This document discusses requirements for the proper disposal of COPs (persistent organic pollutants) and hazardous waste. It begins by discussing international conventions for restricting COPs. It then provides examples of pesticides that are considered COPs. Next, it discusses the requirements proposed for adequate COP disposal, including achieving destruction and removal efficiencies of 99.9999%. Finally, it summarizes tests conducted demonstrating cement kilns can meet these requirements when incinerating organic hazardous waste, with temperatures and retention times sufficient to destroy COPs.

1. Requisitos paraRequisitos para
unauna
DisposiciDisposicióónn
adecuada deadecuada de
COPs y ResiduosCOPs y Residuos
PeligrososPeligrosos
DR FERNANDO MARQUEZDR FERNANDO MARQUEZ
UNIVERSIDAD DEUNIVERSIDAD DE
CONCEPCIONCONCEPCION

2. LOS COMPUESTOS QUIMICOS Y
LOS CONVENIOS
INTERNACIONALES

3. ““LaLa eliminacieliminacióónn oo restriccionrestriccion de lade la
producciproduccióónn yy usouso dede todos los COPstodos los COPs
intencionalmenteintencionalmente producidosproducidos y lay la
minimizaciminimizacióón continua y,n continua y, cuando seacuando sea
posible,posible, lala eliminacieliminacióónn de las emisiones dede las emisiones de
los COPS no intencionales tales como laslos COPS no intencionales tales como las
dioxinasdioxinas yy furanosfuranos””
Entra en vigenciaEntra en vigencia 1717 MayoMayo 20042004
La ConvenciLa Convencióón de Estocolmo sobren de Estocolmo sobre
Compuestos Organicos PersistentesCompuestos Organicos Persistentes
(COP(COP’’ss))

4. pesticidas COPspesticidas COPs
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Chlordane - 1,2,4,5,6,7,8,8-
octachloro-2,3,3a,4,7,7a-hexahydro-
4,7-methano-1H-indene Cl CH
CCl3
Cl
DDT
Cl
Cl
Cl
Cl Cl
Cl
Cl
Heptacloro
Cl
Cl
Cl
Cl
Cl
Cl
Hexaclorobenceno

5. Procesos de destilaciProcesos de destilacióón global de Contaminantesn global de Contaminantes
Organicos PersistentesOrganicos Persistentes

6. Requerimientos propuestos paraRequerimientos propuestos para
una disposiciuna disposicióón adecuada de COPsn adecuada de COPs
La destrucciLa destruccióónn y/y/óó
transformacitransformacióónn
irreversibleirreversible
de residuosde residuos dede
COPsCOPs debe logrardebe lograr
unauna eficiencia deeficiencia de
destruccidestruccióónn (DE)/(DE)/yy
una eficiencia deuna eficiencia de
destruccidestruccióónn yy
remociremocióónn (DRE)(DRE) dede
99.9999%99.9999%

7. Las siguientes operaciones de disposición, de acuerdo a Anexos IVA y IVB de
la Convención de Basilea, deberían servir para el proposito de la destrucción
y transformación irreversible de los COPs contenidos en residuos cuando se
usa de modo de asegurar que los residuos restantes y emisiones no exhiben
caracteristicas de COPs (algunos todavía en demostraciones piloto)
Proceso DE/DRE (%) Costo
Reducción Alcalina No
Descomposición Catalizada 99.99-99.9999 ↑
Co-Incineración Horno Cemento 99.99-99.9999 ←
Reducción Química Fase Gas 99.99-99.9999 ↑
Incineración Residuos peligrosos 99.99-99.9999 ↑
Oxidación electroquímica 99.995
Oxidación con Plata No
Arco Plasma 99.99-99.9999 ↑
Oxidación Super critica No

8. Gas-Phase
Chemical
Reduction
(GPCR™)
Reactor
Gas
Scrubbing
System
Product Gas
Compression
and Storage
Treated Solids Water
Auxiliary
Burner
Gas
Liquid
Solid
Fuel for Front-end Systems
Recirculation Gas
Mixer
Hydrogen and
Steam Preheater
Liquid/Gaseous
Waste Injection
Thermal Desorber
Thermal Reduction
Batch Processor (TRBP)
Front-End Waste Feed Waste Destruction Output Recovery

