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ENVIRONMENTAL COMPANY OF SAO PAULO STATE – CETESB
REGIONAL CENTRE OF STOCKHOLM CONVENTION ON POPs FORLATIN AMERICA AND THE CARIBBEAN REGION
V INTERNATIONAL TRAINING PROGRAM ON ENVIRONMENTAL SOUND MANAGEMENT ON CHEMICALS AND WASTES, ESPECIALLY ON PERSISTENT
ORGANIC POLLUTANTS (POPs) AND MERCURY (Hg)
General Concepts Control Technologies and BAT/BEP- Hg
PhD Ing. Ligia Cristina Gonçalves de Siqueira
2016
Sao Paulo – SP – Brazil
Mercury collection
Primary: Hg mines or gold mines (as by-product)
Secondary: from waste (slag) generatingenvironmental pollution (air, water, soil)
MMA - Brazil
CONTROL IN GOLD MINESRetorts
Uses of Mercury- Production of inorganic compounds with metallic
mercury (mercury chloride (HgCl2), mercury chloride(Hg2Cl2) – purgative and anthelmintic, mercuryfulminate (Hg(CNO)2) – explosives detonator,mercuric sulfide (HgS) - pigment).
- Chlor-alkali production (mercury cells)- Battery production (mercury oxide)- Production of control and measurement instruments
(atmospheric pressure, temperature)- Production of electrical materials: lighting, wiring and
switches
CETESB
PRIMARY EMISSION SOURCES
- Combustion of coal and oil for generatingenergy and heat
- Production of iron and steel, cement and non-ferrous metals
- Waste incineration- Production and uses of mercury
USEPA
PRIMARY Hg EMISSION SOURCES - BRAZIL
SOURCES Emission (t/year) Emission (%)
Gold mine 20 29.7Chlor-alkali 17 25.2Steel and Iron 12 17.8Burnt in the Amazon 8.7 12.9
Pyrometallurgy 4.5 6.7
Generation of energy 4.2 6.2Other sources 1.0 1.5Total 67.4 100
Lacerda et al., 2007
Country Particulate matter control (+Hg)
Acid gas control (SO2) Total efficiency
USA Fabric filter - 32
Electrostatic precipitator - 42
USA + Canada
Fabric filter orElectrostatic precipitator
Wet desulfurization (FGD) 18 – 97
USA Fabric filter Spray dryer system (SDA) 23 – 83
Electrostatic precipitator Spray dryer system (SDA) 6 - 97
USA Fabric filter orElectrostatic precipitator
FGD or SDA > 50
USEPA
Combustion of coal and oil for generating energy and heat
Hg emissions through burning of Natural Gas - Brazil
SOURCES Emission (kg/year) Emission (%)Thermoelectric 38.5 88Industries 3.3 7.6Automotive 0.4 0.9Residential 0.09 0.2Commercial 0.04 0.1Others 1.4 3.2Total 43.7 100
Lacerda et al., 2007
Steel and iron production
Metallurgical coke
Coal or bituminous
charcoal
- Coal burning (indirect heating)
- Absence of air
Hg
Hg
Bag filter
Electrostatic precipitatoror
-Discharging-Cooling -Obliteration
Hg
Emissions Hg
Particulate Matter
USEPA
Cement productionDry system
RAW MATERIALS:
Clay
Limestone
Silicon
Iron
Aluminum
Cement Kiln
ClinkerMill Cement
Additives(Gypsum, others)
Clinker
CrudeMill
Fuels(Oil, coal)
WASTE
ControlDevice Dust collection
Emissions
Process
CO-PROCESSING
Hg
Hg
Hg Hg
Hg
Hg
Hg
Country Particulate matter control (+Hg)
Acid gas or Hg vapor control
Totalefficiency
USA Fabric filter - 50
Electrostatic precipitator (EP) - 25
USA + Canada
Fabric filter (FF) orElectrostatic precipitator (EP)
- -
Cement production
USEPA
Non-ferrous metal productionOre
Casting (Lead, Copper)
- Roasting- Smelting furnace- Converting
Sources
Particulate matter Acid gases (SO2)Vapors
Fabric filter orElectrostatic precipitator
Absorption
Emissions
Hg
HgHg
Hg
USEPA
Waste incineration
Type Country Particulate matter control
Hg vapor control
Total efficiency
MunicipalUSA
Fabric filter - -
Electrostatic precipitator - -
Washers - -
Temperature reduction - -
Canada, Japan and Europe
Fabric filter or Electrostatic precipitator
Injection of carbon or sodium sulfite
50 - 95
Medical USAWashers Absorbents -
Fabric filter orElectrostatic precipitator
Carbon injection -
Sludges USA Washers (Venturi or Venturi + impaction)
- -
USEPA
Chlor-alkali Industry
UNILINS
Best Available Tecnologies (BAT)
- Coal boilers- Casting- Cement kilns- Incinerators
- Bag filters-Electrostatic precipitator
Retention of particulate matter
(90 - 95%)
- Casting of steel and non-ferrous metals (lead, copper)
-Activated selenium filter (up to 90%)
-Washer with acid solution with activated selenium (90 - 95%)
Reduction of gaseous Hg
- Casting of non-ferrous metals
-Activated carbon filter (90%)-Absorption tower with lead sulfide beads (99%)
Reduction of gaseous Hg
- Chlor-alkali industry with mercury cells
-Substitution with membrane process
Reduction of gaseous Hg
USEPA
IMPORT AND EXPORT OF PRODUCTS CONTAINING MERCURY
Reduced use:• Banning of Hg• Don’t use Hg in key sectors (e.g. automobile industry).• Substitution of devices that does not contain Hg.
