fate and behaviour of nanomaterials in incineration processes · pawel baran “fate and behaviour...

Fate and behaviour of nanomaterials in incineration processes

Pawel Jan Baran M. Eng.

Unit of Technology of Fuels (TEER)

RWTH Aachen University

8th CEWEP Waste-to-Energy Congress 2016

16-17 June in Rotterdam

Pawel Baran

“Fate and behaviour of nanomaterials in incineration processes”



Outline

Introduction

Project NanoEmission

Basic research

Measurement campaign in WtE plant Weisweiler

Methods

Results

Conclusions

2/25

Introduction

Pawel Baran




Definition

Nanomaterial: „A natural, incidental or manufactured

material containing particles, in an unbound state or as an

aggregate or as an agglomerate and where, for 50 % or more

of the particles in the number size distribution, one or more

external dimensions is in the size range 1 nm - 100 nm. …"[1]

CeO2

BaSO4

Source: Recommendation on the definition of a nanomaterial (2011/696/EU), 18.10.2011 (updated on 08.06.2016)

http://ec.europa.eu/environment/chemicals/nanotech/faq/definition_en.htm#top-page

ZnO

4/25

Ag

TiO2

Quantum Dots

CNT

Project NanoEmission

Pawel Baran




Approach

Extension of the knowledge in the field of emission behavior of nanoparticles in

waste incineration process:

6/25

Characterization of the emission behaviour of nanoparticles during combustion

Evaluation and optimization of filter media with focus on reduction of nanoparticles in exhaust gases

Human- and ecotoxicological assessment of nanoparticle fractions found in exhaust gases

Basic research

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Project-specific nanomaterial

8/25

Barium sulfateThe primary particle size:~40 nm;Particle size distribution: d50= ~100 nm

Fig. 2: SEM picture of BaSO4 agglomerates and particle size distribution by number in aqueous suspension (0,7% Ecodis P-30) (DLS)

Source: LFG Erlangen, MLU Halle

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Sintering behaviour of BaSO4

9/25

Fig.3 Change of the test samples’ surface area during heating in the presence of air (heating microscope)

Source: TEER RWTH Aachen

Shrinkage starting temperature of BaSO4

BaSO4 d50= 1,7µm

BaSO4 d50= 40nm

532 °C 650 °C

25°C 1500°C

25°C 1500°C

Change o

fsurf

ace

are

a[%

]

temperature (°C)

Melting point (Bulk): 1580°CSource: Handbook of Chemistry and Physics (85th ed.). CRC Press. 2004.

pp. 4–45.

Measurement campaign in WtE plant Weisweiler (Germany) (16-20.11.2015)

Pawel Baran




11/25

Experiments in waste incineration plant Weisweiler

A. Waste bunker

B. Firing system

C. Evaporating cooler

D. Fabric filter

E. Catalysts

BaSO4 dosing system

total dust content / Impaktor

combustion residues sampling

Measurement points

R1. after boiler

R2. after evaporating cooller

R3. after fabric filter

E1. Bottom ash discharger

E2. Boiler ash discharger

E3. Residue from fabric filter

AB

C

D

E

R1

R2E3

E1 E2

R3

Z1

Methods

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Z1: Addition of nanomaterial

13/25

Fig.4: Production and dosing of nanosuspension

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E1-3: Sampling points for combustion residues

14/25

E1: Bottom ash E2: Boiler ash E3: Residue from fabric filter

Determination of Ba concentration ICP-MS Analysis

Fig.5: Sampling und preparation of combustion and filtration residues conducted according to DIN 22022 and DIN 51701

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R1-3: Dust measurement techniques

15/25

Fig.6: Devices for the dust measurement (left), principle of particle impaction (right, above) and precipitator with collected dust (right, below).

Mobile filter probe

Gravimetric determination of dust load

Particle size selective

measurement (cascade impactors)

Determination of Ba

concentration ICP-MS

Analysis

Determination of dioxin and

heavy metals content

toxicological examinations

Results

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E1-3: Mass concentration of Ba in combustion residues

17/25

0

0.5

1

1.5

2

2.5

Ma

ssco

nce

ntr

ati

on

of

Ba

[%]

time [hh:mm]

Entnahmepunkt E1: Rostaasche

Entnahmepunkt E2: Kesselasche

Entnahmepunkt E3: Gewebefilterasche

18.11.2016

19.11.2016

E1: Bottom ash

E2: Boiler ash

E3: Residue from fabric filter

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R1: Gravimetric determination of particle mass concentrationflue gas after boiler

18/25

0

2000

4000

6000

8000

10000

12000

0

2000

4000

6000

8000

10000

12000

Bari

um

[µ

g/m

³ i.

N., t

r.]

Du

st[m

g/m

³ i.

N., t

r.]

