Fate and behaviour of nanomaterials in incineration processes

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1 Fate and behaviour of nanomaterials in incineration processes Prof. Dr.-Ing. Pawel Jan Baran M. Eng. Unit of Technologies of RWTH Aachen University ISWA World Congress WGER Meeting Novi Sad 2016

2 Project NanoEmission

3 Approach Extension of the knowledge in the field of emission behavior of nanoparticles in waste incineration process: 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 7/26

4 Basic research

5 Project-specific nanomaterial Barium sulfate The primary particle size:~40 nm; Particle size distribution: d50= ~100 nm Source: LFG Erlangen, MLU Halle Fig. 2: SEM picture of BaSO4 agglomerates and particle size distribution by number in aqueous suspension (0,7% Ecodis P-30) (DLS) 9/27

6 Sintering behaviour of BaSO4 Melting point (Bulk): 1580 C Source: Handbook of Chemistry and Physics (85th ed.). CRC Press pp Change of surface area [%] Shrinkage starting temperature of BaSO4 532 C 650 C BaSO4 d50= 1,7µm 25 C 1500 C BaSO4 d50= 40nm 25 C 1500 C temperature ( C) Fig.3 Change of the test samples surface area during heating in the presence of air (heating microscope) Source: TEER RWTH Aachen 10/27

7 Measurement campaign in WtE plant Weisweiler [Germany] [ ]

8 Experiments in waste incineration plant Weisweiler A. Waste bunker B. Firing system C. Evaporating cooler D. Fabric filter E. Catalysts BaSO4 dosing total dust content / Impaktor combustion residues sampling Z1 E1 R1 E2 R2 E3 R3 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 12/27

9 MVA Weisweiler 11

10 Generation of suspension Material Share nano-baso4 35% Ecodis P30 0,7 % 11

11 Generation of suspension 900 kg BaSO kg suspension 192 x 10L buckets in 12 h ca. 75 kg BaSO4 [ca. 44,15 kg Barium] per 16t waste / h Factor 8 Mass share of Ba in the waste Addition ca. 0,28 % Reference ca. 0,035 % 12

12 Dosing of suspension 13

13 Input mass concentration of Ba 0,6 Theoretical mass concentration Barium [%] Abfall Waste [t] Mittelwert Average Barium [%] Concentration increase 6 0,5 5 Mass concentration of Ba [%] 0,4 0,3 0,2 0, Mass of waste [t] 0 0 time [hh:mm] 18/27

14 Results

15 E1-3: Sampling points for combustion residues E1: Bottom ash E2: Boiler ash E3: Residue from fabric filter Fig.5: Sampling und preparation of combustion and filtration residues conducted according to DIN and DIN Determination of Ba concentration ICP-MS Analysis 15/27

16 E1-3: Sampling points for combustion residues E1: Bottom ash E2: Boiler ash E3: Residue from fabric filter Fig.5: Sampling und preparation of combustion and filtration residues conducted according to DIN and DIN Determination of Ba concentration ICP-MS Analysis 15/27

17 E1-3: Mass concentration of Ba in combustion residues Mass concentration of Ba [%] 2,5 2 1,5 1 0,5 Entnahmepunkt E1: Bottom ash E1: Rostaasche Entnahmepunkt E2: Boiler ash E2: Kesselasche Entnahmepunkt E3: Residue from E3: fabric Gewebefilterasche time [hh:mm] 19/27

18 R1, R2, R4: Sampling points for raw and clean gas R1 Raw gas [4th path] R2 Rohgas downstream evaporation cooler R4 Clean gas 17

19 R1: Gravimetric determination of particle mass concentration flue gas after boiler Gesamtstaub Dust load (VDI 2066) Barium (ICP-MS) (without BaSO 4 ) (with BaSO 4 ) Dust [mg/m³ i.n., tr.] Barium [µg/m³ i.n., tr.] (hh:mm) 20/27

20 R1: Determination of particle size distribution [cascade impactor] flue gas after boiler Dust dmc/dlogd ae50 [mg/m³ i.n., tr.] Dust dmc/dlogd ae50 [mg/m³ i.n., tr.] ; 15:12 Ba <100 nm: 595 µg/m³ i.n., tr ,01 0, Particle diameter D ae50 [µm] 18.11; 15:23 Ba<100 nm: 214 µg/m³ i.n., tr ,01 0, Barium dc/dlogd ae50 [µg/m³ i.n., tr.] :00 Ba <100 nm: 543 µg/m³ i.n., tr. Staub Barium 0 0 0,01 0, Particle diameter D ae50 [µm] Barium dc/dlogd ae50 [µg/m³ i.n., tr.] 22/27

