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Thermal degradation of amines for CO2 capture

Gary T Rochelle
Amine scrubbing will be an important technology for CO2 capture and storage. The degradation of the amine at 100 150 8C limits the maximum T/P and therefore the energy performance of the solvent regeneration. This is a review of the rate, products, and mechanisms of thermal degradation. Primary and secondary ethanolamines and ethylenediamines degrade at 100130 8C as they form cyclic oxazolidinones and ureas. Tertiary amines can be more resistant to degradation if they do not include methyl and ethanol groups. Piperazine structures and long chain diamines such as hexamethylenediamine degrade by ring opening and closing and can be used at 150160 8C. Thermal degradation can produce products that are more volatile than the parent amines.
Address Luminant Carbon Management Program, Department of Chemical Engineering, The University of Texas at Austin, 1 University Station, C0400, Austin, TX 78712, United States Corresponding author: Rochelle, Gary T (gtr@che.utexas.edu)

minimize the economic loss of amine and the environmental impact of the degradation products. In CO2 capture from coal-red power plants by amine absorption/stripping, amine losses can occur by ve mechanisms [3]. Nonionic amines with a nite vapor pressure can vaporize into the ue gas. Flue gas typically contains 35% oxygen that can oxidize the amine in the absorber packing or absorber sump at 4070 8C or at 100 145 8C in the hot solution leaving the crossexchanger. Oxygen is rapidly removed at the top of the stripper and should not cause oxidation there. Thermal degradation occurs at the greatest rate at 120150 8C in the liquid hold-up of the stripper sump and reboiler. This paper will review work published from 2009 to 2011 on the thermal degradation of amines in this process. A previous review of this topic was prepared in 2001 [4].

Thermal degradation limits the maximum T/P and therefore the energy performance of the stripper
Thermal degradation of amines is easily managed by reducing the temperature and liquid holdup at the stripper bottom. However, greater heat of CO2 absorption and greater stripper temperature reduce the overall energy requirement of the stripper [2,5]. A condition of higher stripper temperature (T) and pressure (P) is energetically preferred because thermal compression is more efcient than mechanical compression. Greater stripper pressure will also reduce the size and capital cost of the stripper and compressor. Increasing the temperature of a single stage heated ash from 90 to 150 8C reduced the equivalent work required by as much as 30% [2]. This equivalent work (Weq) includes reboiler heat duty (Qi), compression work (Wcomps) and pump work (Wpumps) and depends upon the reboiler temperature (Ti) and the ambient temperature (Tsink).   nX reboilers T i 5K T sink W eq 0:75 Qi W pum ps T i 5K i 1 W com ps Therefore the maximum and optimum operating temperature of the amine regenerator is determined by thermal degradation. It should be expected that stripper systems will be optimized to the temperature at which thermal degradation affects economic makeup of the amine and environmental impact of the degradation products. Davis [6] estimated that the optimum temperature for 7 m monoethanolamine (MEA) should
Current Opinion in Chemical Engineering 2012, 1:183190

Current Opinion in Chemical Engineering 2012, 1:183190 This review comes from a themed issue on Separation engineering Edited by W.S. Winston Ho and K. Li

2211-3398/$ see front matter # 2012 Elsevier Ltd. All rights reserved. DOI 10.1016/j.coche.2012.02.004

Introduction
Amine scrubbing with thermal regeneration will be an important technology for CO2 capture from fossil fuel combustion to manage global climate change [1]. In this process (Figure 1), CO2 is absorbed in a countercurrent contactor at 4070 8C. The solvent is heated to 100 150 8C and stripped with steam to produce pure CO2. For geologic storage the CO2 is further compressed to 150 bar. To minimize energy consumption, the amine solvent should have a large operating CO2 capacity, fast CO2 absorption kinetics, and a high heat of CO2 absorption [2]. If the amine is resistant to thermal degradation, the stripper can be operated at greater temperature and pressure to further reduce compression work and capital costs. Excessive thermal degradation must be avoided to
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184 Separation engineering

