processing lignins guozhan jiang. objectives to find a method to convert etek and asian lignins into...
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Processing Lignins
Guozhan Jiang
Objectives
• To find a method to convert Etek and Asian lignins into bio-oils.
• To characterise the products using PyGC/MS and other chromatographic or spectroscopic methods.
• To upgrade the bio-oils to valuable chemicals or transportation oils.
Outline
• Component determination
• PyGC-MS work
• Preliminary work for run on 150g/h rig
• Alternative way to pyrolysis
• Future work
Component determination: wet chemistry method
Extractives: Extracted using: ethanol/toluene (6hrs)ethanol (4hrs)water (2hrs)
Lignin (Klason): 0.1M NaOH boiling 1hr72% H2SO4 treatment 4hrs
Cellulose: NaClO2 bleaching of holocellulose
Hemicellulose: 17.5% NaOH treatment of cellulose
Biomass
Results
Etek lignin Asian lignin
Extractive (%) 12.74 39.68
Lignin (%) 29.20 -
Cellulose (%) 45.70 -
Hemicellulose (%)
9.32 -
Component determination
• The component of Etek lignin can be determined using this method.
• This method is not suitable for Asian lignin since the extractive free samples can be completely dissolved in 0.1M NaOH.
• Asian lignin must have a much less cross-linking density in its molecular structure.
Conclusions
PyGC-MS work, 06-Sep-2007 + 20:02:03
1.50 11.50 21.50 31.50 41.50 51.50 61.50 71.50 81.50 91.50 101.50Time0
100
%
0
100
%
asian lignin 1 Scan EI+ 78+94
1.51e929.59
41.32
38.9035.14
33.52
41.39
52.4147.3543.66 50.24 60.5652.77
57.11
asian lignin 1 Scan EI+ TIC
2.06e1041.32
30.36
29.59
3.64
17.318.554.29 10.23 26.80
35.13
33.52
31.86
38.90
41.39
43.66
47.35
46.78 60.5650.24 52.41
57.11
53.1263.88
Species containing m/z =94 and 78
Asian lignin @600oC for 15s
, 06-Sep-2007 + 23:52:10
1.50 11.50 21.50 31.50 41.50 51.50 61.50 71.50 81.50 91.50 101.50Time0
100
%
0
100
%
etek lignin 1 Scan EI+ 78+94
5.68e835.17
29.59
8.886.86
30.37
41.35
38.89
35.66
46.79
42.37
44.68
49.97
52.76
57.2854.42
etek lignin 1 Scan EI+ TIC
1.71e1035.18
30.38
17.36
4.80
3.42
9.86
8.517.28
16.70
14.46
27.9523.02
19.68 25.73 33.34
56.5443.13
41.35
38.89
35.77
46.79
43.36 50.84
54.7757.28
Etek lignin species containing m/z = 94 and 78
Etek lignin@600oC for 15s
, 06-Sep-2007 + 20:02:03
1.50 11.50 21.50 31.50 41.50 51.50 61.50 71.50 81.50 91.50 101.50Time0
100
%
0
100
%
asian lignin 1 Scan EI+ TIC
2.06e1041.32
30.36
29.59
3.64
17.318.554.29 10.23 26.80
35.13
33.52
31.86
38.90
41.39
43.66
47.35
46.78 60.5650.24 52.41
57.11
53.1263.88
asian lignin 400a Scan EI+ TIC
1.73e1041.27
3.68 17.27
30.2326.7438.80
60.49
55.9043.53
47.57 55.0850.75
61.4966.31
Asian lignin @400oC for 15s
Asian lignin@600oC for 15s
, 06-Sep-2007 + 23:52:10
1.50 11.50 21.50 31.50 41.50 51.50 61.50 71.50 81.50 91.50 101.50Time0
100
%
0
100
%
etek lignin 1 Scan EI+ TIC
1.71e1035.18
30.38
17.36
4.80
3.42
9.86
8.517.28
16.70
14.46
27.9523.02
19.68 25.73 33.34
56.5443.13
41.35
38.89
35.77
46.79
43.36 50.84
54.7757.28
etek 400a Scan EI+ TIC
2.29e93.65
3.42
47.59
3.72
3.76
42.91
17.31
4.89
34.5830.26
19.65
41.2738.82 46.72
87.2756.11
50.4654.71
Etek lignin 400 and 600
Etek lignin@400oC for 15s
Etek lignin @600oC for 15s
PyGC-MS work
• The two lignins can not be pyrolysed effectively at 400oC.
• Asian lignin is a ‘real’ lignin.
• Etek lignin has similar composition to normal biomass.
Conclusions
Preliminary work for run lignins on 150g/h rig
• The two lignins are difficult to feed continuously.
• Two approaches to be adopted for feeding properly (1) Modify feeding system, (2) Modify lignins.
• Modification of lignins is chosen in this work by pelitization.
Pellitization
Alcohol extracted compounds as binders
Asian lignin
Ethanol
SuspensionHeating up
80oC
“Dough” like
Drying
Pellet
Mixing
Pelletization of Asian lignin
Before pelleting After pelleting
Pellet
Alternative to pyrolysis
Method % dissolved
0.1 M NaOH aqueous, 4hrs boiling, 10% 10.2
Ethanol + 0.1 M NaOH, 4hrs boiling, 10% 10.5
Isopropanol + 0.1M NaOH, 4hrs boiling, 10% 21.2
Isopropanol + 0.1M H2SO4 + Phenol (13.5% wt), 10% 28.3
Extracted using ethanol/toluene (6hrs), ethanol (4hrs) and water (2hrs), extractive free samples boiling in 0.1M NaOH, 2%
100
Asian lignin
Alternative to pyrolysis
Extractive free sample dissolved in 0.1M NaOH,2%
Future work• Run Asian and Etek lignins on 150 g/h rig for
pyrolysis • Hydrogenation of lignin pyrolytic products to
produce saturated phenol and phenol substitutes, which may be used to produce phenolic resin.
• Quantification of mass balance using Py-GC/MS.• Hydrogen, steam or alcohol assisted pyrolysis to
reduce char formation.
