Progetto: LIFE11 ENV/IT/ «SOREME» «Low cost sorbent for reducing mercury emissions» Start: 01/01/2013 End: 31/12/ month meeting Tartu, June Estonia EPENZ premises
ACTIONS ICCOM-ENEA Involvement/ Responsible ICCOM-ENEA-CONER CONER-EPENZ ICCOM-ENEA ALL PARTNERS-ENEA CONER-EPENZ CONER-EPENZ and ICCOM ICCOM
IMPLEMENTATION (B) AND MONITORING OF THE IMPACT OF THE PROJECT ACTIONS
DISSEMINATION ACTIONS COMPLETED
PROJECT MANAGEMENT AND MONITORING ACTIONS
D2. Activation of the project web site (Actions D2; deadline 31/01/2013) D1. Preparation and installation of the notice boards (Actions D1 deadline 31/03/2013) B1. Report on the SOREME sorbent production plant (Actions B1; deadline 31/03/2013) B2. Report on the SOREME sorbent (Actions B2; deadline 31/03/2013) E1. Inception project report (deadline 30/09/2013) B3. Report on the laboratory level demonstration (Action B3, 30/09/2013) C1. Report on the laboratory level monitoring (Action C1, 30/09/2013) DELIVERABLES produced in the first 12 months submitted to EU with the inception report
Action B4. Demonstration of the innovative project mercury sorbent at semi- industrial level Action B5. Demonstration of the innovative project mercury sorbent at industrial level Ehausted SOREME sorbent FTIR spectroscopy TGA ICP-MS for metal content GCMS of the extracts Milestone DMA80 mercury analyser Study of Hg 0 release from SOREME 4 and S4 pellets by GC-MS LCA study Action C2. Environmental monitoring of the innovative project mercury sorbent at semi-industrial level Action C5: Environmental monitoring of the innovative project mercury sorbent at industrial level Action C4:Feeedback on SOREME mercury sorbent use EPENZ and CONER ICCOM- PI and ENEA ACTIONS of the last 6 months
ACTIONS CARRIED OUT IN THE last 6 MONTHS OF THE SOREME PROJECT by ICCOMCNR (Action C2) In Action C2 ICCOMCNR and ENEA carried out the chemical-physical and the environmental characterization of the exhausted SOREME sorbent employed in semi-industrial test. The performances of the SOREME sorbent tested samples at semi-industrial level have been compared with the results obtained from commercial sorbent samples employed in the same industrial cycles. This action has been developed from month 13 to month 18 of the project development, later than foreseen because of the authorizations required to complete the Action B4.
Mercury sorption at high temperatures: lab- tests to simulate semi-industrial test operating conditons (Action B2 appendix) The mercury adsorption test described in Deliverable B2 was performed also a temperature higher than room temperature to simulate the real operating conditions in which gas flows may be at temperature between °C. DMA80 results obtained on SOREME4 after the mercury sorption lab-test performed at room temperature, 60 and 100°C (A, 10 min exposure) and performed keeping the bed reactor at 100°C for 10, 20 and 30 min (B), respectively.
Release of mercury in gas phase from exhausted SOREME from lab- tests. Two series of experiments were performed in order to verify the release of mercury in the gas phase from exhausted SOREME samples employed in lab tests. 1) 10 sample containing 2-5 ugHg 0 /g SOREME were treated in DMA80 at 100, 150 and 200°C for 10 min and the Hg 0 released at each temperature was quantified. 2) 10 samples were kept at 100°C or 200°C for increasing times and the Hg 0 released was quantified (kinetics study of the release). At 200°C only 31 ±2% Hg 0 was released. 95 ±1% Hg 0 is released only treating the sample at 800°C for 10 min, which are the typical conditions for the analysis of total mercury. 100°C200°C The results obtained with the two procedures confirmed a strong interaction/bond of mercury with SOREME sorbent.
Impregnation of SOREME4 sorbent with NaCl solution. A unforeseen,novel, “green” result In 2014 a novel paper has been published related to the collection of atmospheric gaseous mercury for stable isotope analysis using iodine- and chlorine-impregnated activated carbon (AC) traps [Xuewu Fu, Lars-Eric Heimburgera and Jeroen E. Sonk, Collection of atmospheric gaseous mercury for stable isotope analysis using iodine- and chlorine-impregnated activated carbon traps, J Anal Atom Spectrom 2014, DOI: /c3ja50356a]. In this work the authors propose the impregnation of AC for analytical purposes. Representative raw data of real-time Hg breakthrough curve from mercury adsorption test performed on dried NaCl/KI impregnated SOREME sample (100 mg, 187 min exposure) and not impregnated SOREME 4 (50mg, 90 min exposure). NaCl/KI impregnated SOREME samples had better efficiency than not treated SOREME 4 The mercury sorption capacity is about 4 times higher For about 80 min the sorbent captured all Hg 0 delivered (about 8.5 ug) before showing a saturation trend.
