PCDD/PCDFs AND MERCURY IN POWER AND HEATING GENERATION SECTOR

ANDREA SBRILLI UNIDO CONSULTANT

ESEA FORUM NATIONAL AWARENESS WORKSHOP FOR DEMONSTRATION OF BAT/BEP IN FOSSIL FUEL-FIRED UTILITIES AND INDUSTRIAL BOILERS ON PERSISTENT ORGANIC POLLUTANTS (POPS) BANGKOK, THAILAND 13 JUNE 2011

UNINTENTIONAL POPs AND MERCURY EMITTED DURING BURNING PROCESS

INDUSTRIAL AND NON INDUSTRIAL BURNING PROCESSES CAN BE THE EMISSION SOURCES OF: UNINTENTIONAL PRODUCED PERSISTANT ORGANIC POLLUTANTS UP-POPs DIOXINS AND FURANS (PCDD/PCDF)

POLICHLOROBIPHENYLS (PCBs)
HEXACHLOROBENZENE (HCB)

AND
MERCURY

MAIN FACTORS AFFECTING UP-POPs FORMATION AND EMISSION IN THERMAL PROCESSES

CHORINE INPUT WITH FUEL (FOSSIL OR BIOMASS)

FORMATION DURING BURNING PROCESS VIA OMOGENUOUS AND HETEROGENUOS PHASE REFORMATION DURING GAS COOLING IN THE HEAT EXCHANGER ZONE REFORMATION IN THE DUST FILTERS

RELEASE FROM SCRUBBERS (DRY AND WET)

POWER PLANTS AND INDUSTRIAL BOILERS

LARGE, FOSSIL FUEL-FIRED POWER PLANTS ARE WELL-CONTROLLED, THE COMBUSTION EFFICIENCY IS USUALLY HIGH, THE PROCESS IS STABLE AND THE FUELS USED ARE GENERALLY HOMOGENEOUS THE CONCENTRATION OF PCDD/PCDFSSs IN THE EMISSIONS ARE LOW, BUT MASS EMISSIONS ARE HUGE DUE TO LARGE VOLUMES OF FLUE GASES EMITTED SMALLER INDUSTRIAL PLANTS ARE LESS WELL CONTROLLED EMISSIONS OF PCDD/PCDFs ARE AT HIGHER CONCENTRATIONS BUT WITH AT LOWER MASS EMISSION DUE TO LOWER VOLUMES OF FLUE GASES EMITTED

INFLUENCE OF FUEL
FOSSIL FUELS AND WASTE DERIVED FUELS
FOSSIL FUELS COMBUSTION IN UTILITY OR INDUSTRIAL BOILERS GENERATE MUCH LESS PCDD/PCDFs THAN COMBUSTION OF WASTE-DERIVED FUELS

IN COAL (SULPHUR TO-CHLORINE RATIO 5:1), THE SURPLUS OF SULPHUR ENABLES THE CAPTURE OF THE MOLECULAR CHLORINE, THUS PREVENTING THE FORMATION OF CHLORINATED COMPOUNDS

IN THE COMBUSTION OF WASTE-DERIVED FUELS, CHLORINE DOMINATES OVER SULPHUR AND PCDD/PCDFs FORMATION IS PROMOTED

INFLUENCE OF FUEL
RESIDUALS AND DISTILLATE OILS HEAVY FUEL OIL MAY CONTAIN SIGNIFICANT QUANTITIES OF ASH, NITROGEN, AND SULFUR HOWEVER, THEY GENERALLY RESULT IN LOW LEVELS OF ORGANIC EMISSIONS

LIGHT FUEL OIL AND NATURAL GAS GENERATE LOW AMOUNTS OF PCDD/PCDFs BOTH ARE VERY HIGH CALORIFIC, CLEAN BURNING FUELS WITH LITTLE CONTENT OF ASHES

ONLY IF LIQUID OR SLUDGE WASTE IS CO-FIRED HIGHER CONCENTRATIONS OF PCDD/PCDFs MAY BE FOUND

USE OF BIOMASSES
THE COMBUSTION OF SOME OF THEM INCREASES FOULING OF SURFACES OF BOILERS

DUE TO THE GREAT INPUT OF MINERAL MATTER AND CHLORINE THERE IS AN INCREASE IN EMISSIONS OF DUST, HYDROGEN CHLORIDE AND PCDD/PCDFs

INFLUENCE OF FUEL BIOMASSES

POPs ARE FORMED IN WOOD COMBUSTION PRECURSORS SUCH AS PHENOLS AND LIGNIN, PARTICULATE CARBON AND CHLORINE.