21 R4: Gravimetric determination of particle mass concentration clean gas after fabric filter Dust [mg/m³ i.n., tr.] 2,00 1,80 1,60 1,40 1,20 1,00 0,80 0,60 0,40 0,20 0,00 Gesamtstaub Dust load (VDI 2066) Barium (ICP-MS) (without BaSO 4 ) (with BaSO 4 ) Detection limit 14:10 15:20 16:30 12:45 13:52 15:21 16:25 1,00 0,90 0,80 0,70 0,60 0,50 0,40 0,30 0,20 0,10 0,00 (hh:mm) Barium [µg/m³ i.n., tr.] 21/27

22 Mass balance 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: Filter dust 0,6 t/h Ba 1,4 kg/h 100% 5,8% 3,2% 0,14 ppm Recovery rate 68,1 % 59,1% Separation efficiency of filter: Dust: 99,87 99,94% Barium: 99,98 99,99% <100 nm: 99,97 99,99% *Barium background concentration has been substructed 23/27

23 Results of other investigations

24 Laboratory studies Emission behavior of nano-ceo2 (KIT, Karlsruhe) Burner/Pulveriser system for the combustion of nano-aerosol in propane flame Fig.6: Laboratory set for the investigation of the thermal behavior of nano cerium oxide in flame before after Changed structure and size Quelle: [5] Liesen, I.-M., Baumann W., Hauser M., Mätzing H., Paur H.-R., Seifert H., Freisetzung von Nanopartikeln bei thermischen Prozessen, 2014, DGAW Tagungsband 11

25 Studies in pilot scale facilities Emission behavior of nano-ceo2 in pulverised coal furnace (KIT) ENMs dosing system M3: 60% Ce-separation by thermophoresis in the furnace BRENDA - rotating kiln furnace M4: Fabric filter - 3,5 MW 99,9% efficiency (Ce) - CeO2 Suspension (1g/l) - Concentration in flue gas 2,5 mg/m³ (dry) - 3 measuring points Fig.7: Explanatory illustration of the pilot scale furnace (BRENDA) at KIT, Karlsruhe Quelle: [5] Liesen, I.-M., Baumann W., Hauser M., Mätzing H., Paur H.-R., Seifert H., Untersuchung zur Freisetzung von synthetischen Nanopartikeln bei der Abfallverbrennung, Energie aus Abfall Band 12, 2015 Tagungsband 12

26 Studies in pilot scale facilities Emission behavior of nano-ceo2 (KIT) Gas combustion Coal combustion - Gas combustion: low dust concentration - Coal combustion: nano-ceo2 agglomerates at high dust concentrations with other dust particles Fig.8: Particle size distribution (impactor measurements )in BRENDA furnace after gas and coal combustion. Quelle: [5] Liesen, I.-M., Baumann W., Hauser M., Mätzing H., Paur H.-R., Seifert H., Untersuchung zur Freisetzung von synthetischen Nanopartikeln bei der Abfallverbrennung, Energie aus Abfall Band 12, 2015 Tagungsband 13

27 Studies in waste incineration plant Emission behavior of nano-ceo2 (ETH Zürich) Slag: C1: 81% Ce C2: 53% Ce Fly ash: C1: 19% Ce C2: 45% Ce Quench water: C1: 0,02% Ce C2: 1,7% Ce Electrostatic precipitator C1: 99,1 % efficiency (Ce) C2: 99,6 % efficiency (Ce) Fig.9: Detection of CeO2 nanoparticles in all solid and fluid waste combustion residues 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. 14

28 Conclusion

29 Conclusion Main share of Barium remains in solid incineration residues Bottom ash ca. 60 % Boiler ash ca. 6 % Filter dust ca. 3 % Common bag filters in WtE-plants are able to deposit [Barium-Sulfat] nanoparticles quantitatively Results of other research groups [CeO 2, TiO 2 ]comfirm these findings Nanoparticles were predominantely found in the ash Bag filters are suitable for separation Nanoparticles don t cause problems in WtE plants No relevant emissions to air path 24

30 Thank you for your interest!