Branching ratios for the reactions of OH with ethanol amines used in carbon capture and the potential impact on carcinogen formation in the emission plume from a carbon capture plant

Onel, Lavinia; Blitz, Mark A.; Breen, Jessica R.; Rickard, Andrew R.; Seakins, Paul W.

doi:10.1039/c5cp04083c

Cited by 19 publications

(20 citation statements)

References 52 publications

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“…Further experiments were carried out in a low-pressure (∼20–50 Torr) apparatus (promoting reaction over ), on OH and t -butylamine, where O 2 was added to the system. Under all conditions, no significant OH recycling was observed, although under similar conditions OH recycling has been observed for both amines − and aldehydes. , This result is consistent with the low abstraction branching ratio for of 0.13.…”

Section: Resultssupporting

confidence: 85%

“…Nitrogen-containing compounds have received significant interest in recent years as they have the ability to reversibly complex with carbon dioxide, CO 2 . This makes carbon capture and storage (CCS) possible with N-compounds, in particular, with low-vapor pressure amines, for example, ethanol amine. − Previously, we have studied a range of such compounds in terms of their reactivity toward OH in order to provide knowledge of their kinetics and the breakdown mechanism of these compounds if released into the atmosphere. − …”

Section: Introductionmentioning

confidence: 99%

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OH Kinetics with a Range of Nitrogen-Containing Compounds: N-Methylformamide, t-Butylamine, and N-Methyl-propane Diamine

et al. 2021

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Emissions of amines and amides to the atmosphere are significant from both anthropogenic and natural sources, and amides can be formed as secondary pollutants. Relatively little kinetic data exist on overall rate coefficients with OH, the most important tropospheric oxidant, and even less on site-specific data which control the product distribution. Structure−activity relationships (SARs) can be used to estimate both quantities. Rate coefficients for the reaction of OH with t-butylamine (k 1 ), N-methyl-1,3-propanediamine (k 2 ), and N-methylformamide (k 3 ) have been measured using laser flash photolysis coupled with laser-induced fluorescence. Proton-transferreaction mass spectrometry (PTR-MS) has been used to ensure the reliable introduction of these low-vapor pressure N-containing compounds and to give qualitative information on products. Supporting ab initio calculations are presented for the t-butylamine system. The following rate coefficients have been determined: k 1,298K = (1.66 ± 0.20) × 10 −11 cm 3 molecule −1 s −1 , k(T) 1 = 1.65 × 10 −11 (T/300) −0.69 cm 3 molecule −1 s −1 , k 2,293K = (7.09 ± 0.22) × 10 −11 cm 3 molecule −1 s −1 , and k 3,298K = (1.03 ± 0.23) × 10 −11 cm 3 molecule −1 s −1 . For OH + t-butylamine, ab initio calculations predict that the fraction of N−H abstraction is 0.87. The dominance of this channel was qualitatively confirmed using end-product analysis. The reaction of OH with N-methyl-1,3-propanediamine also had a negative temperature dependence, but the reduction in the rate coefficient was complicated by reagent loss. The measured rate coefficient for reaction 3 is in good agreement with a recent relative rate study. The results of this work and the literature data are compared with the recent SAR estimates for the reaction of OH with reduced nitrogen compounds. Although the SARs reproduce the overall rate coefficients for reactions, site-specific agreement with this work and other literature studies is less strong.

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Section: Resultssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

OH Kinetics with a Range of Nitrogen-Containing Compounds: N-Methylformamide, t-Butylamine, and N-Methyl-propane Diamine

et al. 2021

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“…Well depth, E/kJ mol -1 153.7 ± 5.9 153.5 ± 6.2 156.0 ± 3.9 156.0 ± 4.2 153.6 ± 4.9 153.4 ± 5.1 153.2 ± 5.0 A< E>d / cm -1 He(m=1.00) Ar (m=0.50) N2 (m=0. 25) n/a n/a n/a n/a 150 (Fixed) 150 (Fixed) 100 ± 350 n/a n/a n/a n/a 250 (Fixed) 250…”