Figure 1

Amine volatility lean amine Flue Gas Out Oxidation oxygen mass transfer

Oxidation dissolved oxygen solubility

CO2

100 150 C 1 10 atm

ABS 40 65 C

Heat X

STR

Flue Gas In ~5 % O2 12 % CO2 rich amine Reb

Oxidation kinetics

Thermal degradation
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Amine losses in the CO2 capture process [3].

be about 132 8C with an operating pressure of 3 bar. However, most MEA systems have been designed with a maximum temperature of 120 8C. The maximum temperature of the stripper could be further reduced by innovative equipment design that minimizes liquid hold-up at the high temperature in the bottom of the stripper.

of the measurements in Table 1 were made at greater CO2 loading (0.30.5 mol/equiv. amine).

Principal authors working on thermal degradation

Most of the measurements reported in Table 1 were made by Davis, Lepaumier, Freeman and Eide-Haugmo. Davis (University of Texas at Austin [6,8]) degraded 18 amines in 10 ml cylinders placed in convection ovens at 100150 8C for 116 weeks. He analyzed samples primarily by cation chromatography with and without mass spectrometry. His primary focus and contribution was a comprehensive study of MEA. He also studied a number of MEA analogs, MEA blends with other amines, and a few other amines. Most of his screening studies degraded amines at 7 m alkalinity with 0.4 mol CO2/equiv. N for 4 weeks at 135 8C. Freeman (2011) [7,9] continued to use the methods of Davis at 100175 8C with a primary focus on PZ. She added the use of anion chromatography, HPLC, acid titration for total alkalinity, and acid evolution for total
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Four mechanisms of thermal degradation are evident

Table 1 gives selected results from the literature on the thermal degradation of amine solvents loaded with CO2. Freeman [7] has interpreted the literature measurement to report the temperature where the apparent rst order rate constant for the degradation of total amine is 2.9e8 s1. This rate is approximately that of MEA at 120 8C. It is known that MEA has been commercially used at 120 8C with a tolerable level of thermal degradation. If rate measurements at multiple temperatures are available, the Arrhenius expression was used to interpolate or extrapolate the data. If the measurement is available only at one temperature the rate was extrapolated using the activation energy for the degradation of MEA (157 kJ/mol) or piperazine (PZ) (184 kJ/mol). Most
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Thermal degradation of amines for CO2 capture Rochelle 185

Table 1 Degradation temperature giving k1 = 2.9 10S8 sS1 of selected amines. Amine Diamines that degrade to cyclic ureas N,N0 -Dimethylethylenediamine Diethylenetriamine N-(2-Hydroxyethyl)ethylenediamine 3-(Methylamino)propylamine Ethylenediamine Abbrev N,N0 -diMEDA DETA HEEDA MAPA EDA Structure(s) Stripper T (8C) 104 108, 118 114 114 117128 [11] [6,15] [15] [6,11] [7,15,23] Ref.

Alkanolamines that degrade through an oxazolidinone Diethanolamine DEA N-Methylethanolamine 2-Piperidinemethanol MAE 2-PM

103, 105 102, 105 109

[11,15] [6,11,14] [6]

Monoethanolamine 2-Piperidineethanol

MEA 2-PE

111125 127

[6] [7]

3-Amino-1-propanol 2-Amino-2-methyl-1-propanol

3a1p AMP

126,127 123, 137, 140

[6,15] [6,11,15]

Tertiary amines that degrade by elimination and transalkylation N,N-Dimethylethylenediamine N,N-diMEDA

115

[11]

N,N-Dimethylethanolamine

DMAE

118

[11]

N-(2-Aminoethyl)piperazine

AEP

121

[6]

N,N-Dimethylethanolamine

DMMEA

122

[15]

N-Methyldiethanolamine

MDEA

119129

[3,6,11,15,22]

N-(2-Hydroxyethyl)piperazine 1-Methylpiperazine

HEP 1-MPZ

130 150

[6] [7]

Amines that degrade by ring opening and closing Diglycolamine1 DGA 2-Methylpiperazine 2-MPZ

132 151

[6] [7]

Hexamethylenediamine Piperazine

HMDA PZ

160 162

[7] [7]

Amine blends, degradation rate of total amine Monoethanolamine/piperazine MEA/PZ

104

[6]

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186 Separation engineering

Table 1 (Continued ) Amine Abbrev Structure(s) Stripper T (8C) Ref.

