What is the process of coal sampling

Behavior of trace substances in the HTC of sewage sludge

Transcript

1 Jochen Türk, Claudia vom Eyser, K. Palmu, R. Otterpohl and T.C. Schmidt Institute for Energy and Environmental Technology e.v. Behavior of trace substances in the HTC of sewage sludge

2 Contents 1. Introduction! Trace substances in sewage sludge! Sewage sludge treatment using HTC 2. Hydrothermal carbonation at the IUTA 3. Results! Drug! Perfluorinated substances (PFC)! Polycyclic aromatic hydrocarbons (PAH), dioxins & furans, polychlorinated biphenyls (PCB) 4. Summary IFAT, Munich,

3 Background trace substances in sewage sludge Concentration, ng / g DM thumbs / image_thumb jpg; eintelligence.de/wp-content/ Nieto et al., 2007; Nieto et al., 2010; Jones-Lepp et al., 2007; Nieto et al., 2008; Lillenberg et al., 2009; uploads / 2 Göbel 010/09 / et al., 2005; Maoz & Chefetz, 2010; Ternes et al., 2005; Radjenovic et al., 2009; Ding et al., 2011 arzneimittel_dragees.jpg; http: // static.freepik.com/fotos-kostenlos/stri chmannche n - mannlich_ jpg; Waters sewage sludge full / t / toilet jpg; http: // ueb ersicht-pum pen-fuerklaeranlage.jpg IFAT, Munich,

4 laws, requirements no limit values ​​for pharmaceuticals sewage sludge and biochar sewage sludge: pollutant sink transformation processes hydrothermal carbonization (HTC) possible nature pollutant sink> 1 million years no legal requirements background biochar HTC 2-12 hours C nutrient source agricultural utilization incineration nutrient source (phosphorus, nitrogen) IFAT, Munich,

5 HTC process spark, 2012 IFAT, Munich,

6 Contents 1. Introduction! Trace substances in sewage sludge! Sewage sludge treatment using HTC 2. Hydrothermal carbonation at the IUTA 3. Results! Drug! Perfluorinated substances (PFC)! Polycyclic aromatic hydrocarbons (PAH), dioxins & furans, polychlorinated biphenyls (PCB) 4. Summary IFAT, Munich,

7 HTC at IUTA Büchi Limbo Typical process parameters: - 50 g sewage sludge - 17 ml water 200 ml up to 350 C up to 350 bar stainless steel min C - 4 hours - approx. 15 bar IFAT, Munich,

8 Sample preparation Hydrothermal carbonization of sewage sludge /una_bg_misc_008.jpg Extraction pressure-reactors-agitator-autoclaves / limbo.html Freeze-drying Filtration onaws.com/img/ picts / mixijnyz.jpg Purification, quality clarification control sludge, biochar analysis / wikimedia / wikimedia.upload.wikimedia.or g / wikimedia.or g / wikimedia. da / SPE_Manifold.jpg IFAT, Munich,

9 Contents 1. Introduction! Trace substances in sewage sludge! Sewage sludge treatment using HTC 2. Hydrothermal carbonation at the IUTA 3. Results! Drug! Perfluorinated substances (PFC)! Polycyclic aromatic hydrocarbons (PAH), dioxins & furans, polychlorinated biphenyls (PCB) 4. Summary IFAT, Munich,

10 results trace substances degradation behavior of pharmaceuticals during the HTC! Different substance classes! Different adsorption behavior! Standard addition over the entire process! ASE extraction: 100 C, 100 bar, 1 x 15 min, 10% flush volume! Filtration (0.25 µm)! LC-MS / MS measurement IFAT, Munich,

11 Results trace substances degradation behavior of drugs during the HTC 500 concentration, ng / g DM <5 <26 <64 <12 <113 <1240 <46 <145 <234 <91 <10 <7 <19 sewage sludge biochar HTC parameters: 50 g sewage sludge (Rheinhausen), 17 ml water, 500 min -1, 210 C, 4 hours IFAT, Munich,

12 120% 100% results trace substances degradation behavior of drugs during the HTC Diclofenac degradation c / c 0 80% 60% 40% 20% formation of relevant degradation products? 0% time, min HTC parameters: Diclofenac, c 0 = 10 mg / kg, HTC at 210 C, different running times IFAT, Munich,