(hh:mm)

Gesamtstaub (VDI 2066) Barium (ICP-MS)

18.11.2015 (without BaSO4) 19.11.2015 (with BaSO4)

Dust load (VDI 2066)

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R4: Gravimetric determination of particle mass concentrationclean gas after fabric filter

19/25

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

2.00

14:10 15:20 16:30 12:45 13:52 15:21 16:25

Ba

riu

m [

µg

/m³

i.N

., t

r.]

Du

st[m

g/m

³ i.

N., t

r.]

(hh:mm)

Gesamtstaub (VDI 2066) Barium (ICP-MS)

18.11.2015 (without BaSO4)

Detection limit

19.11.2015 (with BaSO4)

Dust load (VDI 2066)

Pawel Baran




0

2,000

4,000

6,000

8,000

10,000

0

200

400

600

800

1,000

0.01 0.1 1 10

Du

std

mc/

dlo

gD

ae5

0[m

g/m

³ i.

N.,

tr.

]

Particle diameter Dae50 [µm]

0

2,000

4,000

6,000

8,000

10,000

0

200

400

600

800

1,000

0.01 0.1 1 10

Ba

riu

m d

c/d

log

Dae5

0[µ

g/m

³ i.

N.,

tr.

]

Du

std

mc/

dlo

gD

ae5

0[m

g/m

³ i.

N.,

tr.

]

20/25

18.11; 15:23 Ba<100 nm: 214 µg/m³ i.N., tr.

19.11; 15:12 Ba <100 nm: 595 µg/m³ i.N., tr.

0

2,000

4,000

6,000

8,000

10,000

0

200

400

600

800

1,000

0.01 0.1 1 10

Ba

riu

m d

c/d

log

Da

e50

[µg

/m³

i.N

., t

r.]

Particle diameter Dae50 [µm]

Staub Barium

19.11 18:00 Ba <100 nm:

543 µg/m³ i.N., tr.

R1: Determination of particle size distribution (cascade impactor) flue gas after boiler

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Mass balance

21/25

Z1: Waste 16,2 t/h, Ba: 44,2 kg/h E1: Ash 3,95 t/h, Ba: 26,2 kg/h

E2: Ash 0,27 t/h, Ba: 2,6 kg/h

E3: Filtration residue 0,6 t/h Ba:

1,4 kg/h

*Barium background concentration has been substructed

100%

59,1%

5,8% 3,2%0,14 ppm

(1,3 %)

(1,2 %)

Recovery rate 68,1 %

separation efficiency of filter:

Dust: 99,87 – 99,94%

Barium: 99,98 – 99,99%

<100 nm: 99,97 – 99,99%

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Comparison

22/25

Research group /

Incineration plant

ENM Mass distribution Separation efficiency

ETH Zürich / Municipal

waste incineration plant *

nano-CeO2 Slag:

81% Ce

Fly ash:

19% Ce

Quench water:

0,02% Ce

Electrostatic precip.

C1: 99,9 % (Ce)

KIT Karlsruhe / Hazardous

waste incineration plant **

nano-CeO2 Boiler:

10,6 %Ce

Quench water:

68,7 % Ce

Fly ash:

0,1% Ce

Electrostatic precip.

99,99 % (Ce)

Fraunhofer Umsicht /

sewage-sludge-incineration

plant

nano-TiO2 Bottom ash

& boiler:

89,9% Ti

Adsorber & fabrik filter residue:

10,7% Ti

Fabrik filter:

99,99% (Ti)

NanoEmission / Municipal

waste incineration plant

nano-BaSO4 Bottom ash:

59,1% Ba

Boiler:

5,8% Ba

Fabrik filter res

3,2 % Ba

Fabrik filter:

99,98% (Ba)

Source:

Walser, T.; Limbach, L. K.; Brogioli, R.; Erismann, E.; Flamigni, L.; Hattendorf, B.; Juchli, (2012) Persistence of engineered nanoparticles in a

municipal solid-waste incineration plant.

Liesen, I.-M., Baumann W., Hauser M., Mätzing H., Paur H.-R., Seifert H., Untersuchung zur Freisetzung von synthetischen Nanopartikeln bei der

Börner et al. Abfallverbrennung , Energie aus Abfall Band 12, 2015 Tagungsband

Untersuchung möglicher Umweltauswirkungen bei der Entsorgung nanomaterialhaltiger Abfälle in Abfallbehandlungsanlagen

Conclusions

Pawel Baran




Conclusions

24/25

• Emission behaviour dependent on thermochemical properties of ENMs

• High total dust content agglomeration tendency

• Fluctuating background concentration of trace elements in waste and long

residence time of NP difficulties in accurate estimation of the nanoparticle’s

path distribution

• Most significant distribution pathway of ENMs is the bottom ash (50 – 90%)

• High separation efficiency in existing flue gas cleaning systems

• Fate and behavior of ENMs in combustion residues is still to clarify

Thank you for your interest!

Pawel Jan Baran M. Eng.

Wüllnerstraße 2

Raum Be 126

RWTH Aachen University

52056 Aachen

www.teer.rwth-aachen.de

fate and behaviour of nanomaterials in incineration processes · pawel baran “fate and behaviour...

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