lamp coating material[2]
The remaining white sludge contains mercury, fine glass practices and precious rare earth elements such as Ytrium and Europium.
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Mercury Recycling plant in Germany
Figure 22: Rotary kiln for sludge treatment [2]
[2] DELA company in Dorsten, Germany Foto: DW F. Schmidt, Deutsch Welle, DW German broadcast, http://www.dw.de/quecksilber-sicher-endlagern/a-15949000 on 26.02.2015
Figure 21: Mercury sulphide containing sludge[1]
[1] Source: DW F. Schmidt in Deutsch Welle, DW German broadcast, http://www.dw.de/quecksilber-sicher-endlagern/a-15949000 on 26.02.2015
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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 Option for Mercury Wastes p.51 ff
Convención de Minamata
Ref. [1] http://www.unep.org/chemicalsandwaste/Mercury/ReportsandPublications/tabid/3593/Default.aspx
Figure 23: Rovery of Mercury
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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
Vinyl-chloride monomer (VCM) production using catalysts (Hg2Cl2/ 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: chemical- pharmaceutical processes, paints, pigments
Catalysts for polyurethane production, fungicide in water-based latex paints, Vermilion (brilliant red) pigment, and other polymer production
Less than 100 tonnes per year
Rare earth metal catalysts, pigments
Table 5 (1a)
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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: “Guide to the new Mercury Treaty
(4/2013)” &
“An NGO Introduction to Mercury Pollution and the Minamata
Convention on Mercury (4/2014)” [2]
Figure 24: IPEN Guides [1]
Ref. [1] http://www.ipen.org/news/new-guide-mercury-pollution-and-minamata-convention-mercury on 28.05.2016 [2] http://www.ipen.org/documents/ngo-introduction-mercury-pollution-and-minamata-convention-mercury on 28.05.2016
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Prespectivas Futuras: Preparation of National Implementation Plans (NIPs)
Ref: [1] 2014, March, 31, Draft - Guidance for Developing, a National Implementation Plan for the Stockholm Convention on Persistent Organic Pollutants, (updated in 2012 to include the POPs listed in 2011 and 2009)
In order to benefit from the synergies among the Stockholm Convention and the Minamata convention the following guidance should be used for the preparation of a National Implementation Plan (NIP). The guidance is referring to persistent organic pollutants (POPs) but its methodology could be applied on mercury as well:
Figure 25: NIP for POPs [1]
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Prespectivas Futuras -
Ref: [1] http://www.unep.org/chemicalsandwaste/SpecialProgramme/SpecialProgrammeCallsforProposals/tabid/1061027/Default.aspx on 30.05.2016
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 2016. 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]
Proyectos:
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Contacto:
Prof. Dr. F. Schindler (PhD) Letzkauer Steig 14, 13503 Berlin
Alemania Tel. +49 (0) 30 322 99 363 Fax +49 (0) 30 55 52 61 24 Movil +49 (0)151 1462 98 50
e-Mail: [email protected]
web: www.beuth-hochschule.de/fsi Get a personal impression from us!
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