Experimental and kinetic modeling study of n-propanol and i-propanol combustion: Flow reactor pyrolysis and laminar flame propagation

Li, Wei; Zhang, Yan; Mei, Bowen; Li, Yuyang; Cao, Chuangchuang; Zou, Jiabiao; Yang, Jiuzhong; Cheng, Zhanjun

doi:10.1016/j.combustflame.2019.05.040

Cited by 58 publications

(40 citation statements)

References 85 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[34][35][36][37][38] However, Barnard 39 measured the decomposition rate of isopropanol pyrolysis in a batch reactor using classical chemistry techniques and gas chromatography. Considering the existing kinetics data, the consensus in the literature on the main initial decomposition reactions for isopropanol are the dehydra- tion reaction of isopropanol R1 and the C α -C β dissociation reaction R2, 14,15,26,27,29,30,32,40,41 which is similar to findings in other alcohols. 4 iC 3 H 7 OH ⇌ H 2 O + C 3 H 6 (R1)…”

Section: Introductionsupporting

confidence: 53%

“…[8][9][10][11][12][13] Among these fuels, isopropanol has not been studied extensively and is lacking chemical kinetics data for key reactions in its decomposition mechanism. 14,15 Isopropanol has, however, been studied previously in both spark ignition and HCCI engines to examine its potential as a gasoline additive. [16][17][18][19][20][21] Results of these studies show significantly reduced CO and HC emissions, 16 and virtually zero NO emissions in HCCI engines, being noted as more suitable for HCCI combustion in its knock prevention.…”

Section: Introductionmentioning

confidence: 99%

“…Investigations into the kinetics of reaction R1 have produced large discrepancies in the measurement of k 1 , as shown in Figure 1. 14,28,42,43 This reaction was first studied by Ross and Stimson 44 using HBr catalysis in a reactor at pressures between 0.13 and 0.97 atm. However, the rate depends highly on the amount of HBr present, giving a significant overestimation of k 1 .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Isopropanol dehydration reaction rate kinetics measurement using H₂O time histories

Cooper

Mulvihill

Mathieu

et al. 2020

Int J of Chemical Kinetics

View full text Add to dashboard Cite

H 2 O formation during thermal decomposition of isopropanol was measured behind reflected shock waves at temperatures ranging from 1127 to 1621 K at an average pressure of 1.42 atm using a laser absorption technique. Of the five modern chemical kinetics models used to compare the H 2 O time histories, the model from Li et al (Combust. Flame 2019;207:171-185) showed the best overall agreement. Sensitivity and rate of production analyses using the Li et al model (as well as those from AramcoMech 3.0, CRECK, and Togbe et al (Energy Fuel. 2011;25:676-683)) showed unimolecular dehydration of isopropanol, iC 3 H 7 OH ⇌ H 2 O + C 3 H 6 (R1), is nearly the sole reaction controlling H 2 O production at early times, allowing for an a priori measurement of the forward rate constant k 1. The Arrhenius expression k 1 (s-1) = 2.60 × 10 13 exp(−31 120 K/T) was determined to represent best the data from this study. According to the models and previous experimental investigations, the pressure investigated is well within the high-pressure limit (HPL) for this reaction. Additional, higher-pressure experiments also confirmed the HPL assumption. An uncertainty analysis was performed by varying secondary reactions within their uncertainties and examining their effect on the overall prediction, establishing an uncertainty within ±20% for all but the highest temperature cases, which have a maximum uncertainty of ±40%. Experiments conducted with a radical trapper, toluene, showed little influence from radical chemistry, suggesting this estimated uncertainty is fairly conservative. Experimental data from Heyne et al (Z Phys Chem. 2015;229:881-907) were found to be in good agreement with the rate measurements from this study and, therefore, a second Arrhenius expression, k 1 (s-1) = 2.11 × 10 13 exp(−30 820 K/T), was found to represent both datasets well. This second expression has a larger temperature range of 976-1621 K. The present study provides the first high-temperature data collected for this reaction, adding to the limited data available for isopropanol in the literature.

show abstract

Section: Introductionsupporting

confidence: 53%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Isopropanol dehydration reaction rate kinetics measurement using H₂O time histories

Cooper

Mulvihill

Mathieu

et al. 2020

Int J of Chemical Kinetics

View full text Add to dashboard Cite

show abstract

“…Reasonable agreement, i.e., a factor of <3, with our rate constants and those from Sarathy et al 5 and Cai et al 83 is observed only for T > 1350 K. At lower temperatures, deviations as large as 3 orders of magnitude are highlighted. Taking advantage of a very significant number of pyrolysis data, 37 , 54 , 55 , 59 , 84 where the H-atom abstractions by ĊH 3 play a significant role for the validation of our model, we observed negative effects on model performances when implementing the theoretical values. Moreover, our reference kinetic parameters were found to agree quite satisfactorily (by a factor of <3) with the estimates reported in refs ( 5 and 83 ), both in terms of absolute rate constant and relative selectivities, as reported in Figure 7 .…”