Monoethanolamine/DGA1 N-Methyldiethanolamine/PZ

MEA/DGA1 MDEA/PZ

112 120, 143

[6] [3]

Monoethanolamine/AMP

MEA/AMP

123

[6]

Piperazine/AMP

PZ/AMP

134

[7]

Piperazine/1,4-dimethylpiperazine/1-MPZ PZ/1,4-DMPZ/1-MPZ

156160

[7]

Piperazine/2-methylpiperazine

PZ/2-MPZ

155

[7]

CO2. She also measured degradation of PZ analogs and a few additional amines. Lepaumier [10,11,12] degraded 17 amines with 4 mol amine/kg in 100 ml batch reactors at 135 8C for 15 days. She conducted experiments with and without CO2 and oxygen. Table 1 includes her results with CO2 and without oxygen. Lepaumier analyzed her samples primarily by gas chromatography with mass spectrometry. As a postdoc, Lepaumier also conducted thorough studies of MEA [13] and methylaminoethanol (MAE) [14] degradation. Eide-Haugmo (NTNU) [15,16] adapted the methods of Lepaumier and Davis including the use of LCMS and GCMS. She measured 33 amines, primarily at 135 8C for 5 weeks without CO2 and with 0.5 mol CO2/mol amine. She reports results on 11 amines in one paper and gives results for 22 additional amines in her dissertation.

This reaction is reversible, especially at greater temperature [7] (S Freeman, GT Rochelle, Thermal degradation of aqueous piperazine for CO2 capture: 2: Product types and generation rates, IECR, unpublished data). However, the equilibrium concentration of the cyclic urea is substantial and represents an unacceptable loss of active amine. Structures containing secondary N degrade to the urea at lower T (methylaminopropanolamine (MAPA), dietheylenetriamine (DETA), HEEDA). It is possible that the cyclic ureas act as intermediates in further oligomerization with the production of ammonia and other fragments. For example, HEEDA may react with HEI to produce ammonia and hydroxyethyldiethylenetriamine. Simple ureas are also produced reversibly from amines that are resistant to other degradation mechanisms. Diglycolamine1 (DGA1) is known to produce the urea, which can be reversibly decomposed by reclaiming at elevated temperature with low CO2 loading [17]. It is possible this urea is an intermediate in the thermal degradation of DGA to produce morpholine.

Cyclic urea is rapidly produced from ethanediamines or propanediamines

Diamine structures where two secondary or primary Ns are separated by two or three carbons readily degrade at lower T in the presence of CO2 to produce cyclic ureas (imidazolidinone), such as the production of hydroxyethylimidazolidinone (HEI) from hydroxyethylethylenediamine (HEEDA):

Carbamate polymerization
Primary and secondary alkanolamines with two or three carbons between the N and oxygen degrade by reversibly

HO

NH

NH2 + CO2 HO

N O

NH + H2O

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Thermal degradation of amines for CO2 capture Rochelle 187

forming a cyclic oxazolidinone from the carbamate, which then reacts with another amine to form a dimer of the starting amine [6,8,18].

