Progetto: LIFE11 ENV/IT/ 000109 «SOREME»

«Low cost sorbent for reducing mercury emissions»

Start: 01/01/2013End: 31/12/2014

18 month meetingTartu, June 19 2014

EstoniaEPENZ premises

ACTIONS

ICCOM-ENEAICCOM-ENEAICCOM-ENEA

Involvement/Responsible

ICCOM-ENEA-CONERCONER-EPENZ

ICCOM-ENEAICCOM-ENEAALL PARTNERS-ENEACONER-EPENZCONER-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 levelAction B5. Demonstration of the innovative project mercury sorbent at industrial level

Ehausted SOREME sorbent

FTIR spectroscopyTGAICP-MS for metal contentGCMS of the extractsMilestone DMA80 mercury analyser

Study of Hg0 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 levelAction C5: Environmental monitoring of the innovative project mercury sorbent at industrial levelAction 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 50-100°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.

20 40 60 80 1000

1

2

3

4

5

6

adso

rbed

Hg0 ,

g/g

temperature, °C

A

10 20 302

3

4

5

6

7

8

adso

rbed

Hg0 ,

g/g

exposure time, min

B

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 ugHg0/gSOREME were treated in DMA80 at 100, 150 and 200°C for 10 min and the Hg0 released at each temperature was quantified.2) 10 samples were kept at 100°C or 200°C for increasing times and the Hg0 released was quantified (kinetics study of the release).

100°C 150°C 200°C residual tot (800°C)0

20

40

60

80

100A

% H

g0 re

leas

ed

Temperature, °C

At 200°C only 31 ±2% Hg0 was released. 95 ±1% Hg0 is released only treating the sample at 800°C for 10 min, which are the typical conditions for the analysis of total mercury.

10 20 30 40 residual tot (800°C)0

50

100

% H

g0 rele

ased

Time, min

A

10 20 30 40 residual tot (800°C)0

50

100

% H

g0 rele

ased

Time, min

B100°C 200°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: 10.1039/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).

0 2000 4000 6000 8000 10000

0.00

0.05

0.10

0.15

0.20

sign

al

time, s

SOREME 4

NaCl/KI imoregnated SOREME

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 Hg0 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).

SOR

EME4

SOR

EME4

rep

KI/N

aCl S

OR

EME4

KI/N

aCl S

OR

EME4

rep

CA

0

20

40

60

Hg0 ,

g/g

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 Hg0 by I2 and Cl2 as well as their reactive halogen compounds played a major role in uptake of Hg0 by activated carbons.

Release of mercury from SOREME4 with mercury adsorbed in various operating conditions, KI/NaCl impregnated SOREME4 and commercial sorbent samples.

100 150 200 residual total

0.0

0.2

0.4

0.6

0.8

1.0H

g0 rele

ased

, fra

ctio

n

temperature, °C

SOREME4_21°C_10min SOREME4_21°C_10min rep SOREME4_60°C_10min SOREME4_100°C_10min SOREME4_100°C_20min SOREME4_100°C_30min KI/NaCl SOREME4 KI/NaCl SOREME4 rep commercial AC_21°C_10min

@200°C

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)

COMMMERCIAL product SOREME

Gas flow

Gas flow

Conventional bag filters with commercial product

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%

1 Blank- 30 min emissions without cremation

2.0% 32.4%

2 3 h exposition (2 cremations)

1.6% 29.2%

3 3 h 40 min exposition(2 cremations)

1.5% 29.7%

4 6 h 10 min exposition(4 cremations)

4.1% 34.3%

5 6 h 45 min exposition (4 cremations)

7.0% 37.1%

6 6 h exposition (4 cremations)

5.5% 34.3%

7 6 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 #* Hg0 Sorption capacity SOREME (mg/g)

Hg0 Sorption capacity COMMERCIAL SORBENT (CS mg/g)

Improvement factor of sorption capacity(Smg/g) /(CSmg/g)

Improvement factorCorrected*

1 28.9 6.9 4.2 1.4

2 10.5 14.6 - -

3 6.3 38.8 - -

4 15.2 4.5 3.3 1.1

5 520.8 42.7 12.2 4.1

6 364 41 8.9 3.0

7 38.7 15.5 - -

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 Hg0 from exhausted SOREME (experiment 5 and 6) and commercial exhausted carbon samples at increasing temperatures. 

