materials and chemistry 1 theoretical study of amine degradation university of texas, 10 january...

1Materials and Chemistry

Theoretical study of amine degradation

University of Texas, 10 January 2008

Eirik F. da Silva, Karl A. Hoff, Kristin Rist Sørheim, Odd Gunnar Brakstad and Hallvard F. Svendsen

SINTEF Materials and Chemistry, NTNU and University of Florida


Outline

Application of Computational Chemistry

Toxicity and Biodegradation

Mechanistic Interpretation of Results

Carbamate Degradation


Computational Chemistry

Quantum Mechanical calculations (HF, DFT, MP2..) Potentially accurate results without any experimental input. Cost of calculations increase with the quality of results and the

size of the system being studied.

Solvation models (PCM, SM, Cosmo-RS ….) Simplified representation of interactions in a liquid

Classical simulations (Molecular Dynamics, Monte Carlo) Simplified “ball-and-stick” representation of molecules. Can represent a liquid phase explicitly. Quality of results depend

on parameterization.


Exploring Reactions

Computational Chemistry can be used to explore any reaction.

No general answers concerning the stability of species.

Experimental guidance is important.

Illustration from: helix.nih.gov


Snøhvit and REACT


OSPAR ConventionClassification of chemicals

Commercial chemical solvents like MDEA/piperazine are classified as red Red Category: Chemicals shall be phased out and/or substituted

ClassificationWater GreenChemicals on PLONOR list GreenHormone disturbing chemicals BlackList of prioritised chemicals that are contained in "resultatmål 1 (prioritetslisten) St. meld. nr 25 (2002-2003)"

Black

Biodegradability < 20 % and log Pow >= 5 BlackBiodegradability < 20 % and toxicity EC50 or LC50 <= 10 mg/l BlackTwo out of three categories: Biodegradability < 60% log Pow >= 3, IEC50 or LC50 10 mg/l

Red

Inorganic and EC50 or LC50 <= 1 mg/l RedBiodegradability < 20% RedOther chemicals Yellow


Absorption Chemistry

Tertiary amines Secondary amines Sterically hindered

amines

Primary amines Some cyclical

amines


• Regeneration energy requirement• Rate of reaction/Mass transfer • Cyclic capacity

• Molecular weight (per active site)• Foaming properties• Water solubility

• Molecular transport properties• Corrosion• Chemical stability• Toxicity and Biodegradation• Cost

Solvent selection criteria


REACT

Determine experimentally the ecotoxicity and biodegradability of a wide set of process chemicals.

Develop understanding of degradation in both process and environmental conditions.

Chemicals identified as promising shall be characterized by measurement of thermodynamical and kinetic data.

New solvents will be implemented in a process modeling tool and simulations performed to assess the process performance and energy requirements.


REACT

Ecotoxicity/biodegradablity

Molecular modeling/

QSAR studies

Process modeling

Solvent characterization

New solvent with thermal and chemical stability at process conditions

Classified as green or yellow

Degradationmechanisms


Selection of chemicals for testing

28 Candidates for first test campaign selected from Alkanolamines known to be in commercial operation (MEA, MDEA, AMP,

DEA etc.) New candidates deemed promising based upon earlier experience +

molecular modeling studies Cyclic amines Linear polyamines Sterically hindered amines

A larger set of data is required in order to correlate results with molecular structure


Ecotoxicity studies

Ecotoxicity tests recognized by OSPAR and by Norwegian Pollution authorities Phytoplankton: Skeletonema costatum (ISO/DIS 10253) – all

chemicals Marine biodegradation test (OECD 306) – all chemicals Bioaccumulation testing – calculations

Other bioassay studies Microtox assay – all chemicals Response studies in Calanus finnmarchicus – method

development on selected chemicals


Skeletonema – EC-50 resultsSkeletonema - EC50

100

101

102

103

104

EDA1.3-propane-diamine

MEAMPA

4-amino-1-butanolAMP

MMEAEAE

AEEADETAAMPD

DEABHEDGA

DMMEADEEAAEPDMDEAMIPADIPA

PyrrolidinePiperidinePiperazine

MorpholineHydroxyethylpiperazine

EC-50 (mg/L)


BOD resultsBOD

0 20 40 60 80 100

EDA1.3-propane-diamine

MEAMPA

4-amino-1-butanolAMP

MMEAEAE

AEEADETAAMPD

DEABHEDGA

DMMEADEEAAEPDMDEAMIPADIPA

PyrrolidinePiperidinePiperazine

MorpholineHydroxyethylpiperazine

BOD (% of ThOD)


Bioaccumulation test

Chemical test to determine the distribution of a chemical between two immiscible phases; octanol and water

The calculations were based on the difference between free energy of solvation in water (dGswater) and in the water-immiscible solvent octanol (dGsoctanol).

LogPOW =

Results: No tested chemicals were bioaccumulating (all water-soluble)

water octanol 1000

2.303 1.987 298

dGs dGs x

x x

-


Toxicity and log Pow correlation

1

10

100

1000

-2 -1.5 -1 -0.5 0 0.5 1 1.5 2

Calculated log Pow

Sk

ele

ton

em

a E

C5

0


Observations on degradation Sterically hindered amines degrade slowly. No obvious trends between different classes of amines. Initial search for correlation between calculated bond

breaking energies and degradation rates gave no correlation.

EPI suite of models fail to predict trends in biodegradability.

Most of the amines displaying high degradability are known enzyme substrates1: 8/10 Known enzyme substrates had BOD over 20 2/14 Amines not known be enzyme substrates have BOD over 20

1: BRENDA database (www.brenda.uni-koeln.de)


Proposed Mechanism for Copper Amino Oxidase:

Prabhakar and Siegbahn J. Comp. Chem. (2003)


Proposed Mechanism for Trimethylamine Dehydrogenase:

Basran, Sutcliffe and Scrutton J. Bio. Chem. (2001)


Proposed Mechanism for Ethanolamine Oxidase:

Warncke Biochemistry (2005)


Degradation Products


How to understand and predict biodegradation

Can degradation be accounted for by a single enzyme? Determine similarity with known amine substrates.

Develop QSAR based on likely reaction path(s). Quantum Mechanical calculations on key intermediates.

Experimental work to determine intermediates and final products


Carbamate Degradation


Transition State for Carbamate Degradation

Relative barriers: MEA: 55 kcal/mol DEA: 60 kcal/mol MPA: 53 kcal/mol EDA: 1700 kcal/mol


Conclusions

The amines tested show a relatively large span in both ecotoxicity and biodegradability

Most tertiary and sterically hindered amines are red Of the candidates identified as yellow, several are

promising solvents. For natural gas CO2 removal the gas is not oxidative. It

may therefore be easier to find a candidate solvent fulfilling the requirements of process stability and biodegradability

The relevance of these results for large scale post-combustion CO2 capture needs to be investigated further


Acknowledgements:

The REACT project is funded by the Research Council of Norway, through the strategic PETROMAKS program

Co-funded by Shell Technology Norway and Statoil ASA

Thank you for your attention!

materials and chemistry 1 theoretical study of amine degradation university of texas, 10 january...

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