SN2 reactions are catalyzed by CO2 or acid loading to protonate the tertiary amine [3,11,20]. Bedell [21] shows that addition of a quaternary amine catalyzes this

O HO NH2

NH

HO

NH

NH2

CO2

Because the equilibrium concentration of the oxazolidinone will be greater, greater CO2 loading accelerates carbamate polymerization. Table 1 shows that secondary amines degrade most readily (diethanolamine (DEA), 105 8C; MAE, 102 8C). Even the hindered alkanolamines are not resistant to this mechanism. Both aminomethylpropanol (AMP) (126 8C) and 2-PE degrade (127 8C) with the production of the expected dimer. The severely hindered N-tertbutylethanolamine still degrades about half as fast as AMP [15]. If the alkanolamine has more than 3 carbons between the alcohol and the amine, it will degrade by another, usually more resistant, mechanism. DGA (with 5 atoms between the amine and the alcohol) degrades at 132 8C.

process. Tertiary amines react even more readily with a quaternary amine.
CH3 HO N CH3 N H3C
+

CH3 OH + HO OH + HO NH

OH

HO

NH

OH

Elimination from the quatenary amine will result in the net production of the secondary amine. Elimination may be faster with ethyl alcohol or ethyl amine attached to the tertiary N.

CH3 HO N H3C
+

CH3 + OH H2O HO

NH CH3 +

HO

OH

Davis [6] developed a rate model for MEA with six reactions and completed a material balance for reactions at 100150 8C. He found that the apparent activation energy of the individual rate steps is about 138 kJ/mol. Lepaumier [13] and Strazisar [19] identied degradation products found in a ue gas treating unit. The initial product is HEEDA which rapidly degrades to produce the cyclic urea, HEIA. These dimers react by the same mechanisms to produce the cyclic urea of the trimer, 1-[2[(2-hydroxyethyl)amino]ethyl]-2-imidazolidone and other oligomers such as N-(2-hydroxyethyl)triethylenetetramine, and the corresponding cyclic urea, 1-[2-[2-[(2hydroxyethyl)amino]ethyl]amino)ethyl]-2-imidazolidone. Lepaumier [14] conducted a similar study with MAE, which degrades much faster, but produces similar types of products by a comparable mechanism.

Methyldiethanolamine (MDEA) thermally degrades to DEA, dimethylmonoethanolamine (DMMEA), MAE, and other related molecules [3]. Since secondary alkanolamines are produced, further degradation occurs by carbamate polymerization. Table 1 shows that tertiary amines with ethyl amino or ethyl alcohol arms such as MDEA degrade at lower T. Since the degradation rate of tertiary amines is proportional to the CO2 loading there can be wide variations of the reported rate with CO2 loading. It is also possible to strip tertiary amines to very low CO2 loading if there is no primary or secondary amine promoter. A BASF patent application reports degradation rate for six simple substituted tertiary amines saturated with CO2 and H2O at 162 8C and 6.3 bar for 300 hours [22]. These conditions would provide exceptionally low CO2 loading. The two tertiary amines including both methyl groups and ethanol groups had 6% (MDEA) and 4% degradation (dimethylethanolamine). The four other tertiary amines had 1% (or less) degradation (3-dimethylamine-1-propanol, N,N-diethylethanolamine, N-ethyldiethanolamine, and 3-diethylaminopropanol). The results from EideHaugmo conrm this effect with 0.5 mol CO2/mol amine,
Current Opinion in Chemical Engineering 2012, 1:183190

Tertiary amines degrade by transalkylation and elimination

Tertiary amines appear to degrade by two mechanisms. All of the tertiary amines participate in transalkylation, especially in the presence of secondary Ns in the parent molecule or from other degradation mechanisms. These
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188 Separation engineering

the degradation rate at 135 8C for MDEA and DMMEA (dimethylethanolamine) is 23 times faster than that for diethylethanolamine and triethanolamine [15]. This would suggest that the methyl group on a tertiary nitrogen with an ethanol group is more subject to transalkylation and/or elimination. Lepaumier [12] shows that tertiary diamines can also participate in ring closing and other more complicated reactions.