MMA
Waste containing Hg in sanitary landfills:• Hg emissions to atmosphere due to volatility.• Separation and treatment of compounds containing
mercury before final disposal.
Medical Area • Devices for medical use (thermometers)• Reagents, catalysts, preservatives (vaccines)• Dental amalgams (Hg-Ag)
• Actions:• Amalgam waste (Hg-AG):• Correct disposal in the environment• Replacement with new dental repair
techniques and materials (resins) MMA
Lamps - CETESB/SP Contaminated material
(lamp dust, thermometers, dental amalgams and coal)
Retort (high temperature,
low pressure)
Vapors
Activated carbon filter impregnated
with iodine
Hg
HgEmissions
Lamp breaker ("papa-lâmpada")
EmissionsCartridge filter
(polyester)
Hg
HgEmissions
Hg
Hg
Activated carbon impregnated with iodine
Washer with sodium sulfide
Control Practices
- Legislation:- Environmental standards (maximum acceptable
concentration for different means)- Regulation for control of sources- Control of mercury content in products
(pesticides, paper coating, drugs, cosmetics,etc.)
- Establishment of programs and standards (arearecovery, risk analysis, dealing with chemicalemergencies, etc.)
USEPA
Other practices- Processing (washing) of coal (reduction of sulfur and
mercury) or replacement (low sulfur content, use of naturalgas and oil, electricity)
- Separation or reduction of mercury content in waste forincineration
- Reduction of mercury content in batteries- Reduction of mercury content in electrical materials- Use of combustion systems with reduced temperature
(fluidized bed, low type combustors - NOx)- Use of desulfurization systems (acid gases SO2)- Product labeling (Hg free)
USEPA
REFERENCES- ASTSWMO. Association of State and Territorial. Solid Waste Management Officials. Fluorescent Drum-TopCrusher Survey Results. 2012.-Dias BJR, Almeida JRS. Some considerations on the historicity, characteristics, uses and applicationsof mercury metal. Available at URL: <http: //www.webartigos.com/artigos/algumas-considerações-acerca...>.- CETESB. Mercury. Available at: http://www.cetesb.sp.gov.br /userfiles/ file/ laboratorios/ fit/ mercurio.pdf- European Commission. Integrated Pollution Prevention and Control. Reference Document on BestAvailable Techniques in the Chlorine and Alkali Industry. Available at: http://www.netcentro.pt/upl/%7BC16F5627-71C0-486E-B6DA-DB38DAFE1CBD%7D.pdf- Lacerda LD, Santos AF, Marins RV. Emission of Mercury into the atmosphere through natural gasburning in Brazil. Química Nova, vol. 30, no. 2, 2007.- MMA. Ministry of the Environment. Mercury. Available at: http://www.mma.gov.br/ seguranca-quimica/mercurio.
- The Chlorine Institute. Guidelines for mercury cell chlor alkali plants emission control: practices andtechniques. Available at: http://www.epa.gov/region5 /mercury/pdfs/hgcontrolguidancedocument-final.pdf
- UNILINS. Chlorine and alkali industry. Industrial Inorganic Chemistry - Lesson 4. Available at:ftp://ftp.unilins.edu.br/renato.mariano/QU%CDMICA%20INDUSTRIAL%20-%20I/Aula% 20-09/Industria%20de%20Cloro%20e%20%C1lcalis.pdf
- USEPA. Environmental Protection Agency. Position paper on mercury. Chap. 7. Practical opportunities andtechnologies available to reduce anthropogenic emissions of mercury to the environment.- Images: Internet
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