1 Environmental impacts and aspects of absorbents used for CO 2 capture Ingvild Eide-Haugmo 1, Karl Anders Hoff 2, Odd Gunnar Brakstad 2, Kristin R. Sørheim

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Environmental impacts and aspects of absorbents used for CO2 capture

Ingvild Eide-Haugmo1, Karl Anders Hoff2, Odd Gunnar Brakstad2, Kristin R. Sørheim2, Hallvard F. Svendsen1

1Norwegian University of Science and Technology (NTNU),2Sintef Materials and Chemistry,

Trondheim, NORWAY

Ingvild Eide-Haugmo, Research Review Meeting 10-11.01.08

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Outline

• Objective• Plan• Work started

– Marine Biodegradation test

– Marine Phytoplankton test

• Categorization of chemicals• Summary of results


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Objective

• Increase the understanding of environmental effects when amines are released to marine environments.

• Combine this with understanding of properties and degradation chemistry for amines in CO2-removal processes for natural gas.

• This will give a foundation for an optimized choice of process chemicals.

• The work will be divided into two parts: 1. Finding new process chemicals that are ecotoxicologically

acceptable. 2. Attain a detailed understanding of the reaction

mechanisms of decomposing - both in process and environmental conditions.


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Plan – First part

• Experimental characterization: Toxicology and biodegradation studied for a wide range of chemicals by standardized and internationally accepted tests. – Marine biodegradation test (OECD 306) – Marine phytoplankton test with Skeletonema Costatum (ISO/DIS-

10253)

• Results will be treated with statistical methods to find relation between structure, toxicology and degradation. – Quantitative structure-activity relationship (QSAR)

• Further studies of selected chemicals– Bioaccumulation studies (OECD 117)

– Response studies with the copepod Calanus finmarchicus


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Plan – Second part

• Determine potential degradation products both at process conditions and in marine environments, and find methods for characterizing the experimental systems. – Spectroscopic methods (IR/ FTIR, NMR)– Chromatographic methods (LC-MS)

• Measurements of the degradation products over time to gain insight into kinetics.

• Reported degradation products and quantum mechanical calculations will be used to substantiate reaction mechanisms.

• If possible make chemometric model for predicting environmental impact of chemicals.


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Work started

• Marine biodegradation test– Test conducted according to

OECD Guideline 306, ”Closed bottle test”.

– The chemical is solved in seawater and the solution is distributed in air-tight bottles with incubation for 28 days at 20 ºC.

– Oxygen consumption is measured at 0, 5, 15 and 28 days. The biodegradation is determined as percent of the theoretical oxygen demand (ThOD) for the chemical.

Dissolved oxygen meter


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Work started• Marine phytoplankton test

– Test conducted according to ISO/DIS Guideline 10253, using the photosynthesising algae Skeletonema Costatum.

– Algal culture is inoculated in a concentration series of amines, and in pure growth medium.

– Samples incubated at 20 ºC for 72 hours. Inhibition of algal growth measured as reduction in in vivo chlorophyll fluorescens, with measurements at 0, 24, 48 and 72 hours.

– EC-50 concentration determined as concentration of chemicals inhibiting algal growth by 50%.

Fluorometer with sample


8Norwegian offshore oil industry

Categorization of chemicalsCategory Criteria – Ecotoxicity tests Actions

Black

•Priority list (Stortingsmelding Nr. 25)•OSPAR List of Chemicals for Priority Action •Both low biodegradability and high bioaccumulation (BOD28 < 20 %, and Log POW ≥ 5)

•Low biodegradability and toxic (BOD28 < 20 %, and EC50 or LC50 ≤ 10 mg/L)•Compounds expected to be carcinogenic/mutagenic or harmful to reproduction

Not discharged

Red

•Inorganic chemicals with high toxicity (EC50 or LC50 ≤ 1 mg/L)•Organic chemicals with low biodegradability (BOD28 < 20 %)•Organic chemicals or mixtures which meet 2 of the 3 following criteria: Biodegradability < 60 %, bioaccumulation potential (Log POW ≥ 5), or toxicity of EC50 or LC50 ≤ 10 mg/L

Phased out or replaced

Yellow •Include compounds which based on their characteristics are not defined as RED or BLACK, and •NOT included in the PLONOR list

Accepted

Green •Chemicals expected to have NO environmental effects•PLONOR list

Testing not required


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Summary of resultsTwo test campaigns completed, where ecotoxicity and biodegradability have

been tested for 41 potential solvent candidates.Skeletonema - EC50

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101

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EDA1.3-propane-diamine

MEAMPA

4-amino-1-butanolAMP

MMEAEAE

AEEADETA

AMPDDEABHEDGA

DMMEADEEAAEPDMDEAMIPADIPA

PyrrolidinePiperidinePiperazine

MorpholineHydroxyethylpiperazine

TMPDAGlycine

SarcosineAlanineDMAPA

Dimethylam.DMPAPETAACHP

TertBut EtanolamineSpermidine

SpermineSulfolan

TriethylamineDMPDA

MAPA

EC-50 (mg/L)

BOD

0 20 40 60 80 100

EDA1.3-propane-diamine

MEAMPA

4-amino-1-butanolAMP

MMEAEAE

AEEADETA

AMPDDEABHEDGA

DMMEADEEAAEPDMDEAMIPADIPA

PyrrolidinePiperidinePiperazine

MorpholineHydroxyethylpiperazine

TMPDAGlycine

SarcosineAlanineDMAPA

Dimethylam.DMPAPETAACHP

TertBut EtanolamineSpermidine

SpermineSulfolan

TriethylamineDMPDA

MAPA

BOD (% of ThOD)


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Results - Examples


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Thank you

• Questions?

Documents

1 Environmental impacts and aspects of absorbents used for CO 2 capture Ingvild Eide-Haugmo 1, Karl Anders Hoff 2, Odd Gunnar Brakstad 2, Kristin R. Sørheim