The Effect of Ultrasound on Lignocellulosic Biomass as a Pretreatment ...
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The Effect of Ultrasound on Lignocellulosic Biomass as a Pretreatment for Biorefinery and Biofuel Applications Madeleine J. Bussemaker and Dongke Zhang* Centre for Energy (M473), The University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia
(A Manuscript offered for Industrial & Engineering Chemistry Research)
*
Author for correspondence +61 8 6488 7600 [email protected]
TABLE CAPTIONS Table S1
Comparisons of the mechanisms of pretreatment options
Table S2
Comparisons of sonochemical activities of different frequencies
Table S3
Effect of gas atmospheres on reaction rates
Table S4
Studies of the effects of reactor geometry on sonochemical activity
Table S5
Comparisons of different studies on the effects of flow on sonochemical activity in ultrasonic reactors
Table S6
Some typical compositions of different biomass types
Table S7
Summary of literature on studies regarding ultrasound and lignocellulose
Note: Reference numbers correspond to the reference list from the review article.
Formation of inhibitors
Potential option for biorefineries
~
N.R.
> 160
~
> 150
~
N.R.
< 100
N.R.
> 160
~
> 120 Various
~
N.R.
N.R.
> 120
< 100 < 100 < 100
~ .
N.R. N.R. N.R.
. N.R. N.R.
Ionic liquids Dilute acid pretreatment Alkaline Oxidizing gas Wet oxidation Peroxide Peracetic acid Ultrasound ?
Can be operated in batch or flow systems Can be done in water Self-catalysis by acetic acid from hemicellulose degradation Green solvents which can be manipulated for specific purposes High temperatures
Inhibitor production can be reduced under alkaline conditions Selective lignin degradation
Disadvantages
Cellulose degradation
< 160
Advantages
Lignin degradation
Thermal – low temperature Thermal – high temperature Pretreatment with an organic solvent
Hemicellulose degradation
Comparisons of the mechanisms of pretreatment options
Operation temperature (°C)
Table S1
Loss of hemicellulose Inhibitory compounds formed from lignin degradation Expensive Need to recycle the solvent for viability Expensive Need to recycle the solvent for viability Toxic solvents Unselective degradation Unselective degradation Unselective degradation Low efficiency
N.R. = not reported, = evidence found to support, = evidence found to contradict, ~ = some evidence but was not found to occur in large amounts.
Table S2
Conditions
Comparisons of sonochemical activities of different frequencies
Frequency (kHz)
Power
Results
Sonication of 150 mL of 0.2 M KI solution, measuring of the rate of I2 20 formation at 30 ± 3 C16. At the lower frequency an ultrasonic horn 900 was used and at the higher frequency a transducer plate was used33.
W 39.4 ± 0.5
µmol h-1 W-1 710 ± 50
25.1 ± 0.5
21900 ± 50
Treatment of a polyphenylene ester, polystyrene for 30 min at 40 C. 20 Efficacy was determined by weight 40 582 loss and surface oxidation32. 863 Three ultrasonic devices were used ; 1142 a probe with a tip diameter of 300 mm at 20 kHz in 200 mL of solution, 20 a bath at 40 kHz with 2 L of solution 40 and a multifrequency bath system 582 with 430 ml of solution. 863 1142 Control Ten minutes of ultrasonic irradiation in 100 mL solution on a 5.5 cm 213 transducer at a range of powers at 25 355 ± 2C. The yield of I2 was 647 1056 determined30. 1056 Sonication of 300 mL of 0.1 M KI for 20 minutes at room temperature 40 (this work). 376 995 1179
W dm-3 192.5 37.2 25.3 18.8 17.4
Weight loss (mg cm-2) 0.27 0.11 0.08 0.06 0.03 Oxidation (%) 10.9 11 12.2 13.2 10.3 10.6 µmolL-1 3 – 28 6 – 28 0 – 20 0 – 35 5 µmol 2.84 ± 0.2 13.2 ± 1 9.42 ± 0.9 8.36 ± 0.3
192.5 37.2 25.3 18.8 17.4 W 3-19 4-11 3-10 7 – 29 11 W dm-2 92 ± 1 76 ± 4 72 ± 7 75 ± 5
Table S3 Conditions
Effect of gas atmospheres on reaction rates Gas atmosphere
Rate (µmol min-1)
Rate of sonochemical degradation of phenol No gas under different gases. 541 kHz, 12 mm ultrasonic Pure oxygen horn43.
