Amine degradation in CO2 capture. I. A review

Abstract Post-combustion CO2 capture based on CO2 absorption by aqueous amine solutions is the most mature gas separation technology. A main problem is amine degradation due to heat, CO2, O2, NOx and SOx. This review proposes to make a critical survey of literature concerning degradation, to list degradation products and to discuss mechanisms proposed by authors. Benchmark molecule is monoethanolamine (MEA) but diethanolamine (DEA), N-methyldiethanolamine (MDEA), piperazine (PZ) and 2-amino-2-methylpropan-1-ol (AMP) are also studied. Uses of other amines and amine blends are also considered. In the case of MEA, ammonia, N-(2-hydroxyethyl)-piperazin-3-one (HEPO) and N-(2-hydroxyethyl)-2-(2-hydroxyethylamino) acetamide (HEHEAA) are the main identified degradation products in pilot plants. Among lab studies, the most cited degradation products are ammonia, carboxylic acids, N-(2-hydroxyethyl)-formamide (HEF), N-(2-hydroxyethyl)-acetamide (HEA) and N-(2-hydroxyethyl)-imidazole (HEI) for oxidative degradation, and oxazolidin-2-one (OZD), N-(2-hydroxyethyl)-ethylenediamine (HEEDA) and N-(2-hydroxyethyl)-imidazolidin-2-one (HEIA) for thermal degradation. Numerous degradation products have been identified but some are still unknown. A lot of degradation mechanisms have been proposed but some are missing or need proofs. SOx and NOx effects are still few examined and much work remains to be done concerning volatile degradation products potentially emitted to atmosphere: their identification and their formation mechanisms need further investigations.

[1]  M. Attalla,et al.  N-Nitrosopiperazines form at high pH in post-combustion capture solutions containing piperazine: a low-energy collisional behaviour study. , 2010, Rapid communications in mass spectrometry : RCM.

[2]  Shujuan Wang,et al.  Pilot-Scale Experimental Study on the CO2 Capture Process with Existing of SO2: Degradation, Reaction Rate, and Mass Transfer , 2011 .

[3]  Abhoyjit S Bhown,et al.  Analysis and status of post-combustion carbon dioxide capture technologies. , 2011, Environmental science & technology.

[4]  L. Nhamo,et al.  Chemical constituents of the Combretaceae. Part II. Substituted phenanthrenes and 9,10-dihydrophenanthrenes and a substituted bibenzyl from the heartwood of Combretum molle , 1972 .

[5]  A. Meisen,et al.  Gas chromatographic detection of diethanolamine and its degradation products , 1980 .

[6]  M. Mimeault,et al.  Estimation of the CO2 Absorption Capacities in Aqueous 2-(2-Aminoethylamino)ethanol and Its Blends with MDEA and TEA in the Presence of SO2 , 2007 .

[7]  P. Carrette,et al.  New Amines for CO2 Capture. III. Effect of Alkyl Chain Length between Amine Functions on Polyamines Degradation , 2010 .

[8]  Raphael Idem,et al.  Pathways and reaction products for the oxidative degradation of CO2 loaded and concentrated aqueous MEA and MEA/MDEA mixtures during CO2 absorption from flue gases , 2005 .

[9]  O. F. Dawodu,et al.  Degradation of alkanolamine blends by carbon dioxide , 1996 .

[10]  S. A. Bedell,et al.  Oxidative degradation mechanisms for amines in flue gas capture , 2009 .

[11]  Raphael Idem,et al.  Comprehensive study of the kinetics of the oxidative degradation of CO2 loaded and concentrated aqueous monoethanolamine (MEA) with and without sodium metavanadate during CO2 absorption from flue gases , 2006 .

[12]  Tielin Wang,et al.  Oxidative Degradation of Aqueous 2-Amino-2-methyl-1-propanol Solvent for Postcombustion CO2 Capture , 2012 .

[13]  S. Walse,et al.  Quaternary amines as nitrosamine precursors: a role for consumer products? , 2010, Environmental science & technology.

[14]  M. H. Chakrabarti,et al.  Degradation studies of amines and alkanolamines during sour gas treatment process , 2011 .

[15]  Hallvard F. Svendsen,et al.  Comparison of MEA degradation in pilot-scale with lab-scale experiments , 2011 .