PZ disappears at about one mole for every mole of MDEA that degrades [3].
HN HN N NH + HO + HO NH
+

OH OH

+ NH2

Piperazines and long chain diamines degrade by ring closing or opening

Freeman [7] (S Freeman, GT Rochelle, Thermal degradation of aqueous piperazine for CO2 capture: 2: Product types and generation rates, IECR, unpublished data) established that PZ degrades by ring opening catalyzed by protonation in loaded CO2 solutions or in solutions with added acid. The initial product, aminoethylaminoethylpiperazine (AEAEPZ) is subject to further degradation by cyclic urea formation. The cyclic urea reacts with PZ to produce oligomers and fragments such as ethylenediamine (EDA) and ammonia. The most stable nal product is aminoethylpiperazine (AEP).

Some blends may degrade to an equilibrium mixture of useful amines. The blend of N-methylpiperazine with PZ disproportionates at 150 8C to an equilibrium mixture of PZ, 1-methylpiperazine (1-MPZ), and 1,4-dimethyl piperazine [7] (SA Freeman et al., Piperazine/N-methylpiperazine/N,N0 -dimethylpiperazine as an aqueous solvent for carbon dioxide capture, Oil Gas Sci Technol, unpublished data). 1-MPZ by itself degrades to a similar equilibrium mixture.

Formate production at stripper conditions

Freeman [7] observed signicant production of formate and its amide with PZ at 150 8C. She used NMR with C13O2 to demonstrate that the formate is produced

H H

NH HN

NH AEAEPZ

NH2 + H+

HN

NH

Hexamethylenediamine (HMDA) is resistant to degradation and degrades by ring closing to make piperidine and ammonia [7,15].

Blends with alkanolamines degrade faster than either amine

Blends of MEA with other amines always degrade faster than either amine. The blend of MEA with PZ degrades at 104 8C because the reactive PZ reacts with the MEA oxazolidinone to produce the cross dimer [6].
HN NH + O O NH HN HO N NH O

from the CO2 and not from C in the PZ. Closmann [3] also observed formate/formamide formation in the thermal degradation of MDEA and MDEA/PZ. The mechanism is not understood but probably requires oxidation of a C on the amine and reduction of the CO2 in a carbamate to the respective amide or formate. The analytical methods for oxidation products of PZ are known to be incomplete and could easily miss an important oxidation product. Freeman [7] also established that the formate and its respective amide are in equilibrium at 150 8C in less than a week. The equilibrium in loaded PZ provides about equal amount of formate and amide.

Blends of tertiary amines with secondary or primary amines usually degrade faster [3,21]. A reactive secondary amine can pick up arms from the tertiary amine. PZ will react with MDEA to produce N-methylpiperazine and DEA. When MDEA/PZ is thermally degraded, the
Current Opinion in Chemical Engineering 2012, 1:183190

Thermal degradation may be avoided by stripping to very low CO2 loading

The four principal mechanisms for thermal degradation of useful amines require the amine carbamate or protonated amine as an important reactant. Therefore CO2 loading or an amine salt such as sulfate or formate will increase the
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Thermal degradation of amines for CO2 capture Rochelle 189

rate of amine degradation. It should be possible to avoid thermal degradation by overstripping to very low CO2 loading. This is possible with tertiary or hindered amines that make only bicarbonate. However, it is difcult to strip to low loading with primary or secondary amines that produce carbamates. Furthermore Van Wagener [5] has established that minimum energy use is achieved in systems that strip the CO2 only to the level required to achieve adequate CO2 removal. A few amines degrade in the absence of CO2. EideHaugmo [15] found three propanediamines with >20% degradation at 135 8C for 5 weeks without CO2: (MAPA), N-[33-amino-1-methylaminopropane (dimethylamino)propyl]-N,N-dimethyl-1,3-propanediamine (TMBPA), and 3-aminopropanol. It may be that these molecules participate in reversible addition to a heteroconjugated double bond. Eide-Haugmo [15] also observed signicant loss with four amino acids. It is probable that these molecules participate in the reversible formation of the respective amides. LePaumier [14] observed signicant loss of 2-methylaminoethanol in the absence of CO2, with more loss in a metal reactor than in a glass reactor.