0.75 0.99
Air
1.42
75/25 argon and air
2.39
Rate of formation of H2O2 in water under noble Helium gas atmospheres at 200 kHz44. Neon
1.9 2.8
Argon
10.6
Krypton
15.8
Xenon
17.8
Table S4
Studies of the effects of reactor geometry on sonochemical activity
Conditions
Geometry
Effect
Comparison of the rates of Reactor type W mL-1 formation of H2O2 at 20 kHz in 2 two different horn reactors and a 18 cm horn, 50 1.1 ml 1.6 bath reactor45. 1 cm2 horn, 50 0.9 ml 1.3 2 ml glass vial 0.26 suspended in a bath Comparison of reaction vessels Diameter (mm) Calorie (W) of different diameters at the same 1.5 transducer plate width and height 20 5 of sonication zone at 200 kHz. 50 60 8.5 Used the yield of peroxide and 90 16 Cl from 1,2,4-trichlorobenzene 46 120 19 in solution .
µmol min-1 2.4 3.9 2.2 3.6 0.60
H2O2 (µmol) 0 2.8 3.1 6 4 Cl- (µmol)
20 50 60 90 120
A study into the effect of liquid height on sonochemical efficiency (SE). The diameter of transducers were 50 mm for 45 and 128.9 kHz and 45 mm for 231 and 490 kHz47.
1.5 5 8.5 16 19
0 3.5 6 12.5 11
Liquid height in Frequency mm/field zone(s) (kHz)
SE value (x 1010 mol J-1)
500 /far 152 /far 79 /near 400 /far 29 /near
5.5 ± 0.6 6.4 ± 0.3 6.7 ± 0.2 6.2 ± 0.2 7.1 ± 0.1
45 128.9 231 490 490
Liquid height in Frequency mm /field (kHz) zone(s) A study on liquid height effect at 29-348 /far 22 three frequencies; 22, 371 and 504 kHz. The diameter of the 29-348 /near and 371 transducer was 102 mm for the far results reported here48. 504 29-252 /near and far
SE trend (x 1010 mol J-1)
The Effect of Ultrasound on Lignocellulosic Biomass as a Pretreatment for Biorefinery and Biofuel Applications Madeleine J. Bussemaker and Dongke Zhang* Centre for Energy (M473), The University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia
(A Manuscript offered for Industrial & Engineering Chemistry Research)
*
Author for correspondence +61 8 6488 7600 [email protected]
TABLE CAPTIONS Table S1
Comparisons of the mechanisms of pretreatment options
Table S2
Comparisons of sonochemical activities of different frequencies
Table S3
Effect of gas atmospheres on reaction rates
Table S4
Studies of the effects of reactor geometry on sonochemical activity
Table S5
Comparisons of different studies on the effects of flow on sonochemical activity in ultrasonic reactors
Table S6
Some typical compositions of different biomass types
Table S7
Summary of literature on studies regarding ultrasound and lignocellulose
Note: Reference numbers correspond to the reference list from the review article.
Formation of inhibitors
Potential option for biorefineries
~
N.R.
> 160
~
> 150
~
N.R.
< 100
N.R.
> 160
~
> 120 Various
~
N.R.
N.R.
> 120
< 100 < 100 < 100
~ .
N.R. N.R. N.R.
. N.R. N.R.
Ionic liquids Dilute acid pretreatment Alkaline Oxidizing gas Wet oxidation Peroxide Peracetic acid Ultrasound ?
Can be operated in batch or flow systems Can be done in water Self-catalysis by acetic acid from hemicellulose degradation Green solvents which can be manipulated for specific purposes High temperatures
Inhibitor production can be reduced under alkaline conditions Selective lignin degradation
Disadvantages
Cellulose degradation
< 160
Advantages
Lignin degradation
Thermal – low temperature Thermal – high temperature Pretreatment with an organic solvent
Hemicellulose degradation
Comparisons of the mechanisms of pretreatment options
Operation temperature (°C)
Table S1
Loss of hemicellulose Inhibitory compounds formed from lignin degradation Expensive Need to recycle the solvent for viability Expensive Need to recycle the solvent for viability Toxic solvents Unselective degradation Unselective degradation Unselective degradation Low efficiency
N.R. = not reported, = evidence found to support, = evidence found to contradict, ~ = some evidence but was not found to occur in large amounts.