[16]  Raphael Idem,et al.  Pathways for the Formation of Products of the Oxidative Degradation of CO2-Loaded Concentrated Aqueous Monoethanolamine Solutions during CO2 Absorption from Flue Gases , 2005 .

[17]  S. Mirvish.  Formation of N-nitroso compounds: chemistry, kinetics, and in vivo occurrence. , 1975, Toxicology and applied pharmacology.

[18]  Chang-he Chen,et al.  Thermal Degradation of Monoethanolamine in CO2 Capture with Acidic Impurities in Flue Gas , 2012 .

[19]  G. T. Davis,et al.  Oxidations of amines. VII. Chemical and electrochemical correlations , 1969 .

[20]  Jean Kittel,et al.  New Amines for CO2 Capture. IV. Degradation, Corrosion, and Quantitative Structure Property Relationship Model , 2012 .

[21]  Gary T. Rochelle,et al.  Oxidative Degradation of Monoethanolamine , 2002 .

[22]  J. Smith,et al.  Amine oxidation. Part 13. Electrochemical oxidation of some substituted tertiary alkylamines , 1978 .

[23]  Gary T. Rochelle,et al.  Thermal degradation of monoethanolamine at stripper conditions , 2009 .

[24]  G. T. Davis,et al.  Oxidations of Amines. III. Duality of Mechanism in the Reaction of Amines with Chlorine Dioxide , 1967 .

[25]  Peter Moser,et al.  Performance of MEA in a long-term test at the post-combustion capture pilot plant in Niederaussem , 2011 .

[26]  J. Smith,et al.  Amine oxidation. Part VII. The effect of structure on the reactivity of alkyl tertiary amines towards alkaline potassium hexacyanoferrate(III) , 1973 .

[27]  Paitoon Tontiwachwuthikul,et al.  Mechanism of formation of heat stable salts (HSSs) and their roles in further degradation of monoethanolamine during CO2 capture from flue gas streams , 2011 .

[28]  Edward S Rubin,et al.  A technical, economic, and environmental assessment of amine-based CO2 capture technology for power plant greenhouse gas control. , 2002, Environmental science & technology.

[29]  P. C. Rooney,et al.  Oxygen's role in alkanolamine degradation , 1998 .

[30]  A. Meisen,et al.  Degradation of aqueous DEA solutions in a heat transfer tube , 1984 .

[31]  Raphael Idem,et al.  Studies of SO2- and O2-Induced Degradation of Aqueous MEA during CO2 Capture from Power Plant Flue Gas Streams , 2007 .

[32]  W. Fritz.  WHO‐IARC‐Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans, Vol. 17: Some N‐Nitroso‐Compounds. 365 Seiten. International Agency for Research on Cancer, Lyon 1978. Preis: 50.‐ sfrs; 25,‐ US$ , 1979 .

[33]  Gary T. Rochelle,et al.  Monoethanolamine Degradation: O2 Mass Transfer Effects under CO2 Capture Conditions , 2004 .

[34]  H. Svendsen,et al.  Degradation of MMEA at absorber and stripper conditions , 2011 .

[35]  R. C. Doerr,et al.  Formation of N-Nitrosodimethylamine from Naturally Occurring Quaternary Ammonium Compounds and Tertiary Amines , 1972, Nature.

[36]  Gary T. Rochelle,et al.  Reaction Products from the Oxidative Degradation of Monoethanolamine , 2011 .

[37]  A. Meisen,et al.  DEA degradation mechanism , 1982 .

[38]  Amornvadee Veawab,et al.  Electrochemical Investigation on the Effect of Heat-stable Salts on Corrosion in CO2 Capture Plants Using Aqueous Solution of MEA , 2006 .

[39]  P. Carrette,et al.  New Amines for CO2 Capture. I. Mechanisms of Amine Degradation in the Presence of CO2 , 2009 .

[40]  Curt M. White,et al.  Degradation Pathways for Monoethanolamine in a CO2 Capture Facility , 2003 .

[41]  Raphael Idem,et al.  The Role of Methyl Diethanolamine (MDEA) in Preventing the Oxidative Degradation of CO2 Loaded and Concentrated Aqueous Monoethanolamine (MEA)−MDEA Blends during CO2 Absorption from Flue Gases , 2005 .

[42]  Gary T. Rochelle,et al.  Degradation of aqueous piperazine in carbon dioxide capture , 2010 .