Section: This Work Two Adduct Modelmentioning

confidence: 99%

Kinetics of the Reaction of OH with Isoprene over a Wide Range of Temperature and Pressure Including Direct Observation of Equilibrium with the OH Adducts

et al. 2018

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The reaction of the OH radical with isoprene, CH (R1), has been studied over the temperature range 298-794 K and bath gas pressures of nitrogen from 50 to 1670 Torr using laser flash photolysis (LFP) to generate OH and laser-induced fluorescence (LIF) to observe OH removal. Measurements have been made using both a conventional LFP/LIF apparatus and a new high pressure system. The measured rate coefficient at 298 K ( k = (9.90 ± 0.09) × 10 cm molecule s) in the high pressure apparatus is in excellent agreement with the literature, confirming the accuracy of measurements made with this instrument. Above 700 K, the OH decays were no longer single exponentials due to regeneration of OH from adduct decomposition and the establishment of the OH + CH ⇌ HOCH equilibrium (R1a, R-1a). This equilibrium was analyzed by comparison to a master equation model of reaction R1 and determined the well depth for OH addition to carbon C and C to be equal to 153.5 ± 6.2 and 143.4 ± 6.2 kJ mol, respectively. These well depths are in excellent agreement with the present ab initio-CCSD(T)/CBS//M062X/6-311++G(3df,2p)-calculations (154.1 kJ mol for the C adduct). Addition to the less stable C and C adducts is not important. The data above 700 K also indicated that a minor but significant direct abstraction channel, R1b, was also operating with k = (1.3 ± 0.3) × 10 exp(-3.61 kJ mol/ RT) cm molecule s. Additional support for the presence of this abstraction channel comes from our ab initio calculations and from room-temperature proton transfer mass spectrometry product analysis. The literature data on reaction R1 together with the present data were assessed using master equation analysis, using the MESMER package. This analysis produced a refined data set that generates our recommended k( T, [ M]). An analytical representation of k( T, [ M]) and k( T, [ M]) is provided via a Troe expression. The reported experimental data (the sum of addition and abstraction), k = (9.5 ± 0.2) × 10( T/298 K) + (1.3 ± 0.3) × 10 exp(-3.61 kJ mol/ RT) cm molecule s, significantly extend the measured temperature range of R1.

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“…10 It has been estimated that a CO2 capture plant which removes 1 million tons CO2 per year from flue gas using MEA as solvent could potentially emit 80 tons MEA into the atmosphere. 11,12 Therefore, in recent years concern about the atmospheric fate of the representative amine MEA has been increasing, 6, [13][14][15][16][17][18][19][20][21][22] as MEA could potentially form an environmental risk. 11,12,17 Several studies have addressed the removal of MEA by atmospheric oxidation.…”

Section: Introductionmentioning

confidence: 99%

Atmospheric Fate of Monoethanolamine: Enhancing New Particle Formation of Sulfuric Acid as an Important Removal Process

Xie

Elm

Halonen

et al. 2017

Environ. Sci. Technol.

110

161

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Monoethanolamine (MEA), a potential atmospheric pollutant from the capture unit of a leading CO capture technology, could be removed by participating HSO-based new particle formation (NPF) as simple amines. Here we evaluated the enhancing potential of MEA on HSO-based NPF by examining the formation of molecular clusters of MEA and HSO using combined quantum chemistry calculations and kinetics modeling. The results indicate that MEA at the parts per trillion (ppt) level can enhance HSO-based NPF. The enhancing potential of MEA is less than that of dimethylamine (DMA), one of the strongest enhancing agents, and much greater than methylamine (MA), in contrast to the order suggested solely by their basicity (MEA < MA < DMA). The unexpectedly high enhancing potential is attributed to the role of -OH of MEA in increasing cluster binding free energies by acting as both a hydrogen bond donor and acceptor. After the initial formation of one HSO and one MEA cluster, the cluster growth mainly proceeds by first adding one HSO, and then one MEA, which differs from growth pathways in HSO-DMA and HSO-MA systems. Importantly, the effective removal rate of MEA due to participation in NPF is comparable to that of oxidation by hydroxyl radicals at 278.15 K, indicating NPF as an important sink for MEA.

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Branching ratios for the reactions of OH with ethanol amines used in carbon capture and the potential impact on carcinogen formation in the emission plume from a carbon capture plant

Cited by 19 publications

References 52 publications

OH Kinetics with a Range of Nitrogen-Containing Compounds: N-Methylformamide, t-Butylamine, and N-Methyl-propane Diamine

OH Kinetics with a Range of Nitrogen-Containing Compounds: N-Methylformamide, t-Butylamine, and N-Methyl-propane Diamine

Kinetics of the Reaction of OH with Isoprene over a Wide Range of Temperature and Pressure Including Direct Observation of Equilibrium with the OH Adducts

Atmospheric Fate of Monoethanolamine: Enhancing New Particle Formation of Sulfuric Acid as an Important Removal Process

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