100 150 200 residual

0.0

0.2

0.4

0.6

0.8

1.0

Hg0 re

leas

ed, f

ract

ion

temperature, °C

Exp 5a_SOREME Exp 5b_SOREME Exp 5a_COMMERCIAL Exp 5b_COMMERCIAL Exp 6a_SOREME Exp 6b_SOREME Exp 6a_COMMERCIAL Exp 6b_COMMERCIAL

@200°C

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 10802 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 temperatureCentrifugation

DMA 80 and ICP-MS analysis

Thermogravimetric Analysis (TGA) of exhausted SOREME and Sercim commercial product

sample Total weight loss (%)

Commercial sorbent Sercim before its use

45.3*

Commercial sorbent –EXP 1 43.5*Commercial sorbent –EXP 2 48.1*Commercial sorbent –EXP 3 45.0*Commercial sorbent –EXP 4 46.0*Commercial sorbent –EXP 5 43.9*Commercial sorbent –EXP 6 44.2*Commercial sorbent –EXP 7 45.1*SOREME before its use 3.4SOREME –EXP 1 2.59SOREME –EXP 2 3.59SOREME –EXP 3 1.98SOREME-EXP 4 2.49SOREME –EXP 5 7.85SOREME –EXP 6 6.25SOREME –EXP 7  

FTIR Analysis of exhausted SOREME and Sercim commercial product

C5

C1, C2, C3, C4

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450,0cm-1

3358

2434 1914

1610

1449

1272

1045

1031

986684654

1915

1613

1451

1275

1045

1031

990 831 656

A

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600cm-1

Commercial sorbent before use (black)

C7 (green)C6 (pink)

2900

2442

2039

1913

1730

1695

1611

1450

1379

1271

1045

1031

987686

655

A

S5

S1

S2

S3S4

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600cm-1

31052824

2165

1074

780617

465

3063 2555

2180

1525

1074

786

611472

298828822815

2217

1530

1097

3001 2189

1074

785

468

1057

781

A

S7

4000,03600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600cm-1

36392604 2107 1581

1080

S6

A

GC-MS Analysis of exhausted SOREME and Sercim commercial product

RT: 0.00 - 24.00

0 2 4 6 8 10 12 14 16 18 20 22 24Time (min)

0

20

40

60

80

1000

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100 18.60

21.93

4.82

6.129.77

5.52 11.248.48 13.916.48

16.5714.83 16.846.91 13.6510.489.46 21.0219.0022.39

16.247.94 11.99

5.8422.3917.344.65 18.136.04 13.90 17.03 19.90 20.5613.017.57 10.808.77

6.576.0422.40

17.356.89 13.939.76 17.578.50 17.0513.01 19.37 21.4610.63

NL:2.00E6m/z= 35.00-200.00 MS SOR5b

NL:2.00E6m/z= 35.00-200.00 MS ref4rb

NL:2.00E6m/z= 35.00-200.00 MS c5

x20 x20

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

4.82 propane+propene5.52 isobutane6.48 2-butene trans6.91 2-butene cis7.92 isopentene8.45 isopentane9.46 Dimethyl-cyclopropane9.77 pentane+pentene10.48 trans-2-pentene10.99 cis-2-pentene11.24 1-pentene11.99 aceton13.28 ciclopentene13.87 ter-butanolo14.83 metil-pentene15.08 esano16.83 2-butanone18.60 benzene21.93 toluene14.83 methyl-pentene14.83 methyl-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 testsAction B5. Demonstration of the innovative project mercury sorbent at industrial level

Action C2. Environmental monitoring of the innovative project mercury sorbent at semi-industrial levelAction C3. Environmental monitoring of the innovative project mercury sorbent at industrial levelAction C4:Feeedback on SOREME mercury sorbent useAction 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

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 PEOPLE @ ICCOM-PI

Emilia Bramanti Alessandro D’Ulivo

Massimo Onor

Manuela Cempini

Valentina Della PortaSusanna Monti

Emanuela Pitzalis

Marco Carlo Mascherpa

Simone Scardiglia

EU project LIFE+2011 ENV/IT/109 SOREME“Low cost sorbent for reducing mercury emissions”

SimonaBiagi