HIGH EMISSION LEVELS CAN BE EXPECTED FROM BURNING TREATED WOOD THAT CONTAIN CONTAMINANTS (CHROMATED COPPER ARSENATE, PENTACHLOROPHENOL, CREOSOTE, ADHESIVES, RESINS,PAINT AND OTHER SURFACE COATINGS)

THESE MATERIALS CAN PROMOTE THE FORMATION OF PCDD/PCDFs DURING COMBUSTION

INFLUENCE OF CHLORINE

THE CHLORINE CONTENT OF UNTREATED WOOD IS USUALLY BETWEEN 0.001 AND 0.01 % BY WEIGHT. IN BARK IS HIGHER , 0.01 TO 0.02%

DEPENDING ON THE LOCATION, EVEN HIGHER CHLORINE CONTENTS CAN BE FOUND IN UNTREATED WOOD AND BARKS.

SIGNIFICANTLY HIGHER VALUES CAN BE FOUND IN WOOD MATERIALS CONTAINING PLASTICS (PVC)

MAX. CONCENTRATION PERMITTED 0.1 ng ITEQ/m3

FLY ASH FROM BIOMASS COMBUSTION HAS TO BE LANDFILLED DUE TO ITS HIGH HEAVY METAL CONTENT.

COMBUSTION OF CONTAMINATED WOOD SHOULD BE LIMITED TO INCINERATION PLANTS WITH EFFICIENT EMISSION CONTROL SYSTEMS

DIOXINS AND FURANS EMISSION FACTORS FOR FOSSIL FUELS AND BIOMASS BURNING

UNEP TOOLKIT

IT IS EVIDENT THAT THE TYPE OF PLANT AND TYPE OF EMISSIONS CONTROL DEVICES ARE NOT CONSIDERED

12

DIOXINS AND FURANS EMISSION FACTORS FOR BIOMASS POWER PLANTS

LITERATURE DATA EMISSION FACTORS (EF) IN INDUSTRIAL COAL FIRED BOILERS

FLUIDIZED BED BOILER FIRED WITH COAL (OLD) EF = 100-300 g TEQ/TJ

FLUIDIZED BED BOILER FIRED WITH COAL (NEW) EF = 1 g TEQ/TJ

10% ADDITION OF BIOMASS TO COAL AS FUEL CAN INCREASETHE EMISSION FACTOR (EF) ABOUT 10 TIMES

CO-COMBUSTION OF COAL AND WASTES GIVES VERY HIGH EMISSION FACTORS

LITERATURE DATA EMISSION FACTORS (EF) IN INDUSTRIAL WOOD FIRED BOILERS

INDUSTRIAL BOILERS FIRED WITH WOOD (WITHOUT BARK) EF = 1,600 g TEQ/TJ INDUSTRIAL BOILERS FIRED WITH WOOD (WITH BARK) EF = ABOUT 10 TIMES HIGHER EF = 16,400 g TEQ/TJ

WOOD PELLETS FIRED BOILERS WITH CONTINUOUS OPERATION HAVE EF 10 TIMES LOWER THAN THOSE WITH DAILY SHUT DOWNS AND RE-STARTS.

OLD BOILERS FIRED WITH WOOD PELLETS HAVE EF 10 TIMES HIGHER THAN NEW BOILERS FIRED WITH THE SAME FUEL

DIOXINS AND FURANS EMISSION FACTORS CONSIDERED IN THE PROJECT (AVERAGED VALUES)

FORMATION OF DIOXINS AND FURANS DURING COMBUSTION PROCESS

MAIN DESIGN AND OPERATION PROBLEMS IN BOILERS

LOW TEMPERATURES (UNDER 900-1000 DO NOT DESTROY POPs LOW TURBULENCE OF EXHAUST GASES NON CONTINUOUS HOMOGENUOUS BURNING INSUFFICIENT AIR - OXYGEN CONTENT IN COMBUSTION PROCESSES INSUFFICIENT ON-LINE INSTRUMENTATION FOR COMBUSTION CONTROL (TEMPERATURE, OXYGEN, CO, DUST),