13 Results Trace substances degradation behavior of drugs during HTC Diclofenac degradation Name Mass [Da] Ionization mode Retention time [min] Intensity * Literature I 239 positive [1] II 257 positive [2] III 270 negative [1] IV 272 negative V 282 positive [3] , [4], [5] VI 285 positive VII 298 negative VIII 313 positive [5], [6] IX 327 positive [5], [6] X 331 positive / negative XI 345 positive / negative XII 353 positive XIII 353 positive IX 367 positive [7] decarboxy-diclofenac * Determined from the peak area: + <1e7; ++> 1e7; +++> 2e7 [1] Poiger et al. (photodegradation); [2] Eriksson et al. (photochemical degradation); [3] Soufan et al. (chlorination); [4] Aguera et al. (phototransformation), [5] Perez-Estrada et al. (photo-fenton); [6] Calza et al. (photocatalytic with TiO 2); [7] Kosjek et al. (model treatment plant) IFAT, Munich,

14 results trace substances perfluorinated substances (PFC)! Strong adsorption, thermally very stable! DIN draft for the determination of PFC in sludge (DIN)! Standard addition over the entire process! ASE extraction: 70 C, 100 bar, 2 x 7 min! SPE purification! Filtration (0.25 µm)! LC-MS / MS measurement IFAT, Munich,

15 results trace substances perfluorinated substances (PFC) inert tests recovery,% h 180 C 210 C 240 C 24 h 180 C 210 C 240 C PFOA liquid liquid phase phase extracted extracted phase phase PFOS process parameters: "PFOS 50 g sand, temperature-stable 17 ml water , 500 min as -1, PFOA 4 hours, C 0 = 200 ng IFAT, Munich,

16 60 Results PFC Perfluorinated substances (PFC) during the HTC concentration, ng / g TS sewage sludge coal "No significant changes in the PFC concentrations Process parameters: during the HTC 50 g sewage sludge (Hamburg Hollenstedt), 17 ml water, 500 min -1, 210 C, 4 hours IFAT, Munich,

17 Results trace substances Polycyclic aromatic hydrocarbons (PAk), dioxins & furans (PCDD / F) and polychlorinated biphenyls (PCB) during the HTC! Partial limit values ​​for sewage sludge exist! Validated methods for the investigation of sewage sludge available! 16 priority PAHs, 6 DIN PCBs, 7 dioxins and 10 furans! PAHs, dioxins and furans can arise in pyrolysis processes! Demand for legal regulations for biochar IFAT, Munich,

18 Results trace substances Polycyclic aromatic 25 hydrocarbons (PAk), dioxins & furans (PCDD / F) 20 and polychlorinated biphenyls (PCB) 15 during the HTC sewage sludge HTC coal limit value of the German sewage sludge ordinance Polycyclic aromatic 0 hydrocarbons (PAH), mg / kg DM 2.02 Sewage Sludge 3.30 HTC Coal (1) Dioxins & Furans, ng / kg DM Polychlorinated Biphenyls, mg / kg DM concentration, ng / kg DM concentration, mg / kg DM, 35 18.7 100 (30) 4 3 0.02 2 0.03 0.20 (0.1) 1 0 sewage sludge HTC coal sampling 1 sampling 2 sampling 3 IFAT, Munich,

19 Contents 1. Introduction! Trace substances in sewage sludge! Sewage sludge treatment using HTC 2. Hydrothermal carbonation at the IUTA 3. Results! Drug! Perfluorinated substances (PFC)! Polycyclic aromatic hydrocarbons (PAH), dioxins & furans, polychlorinated biphenyls (PCB) 4. Summary IFAT, Munich,

20 summary! Medicines o Some active pharmaceutical ingredients are broken down during the HTC o Example diclofenac: characterization of transformation products o Further investigations are currently underway! PFC o no significant reduction of the PFC load by the HTC o PFOS more temperature stable than PFOA! PAH, Dioxins & Furans, PCB o no significant change in PAH pollution caused by HTC o slight increase in dioxin and furan concentration (no limit value exceeded so far) o no significant change in PCB pollution caused by HTC Investigations not problematic. The exposure to trace substances could be reduced to some extent. IFAT, Munich,

21 Thank you for your attention! IFAT, Munich,

22 IFAT, Munich,