Alkanolamines thermally degrade by carbamate polymerization at a rate that limits stripper operation to 100 130 8C. Internal urea formation limits ethane and propane diamines to 100120 8C. Tertiary amines thermally degrade by transalkylation and elimination at 120140 8C. PZs, HMDA, and related structures degrade by ring closing or opening at 150160 8C. Blends of alkanolamines with reactive amines such as PZ degrade more rapidly as the reactive amine participates in carbamate polymerization. Formate and formamides are thermal degradation products at greater T. Thermal degradation can produce products that are more volatile that the parent amines.

Acknowledgements
This review is based in large part on the work of former PhD students supported by the Luminant Carbon Management Program at the University of Texas at Austin: Jason Davis, Stephanie Freeman, and Fred Closmann.

References and recommended reading Degradation products may be more volatile than parent amines
Ammonia has been observed in the thermal degradation of PZ, probably with PZ addition to a cyclic urea [7]. Methylated amines are typically more volatile than their parent amines. Methyl piperazine and dimethylpiperazine can be signicant products in the thermal degradation of PZ and blends of PZ with other amines [3,7]. The volatility of the DMPZ makes this an unacceptable blend for commercial practice [7] (SA Freeman et al., Piperazine/N-methylpiperazine/N,N0 dimethylpiperazine as an aqueous solvent for carbon dioxide capture, Oil Gas Sci Technol, unpublished data). Transalkylation with MDEA can produce DMMEA and other amines more volatile than MDEA itself [3]. Other impurities in the ue gas may react with amines in the stripper. Sulte will react with MEA to produce specic sulfo-amine products, possibly identied as N(2-hydroxyethyl)-amidosulfurous acid to N-(2-hydroxyethyl)-sulfamic acid [22].
Papers of particular interest, published within the period of review, have been highlighted as:  of special interest  of outstanding interest 1. 2.  Rochelle GT: Amine scrubbing for CO2 capture. Science 2009, 325:1652-1654.

Rochelle GT, Chen E, Freeman S, VanWagener D, Xu Q, Voice A: Aqueous piperazine as the new standard for CO2 capture technology. Chem Eng J 2011, 171:725-733 http://dx.doi.org/ 10.1016/j.cej.2011.02.011. This work provides a basis for the importance of elevated stripper T. Closmann F: Oxidation and thermal degradation of methyldiethanolamine/piperazine in CO2 capture, PhD dissertation, The University of Texas at Austin, December 2011 http://research.engr.utexas.edu/rochelle/images/stories/ publications/closmann_dissertation_20119.pdf This comprehensive work on MDEA/PZ degradation includes data at cyclic absorber and stripper T. Rochelle GT: Research needs for CO2 capture from ue gas by aqueous absorption/stripping. DE-AF26-99FT01029; 2011. Van Wagener D: Stripper modeling for CO2 removal using monoethanolamine and piperazine solvents, PhD dissertation, The University of Texas at Austin, 2011, http:// repositories.lib.utexas.edu/bitstream/handle/2152/ETD-UT-201108-4302/VAN-WAGENER-DISSERTATION.pdf.

3. 

4. 5.

6. 