SMALL INDUSTRIAL BOILER

NOT OPTIMIZED BURNING PROCESS

PARAMETERS TO BE CONTROLLED TO REDUCE PCDD/PCDFs EMISSIONS

UNIFORM HIGH COMBUSTOR TEMPERATURE

GOOD MIXING WITH SUFFICIENT AIR

MINIMIZE ENTRAINED, UNBURNT PARTICULATE MATTER

FEED RATE UNIFORMITY

ACTIVE MONITORING AND CONTROL OF CO AND TOTAL HYDROCARBONS

COOLING SECTION
THE CONDITIONS INSIDE THE GAS COOLING SECTION COULD FAVOUR PCDD/PCDF FORMATION

TEMPERATURES VARYING IN THE RANGE 250-400 C

ACCUMULATION OF PARTICLES ON THE COLD SURFACES OF THE TUBES

POSSIBLE CLOGGING-CONDENSATION OF FLY ASHES

PERIODICAL CLEANING OF TUBES IS RECOMMENDED ( MANUAL, MECHANICAL, STEAM INJECTION)

MERCURY EMISSION SOURCES

COAL COMBUSTION IS THE MAIN SOURCE (>60%) OF MERCURY EMISSIONS TO THE ATMOSPHERE. MERCURY IS PRESENT IN COAL IN TRACE AMOUNTS (0.011.8 mg/kg).

CONCENTRATION IN CRUDE OILS SHOW WIDE RANGES (0.01-30 PPM). IN RESIDUAL OILS HIGHER CONC. THAN DISTILLATE OILS NATURAL GAS HAS VERY LOW AMOUNTS (0.02 0.2 ppb)

SMALL COMBUSTION PLANTS AND RESIDENTIAL COAL BURNING ARE ALSO SIGNIFICANT MERCURY SOURCES

MERCURY CONTENT IN SOME TYPES OF COAL

ESTIMATED MERCURY EMISSION FACTORS (mg/TJ) FOR DIFFERENT TYPES OF FUEL IN SMALL BOILERS IN EUROPE

REF: Costs and environmental effectiveness of options for reducing mercury emissions to air from small-scale combustion installations.AEA Technology / NILU-Polska 2005

MERCURY EMISSIONS
MERCURY EMISSIONS FROM COMBUSTION SOURCES OCCUR IN THREE FORMS: SOLID PARTICULATE-ASSOCIATED MERCURY (HGP ) GASEOUS DIVALENT MERCURY, (HG2+) AND GASEOUS ELEMENTAL MERCURY, (HG0)

AT HIGH TEMPERATURES IN BOILERS, MERCURY IS RELEASED AS ELEMENTAL MERCURY (HG0). IT IS THEN OXIDIZED BY CHLORIDE ACID, SO2 AND FLY ASH IN FLUE GAS IN HG2+. THIS IS SOLUBLE AND ASSOCIATES WITH THE PARTICLES IN FLUE GAS TO FORM HGP.

HG2+, HGP AND HG0 HAVE VERY DIFFERENT PHYSICO-CHEMICAL CHARACTERISTICS AND, CONSEQUENTLY, DIFFERENT EMISSION PATHWAYS

MERCURY REDUCTION
CONTROLLING MERCURY EMISSIONS FROM BOILERS INVOLVES 3 SEPARATE STEPS;

PRE-COMBUSTION CONTROL, PRE-CLEANING AND PRE-TREATMENT OF RAW COALS AND IMPROVEMENT OF THEIR QUALITY TO REDUCE THE ASH CONTENT, SULPHUR CONTENT AS WELL AS CHLORINE AND MERCURY

IN-FURNACE CONTROL LOW EXCESS AIR COMBUSTION, AMMONIA INJECTION, AND UREA INJECTION.

POST-COMBUSTION CONTROL. USE OF EMISSION ABATEMENT DEVICES

INFLUENCE AND EFFICIENCY OF ABATEMENT DEVICES FOR PCDD/PCDFS AND MERCURY

THE SIZE OF THE UTILITY BOILERS ALLOWS TO HAVE SIGNIFICANTECONOMIES OF SCALE, THAT ARE NOT AVAILABLE TO INDUSTRIAL BOILERS. FEW TECHNICAL OPTIONS EXIST FOR SMALL BOILERS

PCDD/PCDFs ARE REMOVED IN A LARGE EXTENT BY FILTERING SYSTEMS COUPLED WITH ADSORBERS MEDIA (ACTIVE CARBON) AND CATALYTIC DEVICES (SCR)

MERCURY IS REDUCED IN A LESSER EXTENT BY MECHANICAL SEPARATORS DESULPHURIZATION DEVICES FILTERING SYSTEMS COUPLED WITH ADSORBERS MEDIA (ACTIVE CARBON)

FLUE GAS DESULPHURIZATION DEVICES

PCDD/PCDFs IN WET SCRUBBERS

USED IN LARGE BOILERS OPERATING TEMPERATURE IS 45-80 C USUALLY TWO STAGES ARE USED (ACID AND BASIC) FOR REMOVAL OF ACIDS AND METALS, AND SO2