9. Costos y necesidad de altas temperaturas deCostos y necesidad de altas temperaturas de
combustion de cantidades a granel decombustion de cantidades a granel de
residuos peligrososresiduos peligrosos
Incinerador DedicadoIncinerador Dedicado Horno CementoHorno Cemento
Infraestructura Confiable Infraestructura Confiable
Incinerador Nuevo Introducción de residuos
Estación de residuos Estación de residuos
Competencia y entrenamiento Competencia y
entrenamiento
→200 USD millones 0,1-? USD millones
Costos operación altos Costos operación bajos
Costos disposición residuos Usualmente sin residuos

10. En Chile NoEn Chile No existenexisten plantasplantas dede incineraciincineracióónn dede ResiduosResiduos
PeligrososPeligrosos,, peropero existenexisten hornoshornos dede cementocemento¡¡¡¡¡¡¡¡¡¡¡¡

11. Son adecuados los
hornos de cemento
para destruir COPs
de una manera
irreversible y
además cumplir
con los
requiremientos de
la Convención de
Estocolmo?

12. Producción de cemento
Materia Prima
cantera
mezclado
Rohmühle
horno
despachoalmacenamientoalmacenamiento Molino de cemento
ESPCemento
crudo
CementoClinker
gas
solido

13. HornoHorno humedohumedo
largolargo

15. HornoHorno secoseco concon
precalentadorprecalentador yy
precalcinadorprecalcinador

18. Quemador
principal

19. Rotary Kiln
Cyclone
Preheater
Clinker Cooler
«De-Novo-Synthesis»
550 [°C]
720 [°C]
1200 [°C]
2000 [°C]
850 [°C]
0 [sec] 8 [sec]
25 [sec]
Gas FlowMaterial Flow
800 [°C]
30 [°C]
1450 [°C]
900 [°C]
350 [°C]
Range 400-800 [°C]
Temperaturas y tiempo de retención en horno con precalentador

24. CoCo--procesamientoprocesamiento dede ResiduosResiduos
PeligrososPeligrosos enen HornosHornos dede CementoCemento
• ...is aceptada de ser una opción
posible de tratamiento en regulaciones
Europeas, US y otras (necesitan cumplir
con requisitos de ELV’s y DRE).
• Mas de 10 millones de tons/anuales de
Residuos Peligrosos son co-procesados
en hornos de cemento alrededor del
mundo.

25. Requerimientos Performance
EU USA Incinerador Dedicado Horno Cement
Temperatura 850 -1100 o
C 850 – 1600 o
C 900 –1200 o
C 1450 – 2000 o
C
Tiempo Residencia ≥ 2 segundos ≥ 2 segundos 0,3 – 4 segundos 4-8 segundos
Disponibildad de O2
3 – 6 % 2 – 3% > 4 % > 4%
Turbulencia/mezclado Si Si Si Si
Estabilidad Termica Quemador
auxiliar
Quemador auxiliar Quemador auxiliar Bufer térmico
Limpieza gas salida ELVs ELVs & DRE Avanzada EP/filtros& absorción
sosa
CombustiCombustióónn dede ResiduosResiduos PeligrososPeligrosos --
UnaUna ComparaciComparacióónn dede RequerimientosRequerimientos &&
PerformancePerformance InternacionalInternacional Legal enLegal en
IncineradoresIncineradores DedicadosDedicados && HornosHornos dede
CementoCemento

28. Hornos de
Cemento han sido
usados para co-
incineración de
residuos
peligrosos
orgánicos en
Noruega por más
de 20 años

29. Las autoridades ambientales y las compañias locales de
cemento han cooperado para desarrollar una opción
adecuada para la disposición de residuos peligrosos
orgánicos procedentes de la industria Noruega...
INDUSTRIA DEL CEMENTO EN NORUEGA