Davis J: Thermal degradation of aqueous amines used for carbon dioxide capture, Ph.D. dissertation, The University of Texas at Austin; 2009, http://repositories.lib.utexas.edu/handle/ 2152/6581 This work develops a comprehensive model of MEA thermal degradation and provides rate data on 17 other amines. Freeman S: Thermal degradation and oxidation of aqueous piperazine for carbon dioxide capture, PhD dissertation, The University of Texas at Austin, May 2011, http://hdl.handle.net/ 2152/ETD-UT-2011-05-3290, May 2011 Current Opinion in Chemical Engineering 2012, 1:183190

Conclusions
Thermal degradation limits the maximum T/P and therefore the energy performance of the stripper.
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190 Separation engineering

This is a comprehensive study of piperazine degradation. It includes data for a number of piperazine derivatives. It summarizes all of the rate data from the literature. 8. Davis J, Rochelle GT: Thermal degradation of monoethanolamine at stripper conditions. Energy Procedia 2009, 1:327-333. Freeman SA, Davis J, Rochelle GT: Degradation of aqueous piperazine in carbon dioxide capture. Int J Greenhouse Gas Control 2010, 4:756-761.

15. Eide-Haugmo I: Environmental impacts and aspects of  absorbents used for CO2 capture, PhD thesis, Norwegian University of Science and Technology, ISBN 978-82-471-3046-9, 2011 Chapter 4 provides data on rates and degradation products for 33 amines. 16. Eide-Haugmo I, Lepaumier H, Einbu A, Vernstad K, da Silva EF,  Svendsen HF: Chemical stability and biodegradability of new solvents for CO2 capture. Energy Procedia 2011, 4:1631-1636. Provides measured thermal degradation rates for 11 amines. 17. Al-juaied MA: Carbon dioxide removal from natural gas by membranes in the presence W of heavy hydrocarbons and by aqueous Diglycolamine /Morpholine, PhD dissertation, The University of Texas at Austin, May 2004. 18. Polderman LD, Dillon CP, Steele AB: Why MEA solution breaks down in gas-treating service. Oil Gas J 1955, 54:180-183. 19. Strazisar BR, Anderson RR, White CM: Degradation pathways for monoethanolamine in a CO2 capture facility. Energy Fuels 2003, 17:1034-1039. 20. Chakma A, Meisen A: Methyl-diethanolamine degradation mechanism and kinetics. Can J Chem Eng 1997, 75:861-871. 21. Bedell SA, Worley CM, Al-Horr RS, McCrery DA: Quaternaries as intermediates in the thermal and oxidative degradation of alkanolamines. Ind Eng Chem Res 2011, 49:7147-7151. 22. Lichtfers U, Asprion N, Claessen M, Umino H, Tanaka K: Process  for the recovery of carbon dioxide. PCT Int. Appl. (2007), WO 2007068695 A1 20070621. 23. Zhou S, Chen X, Nguyen T, Voice Alexander K, Rochelle GT: Aqueous ethylenediamine for CO2 capture. ChemSusChem 2010, 3:913-918.

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tude des mecanismes de de gradation des 10. Lepaumier H: E es pour le captage du CO2 dans les fume es. amines utilise nieur, Ph.D. thesis, University of Savoie, Sciences Pour lInge France, October 2008. 11. Lepaumier H, Picq D, Carrette P-L: New amines for CO2 capture.  I. Mechanisms of amine degradation in the presence of CO2. Ind Eng Chem Res 2009, 48:9061-9067. Lepaumier presents results on thermal degradation of 12 amines, including a series of substituted ethylenediamines and several consistent mechanisms/pathways to describe expected products. 12. Lepaumier H, Martin S, Picq D, Delfort B, Carrette PL: New  amines for CO2 capture. III. Effect of alkyl chain length between amine functions on polyamines degradation. Ind Eng Chem Res 2010, 49:4553-4560. This work provides data and interpretations for several tertiary polyamines. 13. Lepaumier H, da Silva EF, Einbu A, Grimstvedt A, Knudsen JN,  Zahlsen N, Svendsen HF: Comparison of MEA degradation in pilot-scale with lab-scale experiments. Energy Procedia 2011, 4:1652-1659. This work gives bench-scale and pilot-scale results on MEA oxidation and thermal degradation. 14. Lepaumier H, Grimstvedt A, Vernstad K, Zahlsen K, Svendsen HF: Degradation of MMEA at absorber and stripper conditions. Chem Eng Sci 2011, 66:3491-3498.

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