The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 speci...The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency （PIE） spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane,i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.展开更多
In an optical high--pressure autoclave with saphire windows and magnetic stirring, phase equilibria data in mixtures of water-n--butane and water-iso--butane were measured in a temperature range from 500K to 600K and ...In an optical high--pressure autoclave with saphire windows and magnetic stirring, phase equilibria data in mixtures of water-n--butane and water-iso--butane were measured in a temperature range from 500K to 600K and at a pressure from 10MPa to 300MPa. The critical curves of these systems start at the critical point of pure water and tend to higher pressures and lower temperatures. These curves pass a temperature minima 624K and 625K respectively and then tend to a high temperature and pressure. Excess volumes on the phase equilibria surface were given. The results are discussed in view of the phase equilibria of other water--n--alkane systems.展开更多
Ignition delay times of butanol isomers/n-heptane mixture were measured using a rapid compression machine at compressed pressures of 15,20 and 30 bar,in the compressed temperature range of 650–830 K and equivalence r...Ignition delay times of butanol isomers/n-heptane mixture were measured using a rapid compression machine at compressed pressures of 15,20 and 30 bar,in the compressed temperature range of 650–830 K and equivalence ratio of 1.0.Sensitivity analysis and reaction fluxes analysis were performed using a detailed mechanism of blend fuels so as to evaluate the impact of n-heptane addition and temperature variation on the ignition and combustion process.Over the experimental conditions in this study,the blend fuels displays apparent low and high temperature reactions and a negative-temperature-coefficient(NTC)behavior.With increasing butanol isomers mole fraction in the mixtures,the ignition delay times increase.It is worth noting that the suppression to n-heptane ignition from tert-butanol is very limited.The ignition delay time of 40/60 tert-butanol/n-heptane mixture is smaller than other three kinds of blends.With the increasing of tert-butanol mole fraction,the increasing range of its ignition delay time is very large.Moreover,compressed pressure has a limited effect on the ignition of blend mixture at low temperature but certain influence at medium temperature arrange.Tert-butanol/n-heptane mixture is not sensitive to the pressure.The chemical analysis indicates that butanol isomers also present the NTC behavior because of the low temperature reactivity radicals pool produced by n-heptane.Reaction fluxes analysis shows that the n-heptane addition has little impact on the reaction path.Sensitivity analysis shows that for the pure n-butanol,2-butanol and iso-butanol fuel,H-abstraction from the?-carbon plays the dominant role in the reactions having the inhibiting effect on the low-temperature branching,while the H-abstraction from the?-carbon can promote the ignition;for tert-butanol/n-heptane mixtures,reaction R16.H2O2(+M)<=>OH+OH(+M)plays the leading role.For n-butanol/n-heptane,iso-butanol/n-heptane mixtures,the major promoting reactions include some H-abstraction from n-heptane and OH branching reactions,the influence of H-abstraction from?-carbon is weaken;For 2-butanol/n-heptane,tert-butanol/n-heptane mixtures,R16 plays an absolutely dominant role,while the major inhibiting reactions add some elementary reactions of small radicals.展开更多
基金This work is supported by the National. Natural Science Foundation of China （No.51106146, No.51036007, No.U1232127）, the China Postdoctoral Science Foundation （No.20100480047 and No.201104326）, the Chinese Universities Scientific Fund （No.WK2310000010）, the Anhui Science ＆ Technology Department （No.l1040606Q49）, and the Chinese Academy of Sciences.
文摘The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency （PIE） spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane,i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.
文摘In an optical high--pressure autoclave with saphire windows and magnetic stirring, phase equilibria data in mixtures of water-n--butane and water-iso--butane were measured in a temperature range from 500K to 600K and at a pressure from 10MPa to 300MPa. The critical curves of these systems start at the critical point of pure water and tend to higher pressures and lower temperatures. These curves pass a temperature minima 624K and 625K respectively and then tend to a high temperature and pressure. Excess volumes on the phase equilibria surface were given. The results are discussed in view of the phase equilibria of other water--n--alkane systems.
基金supported by the National Natural Science Foundation of China(Grant No.2013CB228405)
文摘Ignition delay times of butanol isomers/n-heptane mixture were measured using a rapid compression machine at compressed pressures of 15,20 and 30 bar,in the compressed temperature range of 650–830 K and equivalence ratio of 1.0.Sensitivity analysis and reaction fluxes analysis were performed using a detailed mechanism of blend fuels so as to evaluate the impact of n-heptane addition and temperature variation on the ignition and combustion process.Over the experimental conditions in this study,the blend fuels displays apparent low and high temperature reactions and a negative-temperature-coefficient(NTC)behavior.With increasing butanol isomers mole fraction in the mixtures,the ignition delay times increase.It is worth noting that the suppression to n-heptane ignition from tert-butanol is very limited.The ignition delay time of 40/60 tert-butanol/n-heptane mixture is smaller than other three kinds of blends.With the increasing of tert-butanol mole fraction,the increasing range of its ignition delay time is very large.Moreover,compressed pressure has a limited effect on the ignition of blend mixture at low temperature but certain influence at medium temperature arrange.Tert-butanol/n-heptane mixture is not sensitive to the pressure.The chemical analysis indicates that butanol isomers also present the NTC behavior because of the low temperature reactivity radicals pool produced by n-heptane.Reaction fluxes analysis shows that the n-heptane addition has little impact on the reaction path.Sensitivity analysis shows that for the pure n-butanol,2-butanol and iso-butanol fuel,H-abstraction from the?-carbon plays the dominant role in the reactions having the inhibiting effect on the low-temperature branching,while the H-abstraction from the?-carbon can promote the ignition;for tert-butanol/n-heptane mixtures,reaction R16.H2O2(+M)<=>OH+OH(+M)plays the leading role.For n-butanol/n-heptane,iso-butanol/n-heptane mixtures,the major promoting reactions include some H-abstraction from n-heptane and OH branching reactions,the influence of H-abstraction from?-carbon is weaken;For 2-butanol/n-heptane,tert-butanol/n-heptane mixtures,R16 plays an absolutely dominant role,while the major inhibiting reactions add some elementary reactions of small radicals.