30. •• SeSe puedepuede usarusar instalacionesinstalaciones ee infraestructurainfraestructura existenteexistente..
•• ElEl hornohorno dede cementocemento recuperarecupera lala energiaenergia dede loslos residuosresiduos,,
ahorraahorra combustibles nocombustibles no renovablesrenovables yy emiteemite menoresmenores
cantidadescantidades de COde CO22
•• LaLa plantaplanta dede cementocemento puedepuede reducirreducir sussus costoscostos dede
producciproduccióónn..
•• LosLos costoscostos dede disposiciondisposicion sese puedenpueden mantenermantener enen nivelesniveles
razonablesrazonables..
•• No seNo se creancrean nuevosnuevos residuosresiduos peligrosospeligrosos..
•• LasLas pruebaspruebas ee investigacionesinvestigaciones dede loslos test detest de combusticombustióónn
muestranmuestran queque laslas emisionesemisiones no seno se afectanafectan porpor lala
sustitucisustitucióónn de combustiblesde combustibles ffóósilessiles porpor residuosresiduos
peligrosospeligrosos organicosorganicos..
LasLas autoridadesautoridades noruegasnoruegas indicanindican
loslos beneficiosbeneficios queque resultanresultan dede usarusar
hornoshornos dede cementoscementos

31. “... halogenoshalogenos organicosorganicos
complejoscomplejos comocomo loslos PCBsPCBs
requierenrequieren 12001200oo
C y 2C y 2 segundossegundos
dede tiempotiempo dede residenciaresidencia ””
CriteriosCriterios de Incineration US EPAde Incineration US EPA
[[Toxic Substances Control Act (TSCA) PCB]Toxic Substances Control Act (TSCA) PCB]
UnaUna eficienciaeficiencia DRE de 99.9999% seDRE de 99.9999% se requiererequiere porpor lala
EPA (TSCA)EPA (TSCA) parapara lala incineraciincineracióónn de PCBde PCB’’ss

32. ““......sisi masmas de 1 % ofde 1 % of sustanciassustancias
organicasorganicas halogenadashalogenadas,,
expresadasexpresadas comocomo clorocloro, se, se
incineranincineran, la, la temperaturatemperatura debedebe
aumentarseaumentarse comocomo minimominimo aa
11001100°°CC durantedurante alal menosmenos
dosdos segundossegundos””..
DirectivaDirectiva EU 2000/76/ECEU 2000/76/EC sobresobre IncineraciIncineracióónn dede ResiduosResiduos
regularegula la Cola Co--incineraciincineracióónn dede ResiduosResiduos PeligrososPeligrosos enen HornosHornos
CementoCemento

33. Los Test deLos Test de incineraciincineracióónn dede aceitesaceites concon
PCB enPCB en NoruegasNoruegas siempresiempre hanhan
entregadoentregado valoresvalores de DRE >99.9999%de DRE >99.9999%

34. Environment CanadaEnvironment Canada
““What kind of facilities are able to dispose ofWhat kind of facilities are able to dispose of
PCBsPCBs””
“The cement manufacturing process uses high- temperature
rotary kilns which are capable of destroying PCB-
contaminated oil at an efficiency greater than 99.9999
percent. This approach also reduces the fuel needs of the
cement kiln.
A test burn conducted in a Mississauga, Ontario cement kiln
in the mid-1970s resulted in no detectable amounts of PCB or
other hazardous emissions. However, public opposition led
the company to withdraw its proposal to burn hazardous
wastes in the plant”.
http://www.ec.gc.ca/pcb/factsheets/eng/pcb13 e.htm

35. combustion encombustion en HornosHornos dede
CementoCemento aseguraasegura ::
suficientesuficiente
-- temperaturatemperatura;;
–– oxigenooxigeno;;
–– tiempotiempo dede residenciaresidencia;;
–– condicionescondiciones mezcladomezclado;;
yy ambienteambiente alcalinoalcalino......