Table S2
Conditions
Comparisons of sonochemical activities of different frequencies
Frequency (kHz)
Power
Results
Sonication of 150 mL of 0.2 M KI solution, measuring of the rate of I2 20 formation at 30 ± 3 C16. At the lower frequency an ultrasonic horn 900 was used and at the higher frequency a transducer plate was used33.
W 39.4 ± 0.5
µmol h-1 W-1 710 ± 50
25.1 ± 0.5
21900 ± 50
Treatment of a polyphenylene ester, polystyrene for 30 min at 40 C. 20 Efficacy was determined by weight 40 582 loss and surface oxidation32. 863 Three ultrasonic devices were used ; 1142 a probe with a tip diameter of 300 mm at 20 kHz in 200 mL of solution, 20 a bath at 40 kHz with 2 L of solution 40 and a multifrequency bath system 582 with 430 ml of solution. 863 1142 Control Ten minutes of ultrasonic irradiation in 100 mL solution on a 5.5 cm 213 transducer at a range of powers at 25 355 ± 2C. The yield of I2 was 647 1056 determined30. 1056 Sonication of 300 mL of 0.1 M KI for 20 minutes at room temperature 40 (this work). 376 995 1179
W dm-3 192.5 37.2 25.3 18.8 17.4
Weight loss (mg cm-2) 0.27 0.11 0.08 0.06 0.03 Oxidation (%) 10.9 11 12.2 13.2 10.3 10.6 µmolL-1 3 – 28 6 – 28 0 – 20 0 – 35 5 µmol 2.84 ± 0.2 13.2 ± 1 9.42 ± 0.9 8.36 ± 0.3
192.5 37.2 25.3 18.8 17.4 W 3-19 4-11 3-10 7 – 29 11 W dm-2 92 ± 1 76 ± 4 72 ± 7 75 ± 5
Table S3 Conditions
Effect of gas atmospheres on reaction rates Gas atmosphere
Rate (µmol min-1)
Rate of sonochemical degradation of phenol No gas under different gases. 541 kHz, 12 mm ultrasonic Pure oxygen horn43.
0.75 0.99
Air
1.42
75/25 argon and air
2.39
Rate of formation of H2O2 in water under noble Helium gas atmospheres at 200 kHz44. Neon
1.9 2.8
Argon
10.6
Krypton
15.8
Xenon
17.8
Table S4
Studies of the effects of reactor geometry on sonochemical activity
Conditions
Geometry
Effect
Comparison of the rates of Reactor type W mL-1 formation of H2O2 at 20 kHz in 2 two different horn reactors and a 18 cm horn, 50 1.1 ml 1.6 bath reactor45. 1 cm2 horn, 50 0.9 ml 1.3 2 ml glass vial 0.26 suspended in a bath Comparison of reaction vessels Diameter (mm) Calorie (W) of different diameters at the same 1.5 transducer plate width and height 20 5 of sonication zone at 200 kHz. 50 60 8.5 Used the yield of peroxide and 90 16 Cl from 1,2,4-trichlorobenzene 46 120 19 in solution .
µmol min-1 2.4 3.9 2.2 3.6 0.60
H2O2 (µmol) 0 2.8 3.1 6 4 Cl- (µmol)
20 50 60 90 120
A study into the effect of liquid height on sonochemical efficiency (SE). The diameter of transducers were 50 mm for 45 and 128.9 kHz and 45 mm for 231 and 490 kHz47.
1.5 5 8.5 16 19
0 3.5 6 12.5 11
Liquid height in Frequency mm/field zone(s) (kHz)
SE value (x 1010 mol J-1)
500 /far 152 /far 79 /near 400 /far 29 /near
5.5 ± 0.6 6.4 ± 0.3 6.7 ± 0.2 6.2 ± 0.2 7.1 ± 0.1
45 128.9 231 490 490
Liquid height in Frequency mm /field (kHz) zone(s) A study on liquid height effect at 29-348 /far 22 three frequencies; 22, 371 and 504 kHz. The diameter of the 29-348 /near and 371 transducer was 102 mm for the far results reported here48. 504 29-252 /near and far
SE trend (x 1010 mol J-1)