Section: Kinetic Model Developmentmentioning

confidence: 99%

Combustion of n-C₃–C₆ Linear Alcohols: An Experimental and Kinetic Modeling Study. Part I: Reaction Classes, Rate Rules, Model Lumping, and Validation

et al. 2020

View full text Add to dashboard Cite

This work (and the companion paper, Part II) presents new experimental data for the combustion of n -C 3 –C 6 alcohols ( n -propanol, n -butanol, n -pentanol, n -hexanol) and a lumped kinetic model to describe their pyrolysis and oxidation. The kinetic subsets for alcohol pyrolysis and oxidation from the CRECK kinetic model have been systematically updated to describe the pyrolysis and high- and low-temperature oxidation of this series of fuels. Using the reaction class approach, the reference kinetic parameters have been determined based on experimental, theoretical, and kinetic modeling studies previously reported in the literature, providing a consistent set of rate rules that allow easy extension and good predictive capability. The modeling approach is based on the assumption of an alkane-like and alcohol-specific moiety for the alcohol fuel molecules. A thorough review and discussion of the information available in the literature supports the selection of the kinetic parameters that are then applied to the n -C 3 –C 6 alcohol series and extended for further proof to describe n -octanol oxidation. Because of space limitations, the large amount of information, and the comprehensive character of this study, the manuscript has been divided into two parts. Part I describes the kinetic model as well as the lumping techniques and provides a synoptic synthesis of its wide range validation made possible also by newly obtained experimental data. These include speciation measurements performed in a jet-stirred reactor ( p = 10 7 kPa, T = 550–1100 K, φ = 0.5, 1.0, 2.0) for n -butanol, n -pentanol, and n -hexanol and ignition delay times of ethanol, n -propanol, n -butanol, n -pentanol/air mixtures measured in a rapid compression machine at φ = 1.0, p = 10 and 30 bar, and T = 704–935 K. These data are presented and discussed in detail in Part II, together with detailed comparisons with model predictions and a deep kinetic discussion. This work provides new experimental targets that are useful for kinetic model development and validation (Part II), as well as an extensively validated kinetic model (Part I), which also contains subsets of other reference components for real fuels, thus allowing the assessment of combustion properties of new sustainable fuels and fuel mixtures.

show abstract

“…22 Work to understand the mechanism of isopropanol combustion is in progress. 21,[23][24][25][26][27][28][29] Combustion chemistry is often initiated by decomposition reactions, and previous studies suggest that alcohols decompose mainly through molecular dehydration or through C−C bond scissions ubiquitous to hydrocarbon chemistry. 6,[30][31][32][33] Fission of the C−O bond has too large a barrier to play a significant role.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of isopropanol decomposition and reaction with H atoms from shock tube experiments and rate constant optimization using the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE)

Mertens

Manion

2020

Int J of Chemical Kinetics

View full text Add to dashboard Cite

We have used the single-pulse shock tube technique with postshock GC/MS product analysis to investigate the mechanism and kinetics of the unimolecular decomposition of isopropanol, a potential biofuel, and of its reaction with H atoms at 918-1212 K and 183-484 kPa. Experiments employed dilute mixtures in argon of isopropanol, a radical scavenger, and, for H-atom studies, two different thermal precursors of H. Without an added H source, isopropanol decomposes in our studies predominantly by molecular dehydration. Added H atoms significantly augment decomposition, mainly by abstraction of the tertiary and primary hydrogens, reactions that, respectively, lead to acetone and propene as stable organic products. Traces of acetaldehyde were observed in some experiments above ≈ 1100 K and establish branching limits for minor decomposition pathways. To quantitatively account for secondary chemistry and optimize rate constants of interest, we employed the method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) to carry out a unified analysis of all datasets using a chemical model-based originally on JetSurF 2.0. We find: k(isopropanol → propene + H 2 O) = 10 (13.87 ± 0.69) exp(−(33 099 ± 979) K/ T) s −1 at 979-1212 K and 286-484 kPa, with a factor of two uncertainty (2σ), including systematic errors. For H atom reactions, optimization yields: k(H + isopropanol → H 2 + p-C 3 H 6 OH) = 10 (6.25 ± 0.42) T 2.54 exp(−(3993 ± 1028) K /T) cm 3 mol −1 s −1 and k(H + isopropanol → H 2 + t-C 3 H 6 OH) = 10 (5.83 ± 0.37) T 2.40 exp(−(1507 ± 957) K /T) cm 3 mol −1 s −1 at 918-1142 K and 183-323 kPa. We compare our measured rate constants with estimates used in current combustion models and discuss how hydrocarbon functionalization with an OH group affects H abstraction rates.

show abstract

Experimental and kinetic modeling study of n-propanol and i-propanol combustion: Flow reactor pyrolysis and laminar flame propagation

Cited by 58 publications

References 85 publications

Isopropanol dehydration reaction rate kinetics measurement using H₂O time histories

Isopropanol dehydration reaction rate kinetics measurement using H₂O time histories

Combustion of n-C₃–C₆ Linear Alcohols: An Experimental and Kinetic Modeling Study. Part I: Reaction Classes, Rate Rules, Model Lumping, and Validation

Kinetics of isopropanol decomposition and reaction with H atoms from shock tube experiments and rate constant optimization using the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE)

Contact Info

Product

Resources

About

Experimental and kinetic modeling study of n-propanol and i-propanol combustion: Flow reactor pyrolysis and laminar flame propagation

Cited by 58 publications

References 85 publications

Isopropanol dehydration reaction rate kinetics measurement using H2O time histories

Isopropanol dehydration reaction rate kinetics measurement using H2O time histories

Combustion of n-C3–C6 Linear Alcohols: An Experimental and Kinetic Modeling Study. Part I: Reaction Classes, Rate Rules, Model Lumping, and Validation

Kinetics of isopropanol decomposition and reaction with H atoms from shock tube experiments and rate constant optimization using the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE)

Contact Info

Product

Resources

About

Isopropanol dehydration reaction rate kinetics measurement using H₂O time histories

Isopropanol dehydration reaction rate kinetics measurement using H₂O time histories

Combustion of n-C₃–C₆ Linear Alcohols: An Experimental and Kinetic Modeling Study. Part I: Reaction Classes, Rate Rules, Model Lumping, and Validation