36. Test de
incineración de
suelo
contaminado
con COP’sO
P(OCH3)2
S
O2N
COLOMBIA

38. DRE >99.9999%DRE >99.9999%
for DDT, Aldrin,for DDT, Aldrin,
Dieldrin andDieldrin and
PentachlorbenzenePentachlorbenzene

39. Australian Pesticide &Australian Pesticide &
Hazardous Chemical CollectHazardous Chemical Collect
and disposal programand disposal program

46. Test Burn with solvent based fuel in Queensland Cement Company sTest Burn with solvent based fuel in Queensland Cement Company showed nohowed no
influence on the emissionsinfluence on the emissions

47. Test Burn with insecticides in Hon Chong, Kien
Giang Province, South Vietnam, October 2003.
O
C H C H 2C H 3
C H 3
O
C
C H 3N H
F3C N
Cl
Cl
N CN
S
O
CF3
NH2

60. Emissions of PCDD/FEmissions of PCDD/F’’s ng Is ng I--TEQ/NmTEQ/Nm33
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Baseline
Test burn
ELV
No congenersNo congeners
identifiedidentified
(50% of LOD values)(50% of LOD values)

61. Emission of dioxin like PCBs (ng/NmEmission of dioxin like PCBs (ng/Nm33
))--
No ELV in VietnamNo ELV in Vietnam
NonNon--orthoortho PCBPCB’’ss BaselineBaseline Test burnTest burn
3,3’,4,4’-Tetrachlorobiphenyl (PCB 77) < 0.034 < 0.051
3,4,4’,5-Tetrachlorobiphenyl (PCB 81) < 0.017 < 0.025
3,3’,4,4’,5-Pentachlorobiphenyl (PCB 126) < 0.009 < 0.013
3,3’,4,4’,5,5’-Hexabiphenyl (PCB 169) < 0.009 < 0.013
MonoMono--orthoortho PCBPCB’’ss
2,3,3’,4,4’-Pentachlorobiphenyl (PCB105) < 0.170 < 0.254
2,3,4,4’,5-Pentachlorobiphenyl (PCB114) < 0.034 < 0.051
2,3’,4,4’,5-Pentachlorobiphenyl (PCB118) < 0.341 < 0.507
2’,3,4,4’,5-Pentachlorobiphenyl (PCB123) < 0.034 < 0.051
2,3,3’,4,4’,5-Hexabiphenyl (PCB 156) < 0.170 < 0.254
2,3,3’,4,4’,5’-Hexabiphenyl (PCB 157) < 0.034 < 0.051
2,3’,4,4’,5,5’-Hexabiphenyl (PCB 167) < 0.170 < 0.254
2,3,3’,4,4’,5,5’-Heptabiphenyl (PCB 189) < 0.034 < 0.051

62. Cement kilns firing hazardous waste areCement kilns firing hazardous waste are
explicitly mentioned in the Stockholmexplicitly mentioned in the Stockholm
Convention, Annex C part II, asConvention, Annex C part II, as
““industrial source having theindustrial source having the
potential for comparatively highpotential for comparatively high
formation and release offormation and release of
dioxins to the environmentdioxins to the environment””
The Stockholm ConventionThe Stockholm Convention

63. US EPA revised PCDD/F release estimates forUS EPA revised PCDD/F release estimates for
cement kilns was reduced by 97% in 7 years....cement kilns was reduced by 97% in 7 years....
HWC cement kilns D/F emission reduction
860
431
23 13,1
0
200
400
600
800
1000
EPA first estimate for
1990
EPA revised estimate
for 1990
EPA estimate for
1996
EPA estimate for
1997
gTEQ/y

64. “hazardous waste burning inhazardous waste burning in
cement kilns does not have ancement kilns does not have an
impact on dioxin/furanimpact on dioxin/furan
formation,formation, dioxin/furan isdioxin/furan is
formed postformed post--combustioncombustion”
In the development of the Hazardous WasteIn the development of the Hazardous Waste
Combustor (HWC) Maximum Achievable ControlCombustor (HWC) Maximum Achievable Control
Technology (MACT) rule, EPA noted thatTechnology (MACT) rule, EPA noted that
(Federal Register, 64 FR 52876, September 30, 1999).

