HEALTH AND ENVIRONMENTAL ISSUES USING AMINES IN POST COMBUSTION CO2 CAPTURE

Claus Nielsen/University of Oslo Laila Iren Helgesen/Gassnova

Sun

Photo-oxidation

Dispersion

Cleaned flue gas + amine .. Fluegas

CO2 Capture

Amine waste

CO2

Environment 2

RESULTS FROM SELECTED CLIMIT FUNDED PROJECTS • • • • • •

NILU and research partners carried out a literature survey and a worst case study on nitrosamine/nitramine emissions ADA – Atmospheric Degradation of Amines – Testing in the Eufore reactor in Valencia Spain – Three consecutive studies Aminox – Statoil’s testing of nitrosamine formation in a MEA based capture process EXSIRA – a combination of activities studying the behaviour of amines in the environment RedEmm – Aker’s anti mist concept SOLVIT – Sintef, Aker and partners developing next generation solvents. HSE and the nitrosamine issue have been important evaluation criteria

3

AMINE PHOTO-OXIDATION Smog chamber experiments & mechanism development

• 11 European research groups coordinated by UiO – Norway, Sweden, Denmark, Austria, Germany, France, Spain, UK • 7 Experiment campaigns at EUPHORE, Spain – ADA: 2009, 2010, 2011. CCM: 2011. ACA: 2015, 2016 (2) • 9 Generic and 3 Potential Solvent amines – primary, secondary, tertiary, sterically hindered, di-amines – MEA, AMP, Piparazine • 9 Nitrosamines, 4 Nitramines, 3 Amides, 2 Imines

FROM LABORATORY TO ENVIRONMENT TIME RESOLVED SMOG CHAMBER EXPERIMENTS



QUANTUM CHEMISTRY O=N(=O)NCCO [µg/m3]

O=N(=O)NCCO [µg/m3]

(*e-6)

1.60

3.00

1.20



2.00

1.00

0.80

CRT-MODEL

0.40

METEOROLOGY

0.00

monthly mean Jul 2007

(*e-5)

4.00

0.00

monthly mean Jul 2007

5

THE AMINE QUALIFICATION TOOLBOX THE CCM PROJECT DEVELOPED A SET OF METHODS, MODELS AND PROCEDURES TO CLOSE THE KNOWLEDGE GAPS ON HSE IDENTIFIED FOR AMINES USED IN CCS

1. 2. 3. 4. 5. 6.

Toxicity assessment of nitrosamines and nitramines Sampling, preservation and analysis Solvent degradation rig Atmospheric amine chemistry Emission dispersion models Run-off and lake catchment models

Resently published at TCCS-8, Trondheim: “A way of qualifying Amine Based Capture Technologies with respect to Health and Environmental Properties” 6

RESULTS FROM TCM ACTIVITIES

•

•

• • •

Environmental baseline studies • Ambient air and water quality status in Mongstad vicinity • Established monitoring program Degradation studies • Hydrolysis, photolysis and biological degradation of nitrosamines/nitramines Emission control and monitoring • FTIR, PTR-tof-MS, PTR-QMS-MS, Isokinetic sampling/analysis Mist - Challenging in combination with particles and SO3 • Abatement measures – equipment and process parameters MEA and four commercial solvents have been tested • Good understanding of environmental properties • Industrial scale operation within strickt regulatory framework 7

EMISSION MEASUREMENTS: INSTRUMENT DEVELOPMENT @TCM Chemical matrix

• • • • • • • • •

• Challenge: To develop simple, fast, robust and reliable instrument

High humidity >90% CO2 in the stripper Ammonia 0.1 – 10 ppm • Modified commercial Aldehydes 0.1 – 100 ppm PTR-QMS instrument Amines 0.010 – 10 ppm • Verified against Ketones reference instrument Amides Nitrosamines DMA MEA DMEA MDEA LoD/ppbV (S/N=3) 13.2 0.8 0.4 0.6 Nitramines

PZ MEP AEP 0.4 0.5 0.6

DMA, dimethylamine; MEA, ethanolamine; DMEA, Dimethylethanolamine; MDEA, Methyl diethanolamine; PZ, piperazine; MEP, 1-Methylpiperazine; AEP, Aminoethylpiperazine 8

CONCLUDING REMARKS • • • • • • •

Carcinogenicity – Some nitrosamines are classified as probably carcinogenic to humans Nitrosamines and nitramines taken into account both in capture process and in atmosphere Risk reduction through closing knowledge gaps Generated new know-how of high scientific and technical quality Results from Mongstad not directly transferable to other locations – However, methodology and approach applicable elsewhere Sharing knowledge: – Close to 100 reports and publications prepared and made available www.gassnova.no and www.tcmda.com 9