[43]  Peter Moser,et al.  Investigation of trace elements in the inlet and outlet streams of a MEA-based post-combustion capture process results from the test programme at the Niederaussem pilot plant , 2011 .

[44]  A. Chakma,et al.  Methyl‐diethanolamine degradation — Mechanism and kinetics , 1997 .

[45]  G. Rochelle,et al.  Thermal degradation of piperazine and its structural analogs , 2011 .

[46]  A. Meisen,et al.  Mechanisms and kinetics of diethanolamine degradation , 1985 .

[47]  Steinar Pedersen,et al.  Effects of NOx in the flue gas degradation of MEA , 2011 .

[48]  Axel Meisen,et al.  Identification of methyl diethanolamine degradation products by gas chromatography and gas chromatography-mass spectrometry , 1988 .

[49]  Gary T. Rochelle,et al.  Oxidation Inhibitors for Copper and Iron Catalyzed Degradation of Monoethanolamine in CO2 Capture Processes , 2006 .

[50]  Amornvadee Veawab,et al.  Environmental impacts of absorption-based CO2 capture unit for post-combustion treatment of flue gas from coal-fired power plant , 2007 .

[51]  Jason Daniel Davis,et al.  Thermal degradation of aqueous amines used for carbon dioxide capture , 2009 .

[52]  A. Meisen,et al.  Gas chromatographic technique for analysing partially degraded diethanolamine solutions , 1983 .

[53]  M. Fazio.  Nucleophilic ring opening of 2-oxazolines with amines: a convenient synthesis for unsymmetrically substituted ethylenediamines , 1984 .

[54]  Paitoon Tontiwachwuthikul,et al.  Analysis of Monoethanolamine and Its Oxidative Degradation Products during CO2 Absorption from Flue Gases: A Comparative Study of GC-MS, HPLC-RID, and CE-DAD Analytical Techniques and Possible Optimum Combinations , 2006 .

[55]  J. Ridd.  Nitrosation, diazotisation, and deamination , 1961 .

[56]  P. Carrette,et al.  New Amines for CO2 Capture. II. Oxidative Degradation Mechanisms , 2009 .

[57]  G. Versteeg,et al.  CO2 capture from power plants. Part I: A parametric study of the technical performance based on monoethanolamine , 2007 .

[58]  R. Loeppky,et al.  NITROSATIVE CLEAVAGE OF TERTIARY AMINES. , 1967 .

[59]  George Scott Goff.  Oxidative degradation of aqueous monoethanolamine in CO₂ capture processes: iron and copper catalysis, inhibition, and O₂ mass transfer , 2005 .

[60]  A. Meisen,et al.  Corrosivity of diethanolamine solutions and their degradation products , 1986 .

[61]  O. F. Dawodu,et al.  Degradation of aqueous diethanolamine solutions by carbon disulfide , 1996 .

[62]  Hélène Lepaumier.  Etude des mécanismes de dégradation des amines utilisées pour le captage du CO2 dans les fumées , 2008 .

[63]  G. T. Davis,et al.  Oxidations of Amines. II. Substituent Effects in Chlorine Dioxide Oxidations , 1967 .

[64]  G. Rochelle,et al.  Degradation of aqueous methyldiethanolamine by temperature and oxygen cycling , 2011 .

[65]  Gary T. Rochelle,et al.  MDEA/Piperazine as a solvent for CO2 capture , 2009 .

[66]  C. M. White,et al.  Degradation of Monoethanolamine Used in Carbon Dioxide Capture from Flue Gas of a Coal-Fired Electric Power Generating Station , 2001 .

[67]  O. F. Dawodu,et al.  Identification of products resulting from carbonyl sulphide-induced degradation of diethanolamine , 1991 .

[68]  Paitoon Tontiwachwuthikul,et al.  Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams , 2009 .

[69]  H. Svendsen,et al.  Degradation of MEA; a theoretical study , 2011 .

[70]  P. C. Rooney,et al.  Comparing laboratory and plant data for MDEA/DEA blends : Gas processing developments: a special report , 1999 .

[71]  S. A. Bedell.  Amine autoxidation in flue gas CO2 capture—Mechanistic lessons learned from other gas treating processes , 2011 .

[72]  L. Hull,et al.  Oxidations of amines. IV. Oxidative fragmentation , 1967 .