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

ResultsEtek 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+945.68e8

35.17

29.59

8.886.8630.37

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

60.4955.90

43.5347.57 55.08

50.7561.49

66.31

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

19.6541.2738.82 46.72

87.2756.1150.46 54.71

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

EthanolSuspension

Heating 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.