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