Mercury sorption capacity of NaCl/KI impregnated SOREME4, not impregnated SOREME 4 and commercial AC samples (100 mg, 10 min exposure). This unexpected result is fundamental for future applications of SOREME 4: NaCl and KI are safe compounds; in the perspective of a low-cost, “green” exploitation of SOREME sorbent the seawater itself could be employed for impregnation (study in progress). A target for a patent? It was proposed that the oxidation of Hg 0 by I 2 and Cl 2 as well as their reactive halogen compounds played a major role in uptake of Hg 0 by activated carbons.
Release of mercury from SOREME4 with mercury adsorbed in various operating conditions, KI/NaCl impregnated SOREME4 and commercial sorbent samples. The interaction is even stronger with KI/NaCl impregnated SOREME4 and comparable with commercial AC.
Chemical characterization of exhausted SOREME from semi-industrial tests: Sercim samples
Semi-industrial apparatus for semi-industrial test at Sercim Crematorium (Action B4 CONER) Stainless steel “baskets” designed and produced by CONER to contain the SOREME sorbent and the commercial product (0.5 kg) employed by SerCim following the statutory law to adsorb mercury from the gas flow.
Operating conditions adopted in 7 semi- industrial experiments and humidity values measured in each sample. Experiment #Operating conditions Humidity measured in the exhausted SOREME sample* Humidity measured in the exhausted COMMERCIAL SORBENT sample* Not exposed- 0.4%31% 1Blank- 30 min emissions without cremation 2.0%32.4% 23 h exposition (2 cremations) 1.6%29.2% 33 h 40 min exposition (2 cremations) 1.5%29.7% 46 h 10 min exposition (4 cremations) 4.1%34.3% 56 h 45 min exposition (4 cremations) 7.0%37.1% 66 h exposition (4 cremations) 5.5%34.3% 76 h exposition (4 cremations) 4.0%33.6%
Mercury content measured by DMA80 in the exhausted SOREME and commercial samples from the 7 semi-industrial experiments. Exp #* Hg 0 Sorption capacity SOREME (mg/g) Hg 0 Sorption capacity COMMERCIAL SORBENT (CS mg/g) Improvement factor of sorption capacity (Smg/g) /(CSmg/g) Improvement factor Corrected* For each test N=10 samplings (70 tests total); SD < 3%. * commercial sorbent employed contains only 30% activated carbon (AC) and 70% sodium bicarbonate in order to neutralize acid emission coming from cremations. SOREME had better sorption capacities with respect to commercial sorbent with an improvement of its sorption capacity ranging from 1.1 up to 4.1 times, according to the objectives of SOREME project.
Release of mercury in gas phase from exhausted SOREME and commercial carbon used in SerCim semi-industrial tests. Release of Hg 0 from exhausted SOREME (experiment 5 and 6) and commercial exhausted carbon samples at increasing temperatures. The results show that also in real conditions mercury is more strongly adsorbed (chemisorbed) to SOREME4 than to commercial sorbent. The mercury released at 200°C from SOREME is indeed ¼ than mercury released at the same temperature from commercial sorbent (<5% with respect to 20%). This information is fundamental for LCA. SOREME (as well as commercial sorbent) cannot be re-used. The retention of mercury up to 200°C gives indications on its disposal as waste.