LOW EFFICIENCY FOR POPs REDUCTION

POPs ARE ADSORBED ON THE PLASTIC MATERIALS USED IN THE WALLS OF THE SCRUBBER AND CAN BE DESORBED AT HIGH TEMPERATURE

IF POLYPROPYLENE LAYERS ARE ADDED AND EMBEDDED WITH CARBON PCDD/PCDF AND MERCURYCAN BE ADSORBED REMOVAL EFFICIENCY UP TO 70%

DRY AND SEMY-DRY SCRUBBERS

SPRAY INJECTION OF SLAKED OR WET LIME Ca(OH)2 MEDIUM REMOVAL EFFICIENCY

IF ACTIVE CARBON IS ADDED PCDD/PCDFs REMOVAL EFFICIENCY UP TO 99%

LOWER CAPITAL COSTS BUT HIGHER OPERATING COSTS THAN WET SCRUBBERS MORE SOLID RESIDUE TO BE COLLECTED BY THE FILTERS

SPRAY DRY SCRUBBERS ARE MOSTLY USED FOR SMALL TO MEDIUM CAPACITY BOILERS

FILTERING SYSTEMS
IN SMALL BOILERS USUALLY SETTLING CHAMBERS OR CYCLONES THEY COLLECT ONLY COARSE PARTICLES SMALL BAG FILTERS ARE AVAILABLE

IN LARGE FACILITIES ELECTROFILTERS AND FABRIC (BAG) FILTERS CAN COLLECT FINE PARTICLES

FABRIC FILTERS AND ELECTROFILTERS OPERATE NORMALLY AT 200 C HIGHER TEMPERATURE CAN BE CRITICAL FOR PCDD/PCDF REFORMATION

ALL THESE DEVICES MUST BE FREQUENTLY CLEANED, TO AVOID PCDD/PCDF RE-FORMATION

PARTICULATE MATTER ABATEMENT DEVICES

SMOKE RELEASES FROM STACKS. NO ABATEMENT DEVICES WORKING

PCDD/PCDF REMOVAL EFFICIENCY

PCDD/PCDF REMOVAL EFFICIENCY
VERY LOW EFFICIENCY LOW EFFICIENCY MEDIUM EFFICIENCY HIGH FOR FINE PARTICLES MEDIUM EFFICIENCY

DEVICE
SETTLING CHAMBERS CYCLONES VENTURI WET SCRUBBER FABRIC FILTERS (FF) ELECTROSTATIC PRECIPITATORS

PCDD/PCDFs ARE MAINLY ADSORBED ON FINE PARTICULATE MATTER

REDUCTION OF MERCURY EMISSIONS

(HG2+) IS SOLUBLE AND ASSOCIATES WITH THE PARTICLES IN FLUE GAS TO FORM HGP. THEREFORE, EMISSIONS OF HG2+, MAY BE CONTROLLED BY TYPICAL AIR POLLUTION CONTROL DEVICES (APCD), FLUE GAS DESULFURIZATION (FGD) SYSTEMS ELECTROSTATIC PRECIPITATORS (ESP) FABRIC FILTER (FF)

THE VOLATILE FORM HG0 CAN BE CONTROLLED BY ADDING ACTIVE CARBON TO DRY SCRUBBERS

BECAUSE THE RELATIVE PROPORTIONS OF HG2+, HGP AND HG0 CAN VARY, THE CORRESPONDING REDUCTIONS ACHIEVED BY APCD VARY IN WIDE RANGE

REDUCTION OF MERCURY EMISSIONS

THE APPLICATION OF FLUE GAS DESULFURIZATION FGD HAS A VERY DEEP IMPACT ON MERCURY REMOVAL

THE LOW TEMPERATURE OF WET SCRUBBERS ALLOW THE VOLATILE TRACE EMENTS TO CONDENSE AND TO BE REMOVED REMOVAL EFFICIENCY RANGE FROM 30 TO 50%

SPRAY DRY SYSTEMS COUPLED WITH FABRIC FILTERS GIVE GOOD RESULTS REMOVAL EFFICIENCY RANGE FROM 35 TO 85%

THANK YOU FOR YOUR ATTENTION !

Andrea Sbrilli, UNIDO consultant andrea.sbrilli@alice.it

ESEA FORUM NATIONAL AWARENESS WORKSHOP FOR DEMONSTRATION OF BAT/BEP IN FOSSIL FUEL-FIRED UTILITIES AND INDUSTRIAL BOILERS ON PERSISTENT ORGANIC POLLUTANTS (POPS) BANGKOK, THAILAND 13 JUNE 2011