65. Cement kilns in the US coCement kilns in the US co--process 1 millionprocess 1 million
tons of Hazardous Wastes per yeartons of Hazardous Wastes per year
0
200
400
600
800
1000
1200
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
Volumes of Hazardous Waste Burned for Energy
Recovery in U.S. Cement Kilns
Tons (in thousands)

67. More than 1,700 PCDD/FMore than 1,700 PCDD/F
measurements, many PCB andmeasurements, many PCB and
some HCB measurements weresome HCB measurements were
compiled from cement kilnscompiled from cement kilns
around the world. The dataaround the world. The data
represents emission levels fromrepresents emission levels from
both wet and dry kilns, performedboth wet and dry kilns, performed
under normal and worst caseunder normal and worst case
operating conditions, with andoperating conditions, with and
without the cowithout the co--processing of aprocessing of a
wide range alternative fuel andwide range alternative fuel and
raw materials.raw materials.
http://www.pops.int/documents/meetings
/bat_bep/2nd_session/egb2_followup/

68. In the United Nations Environment Programme (UNEP),In the United Nations Environment Programme (UNEP),
““Standardized Toolkit for Identification and Quantification ofStandardized Toolkit for Identification and Quantification of
Dioxin and Furan ReleasesDioxin and Furan Releases”” of May 2003.of May 2003.
“In the USA, earlier tests indicated that higher emissions
were found for some wet kilns where hazardous wastes were
fired. More detailed investigation suggested that – provided
combustion is good - the main controlling factor is the
temperature of the dust collection device in the gas cleaning
system.
The plants equipped with low temperatureThe plants equipped with low temperature
electrostatic precipitators appear to haveelectrostatic precipitators appear to have
well controlled emissions withwell controlled emissions with
or without waste fuelsor without waste fuels “

69. 230 Measurements in 110 kilns and 11230 Measurements in 110 kilns and 11
European countriesEuropean countries
D/Femission

70. Summary of PCDD/F levels measured inSummary of PCDD/F levels measured in
244244 HolcimHolcim kilns (wet and dry) worldwidekilns (wet and dry) worldwide
20012001--20032003

71. 152 PCDD/F measurements from 43152 PCDD/F measurements from 43
Heidelberg kilns in 2001Heidelberg kilns in 2001--20042004
D/FemissioninngTEQ/m3

72. 64 PCDD/F measurements in 6 kilns from64 PCDD/F measurements in 6 kilns from
Lafarge Cement CompanyLafarge Cement Company
0
0,05
0,1
0,15
0,2
0,25
0 10 20 30 40 50 60 70
Measurements
D/Femissioninng/Nm3

73. 106 PCDD/F emission measurements from 37106 PCDD/F emission measurements from 37
German Cement Kilns in 2001German Cement Kilns in 2001

74. AustraliaAustralia
Results of repeated measurements
over a decade show that levels of
dioxin emissions from Australian
cement plants are consistently
below 0.1 ng I-TEQ/m3.
Comparison with all sources, placesComparison with all sources, places
cement manufacturing as ancement manufacturing as an
““insignificantinsignificant”” contributor to overallcontributor to overall
PCDD/F emissions in Australia.PCDD/F emissions in Australia.

75. AustraliaAustralia
PCDD/F emissions have been measured from a range of Australian
cement plants representing different operating and process conditions,
different fuel sources and different raw materials. Both wet and dry
process are represented, as are plants using gas and coal as primary
fuels sources as well as plants using waste-derived fuels.
No significant difference inNo significant difference in
dioxin emissions due todioxin emissions due to
use of waste derived fuelsuse of waste derived fuels
was observed within plantswas observed within plants
(Environment Australia, 2002).