Leaching tests on exhausted SOREME and commercial carbon used in SerCim semi- industrial experiments were performed following the UNI method. No significant amounts of mercury (< LOD 0.2 ppb) were released in aqueous solutions from exhausted SOREME and commercial carbon used in SerCim semi-industrial tests. While in the case of commercial product this result can be due to the low amount adsorbed, in the case of SOREME this could be because mercury is chemisorbed to SOREME through strong covalent bonds C-S. This information if fundamental for LCA to plan the final disposal of exhausted SOREME. Release of mercury in liquid phase from exhausted SOREME and commercial carbon used in SerCim semi-industrial experiments (leaching tests). 1 g SOREME carbon + 10 mL 24 h stirring at room temperature Centrifugation DMA 80 and ICP- MS analysis
Thermogravimetric Analysis (TGA) of exhausted SOREME and Sercim commercial product sampleTotal weight loss (%) Commercial sorbent Sercim before its use 45.3* Commercial sorbent –EXP 143.5* Commercial sorbent –EXP 248.1* Commercial sorbent –EXP 345.0* Commercial sorbent –EXP 446.0* Commercial sorbent –EXP 543.9* Commercial sorbent –EXP 644.2* Commercial sorbent –EXP 745.1* SOREME before its use3.4 SOREME –EXP SOREME –EXP SOREME –EXP SOREME-EXP SOREME –EXP SOREME –EXP SOREME –EXP 7
FTIR Analysis of exhausted SOREME and Sercim commercial product
GC-MS Analysis of exhausted SOREME and Sercim commercial product Comparison of GCMS chromatograms of compound released from SOREME active carbon (S5, blue line) commercial active carbon (C5, magenta line) and blank SOREME active carbon (red line). The commercial sorbent did not adsorbed significant concentrations of VOC, while SOREME adsorbed many compounds. Several compounds were identified. Retention Time (min) Compounds 4.82propane+propene 5.52isobutane butene trans butene cis 7.92isopentene 8.45isopentane 9.46Dimethyl-cyclopropane 9.77pentane+pentene 10.48trans-2-pentene 10.99cis-2-pentene pentene 11.99aceton 13.28ciclopentene 13.87ter-butanolo 14.83metil-pentene 15.08esano butanone 18.60benzene 21.93toluene 14.83methyl-pentene 14.83methyl-pentene
Conclusive remarks to Action C2 The following expected results were completely met and demonstrated: the flexibility of the use of the SOREME sorbent in different incineration cycles the operating conditions of the SOREME sorbent, their mechanical properties, Hg absorption and desorption conditions with a knock on effects on exhausted SOREME final disposal. the innovative higher quality of SOREME, which absorbs mercury about 10 times more that commercial products employed in incineration cycles thanks to the endogenous sulfur content, despite its surface area is about 1/5 of commercial activated carbon samples. the innovative higher Hg loadings after semi-industrial cycles compared with commercial. A possible constraint, i.e. the not efficiency of SOREME in semi-industrial real cycles, was not evidenced. Instead, SOREME sorbent properties were even better in semi-industrial cycles with real gas flows with respect to sorbent properties of commercial products. After use SOREME cannot be reactivated because it does not release mercury up to 200 °C. This information is important in LCA assessment that is in progress.
D7. Preparation of dissemination materials (Actions D7; deadline 31/12/2013) ICCOM CNR (CGS) B4. Report on the semi-industrial level demonstration (Action B4, 31/03/2014) CONER C2. Report on the semi-industrial level monitoring (Action C2, 31/03/2014) ICCOM CNR DELIVERABLES to be prepared to be submitted to EU with the Progress Report (30/06/2014) MILESTONES OF THE PROJECT Semi-industrial level mercury adsorption demo (Action B4, 31/03/2014)- CONER
Action B4. Demonstration of the innovative project mercury sorbent at semi- industrial level-last tests Action B5. Demonstration of the innovative project mercury sorbent at industrial level Action C2. Environmental monitoring of the innovative project mercury sorbent at semi-industrial level Action C3. Environmental monitoring of the innovative project mercury sorbent at industrial level Action C4:Feeedback on SOREME mercury sorbent use Action C5: Environmental monitoring of the innovative project mercury sorbent at industrial level EPENZ and CONER ICCOM- PI and ENEA ACTIONS of the next 6 months Ehausted SOREME sorbent FTIR spectroscopy TGA ICP-MS for metal content GCMS of the extracts Milestone DMA80 mercury analyser Study of Hg 0 release from SOREME 4 and S4 pellets by GC-MS LCA study
B5. Report on the industrial level demonstration (Action B5, 31/12/2014)- EPENZ/CONER C3. Report on the industrial level monitoring (Action C3, 31/12/2014) ICCOMCNR C4. Report on SOREME use feedbacks (Action C4, 31/12/2014) ICCOMCNR/CONER/LEGISLATION/EPENZ C5. Report on the project technical-economical viability (Action C5, 31/12/2014) ENEA-LCA D3. Layman Report (Action D3, 31/12/2014) ICCOMCNR D5. Report on the networking results (Actions D5; deadline 31/12/2014) ICCOMCNR FINAL PROJECT REPORT (with Audit Report) (Acion E1; 31/12/2014) ICCOMCNR DELIVERABLES to be prepared in the next 6 months to be submitted to EU with the Final Report (31/12/2014)
SOREME ICCOM-PI Emilia Bramanti Alessandro D’Ulivo Massimo Onor Manuela Cempini Valentina Della Porta Susanna Monti Emanuela Pitzalis Marco Carlo Mascherpa Simone Scardiglia Simona Biagi