76. Heidelberg kilns using more than 40%Heidelberg kilns using more than 40%
alternative fuel compared with kilns usingalternative fuel compared with kilns using
fossil fuel onlyfossil fuel only

77. (0,29)
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0 20 40 60 80 100 120 140 160
Measurement No.
EmissionsinngI-TEQ/m3
regular fuel
with
secondary
fuel
with
secondary
raw
material
PCDD/F concentration measured by thePCDD/F concentration measured by the
Research Institute of the German CementResearch Institute of the German Cement
IndustryIndustry

78. Measurement
ConcentrationinngITEQ/m3
0.00
0.03
0.06
0.09
0.12
0.15
1999
2000
2001
2002
PCDD/F
PCDD/F emissionPCDD/F emission –– GermanyGermany
1999: substitution level 23%1999: substitution level 23%
2002: substitution level 35%2002: substitution level 35%

79. UNEP dioxin
inventory in
Thailand

80. Among the 7 industrial sectors investigated, cement kilns had the
lowest PCDD/F emissions
““... results clearly revealed that the... results clearly revealed that the
addition of tyres and/or liquidaddition of tyres and/or liquid
hazardous waste had no effect onhazardous waste had no effect on
the emission resultsthe emission results…”…”
The means measured were 0.0105 ng I-TEQ/m3 and 0.0008 ng I-TEQ/m3 for
the normal operation conditions and 0.003 ng I-TEQ/m3 and 0.0002 ng I-
TEQ/m3 for the test performed with substitute secondary fuels, respectively.
In 1997 the Pollution Control Department (PCD) of the GovernmentIn 1997 the Pollution Control Department (PCD) of the Government ofof
Thailand initiated a dioxin program together with UNEPThailand initiated a dioxin program together with UNEP

81. Measures for minimisation andMeasures for minimisation and
control of PCDD/Fcontrol of PCDD/F’’s emissionss emissions
1.1. Quick cooling of kiln exhaust gases to lowerQuick cooling of kiln exhaust gases to lower
than 200than 200ooC in wet kilns (already inherent inC in wet kilns (already inherent in
dry preheater & precalciner kilns)dry preheater & precalciner kilns)
2.2. Limit alternative raw material feed as part ofLimit alternative raw material feed as part of
rawraw--mix if it includes organicsmix if it includes organics
3.3. No alternative fuel feed during startNo alternative fuel feed during start--up andup and
shut downshut down
4.4. Monitoring and stabilisation of processMonitoring and stabilisation of process
parametersparameters

83. When the authorities inWhen the authorities in
1995 decided not to1995 decided not to
build a dedicatedbuild a dedicated
incinerator forincinerator for
hazardous waste inhazardous waste in
Norway, but toNorway, but to
continue to use thecontinue to use the
cement kilns, thiscement kilns, this
decision wasdecision was
supported by thesupported by the
nearby community, bynearby community, by
green NGOgreen NGO’’s etc.s etc.

85. ConclusionConclusionConclusion
•• Most cement kilns can meet an PCDD/F emissionMost cement kilns can meet an PCDD/F emission
limit of 0.1 ng TEQ/Nmlimit of 0.1 ng TEQ/Nm33;;
•• CoCo--processing of alternative fuels and rawprocessing of alternative fuels and raw
materials (and hazardous wastes) does notmaterials (and hazardous wastes) does not
seems to influence or change the emissions ofseems to influence or change the emissions of
PCDD/F & POPPCDD/F & POP’’s;s;••
•• It is doubtful that cement kilns coIt is doubtful that cement kilns co--processingprocessing
hazardous wastes would have been mentionedhazardous wastes would have been mentioned
as a source category for PCDD/F emissions inas a source category for PCDD/F emissions in
the Stockholm Convention if updated informationthe Stockholm Convention if updated information
had been considered.had been considered.

86. ConclusionConclusionConclusion
A suitable cement kiln can comply with theA suitable cement kiln can comply with the
requirements of the Stockholm and the Baselrequirements of the Stockholm and the Basel
Convention on sound irreversible destruction/Convention on sound irreversible destruction/
transformation of hazardous chemicals.transformation of hazardous chemicals.
The cement industry will play an important roleThe cement industry will play an important role
in the urgent global need for sustainable andin the urgent global need for sustainable and
costcost--efficient disposal of hazardous wastes.efficient disposal of hazardous wastes.