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Ethanol Production from the Mixture of Hemicellulose Pre-hydrolysate and Paper Sludge
Li Kang , David Webster, Harry Cullinan and Y. Y. LeeDepartment of Chemical Engineering
Auburn University
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
2
Outline
1. Introduction
2. Pre-extraction process
3. De-toxification of pre-hydrolysate
4. Separation hydrolysis and fermentation (SHF)
of pre-hydrolysate
5. Increasing the ethanol concentration
a. concentrated pre-hydrolysate
b. mixing pre-hydrolysate with paper sludge
6. Conclusion
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Current Kraft pulping process
3
Black Liquor : 80% of hemicelluloses and ligninHeating Value: Hemicellulose (13.6 MJ/kg) Lignin (27 MJ/kg).
Cellulose38 - 50%
Hemicelluloses23 - 32%
Lignin15 - 25%
Other 5 -15%
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Proposed Kraft pulping process
4
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
5
Water
Fresh PineWood Chip
Pre-hydrolysate
Extracted Wood Chip
M/K Laboratory Digester
500-mLCylindrical Batch (bomb)Digesters
2. Pre-extraction Process
Sung-Hoon Yoon, et al., Ind. Eng. Chem. Res., 2010, 49 (13), 5969–5976
Liquor/wood = 5.8 / 1, 170 °C
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
0.00%0.01%0.01%0.02%0.02%0.03%0.03%0.04%
0.00%2.00%4.00%6.00%8.00%
10.00%12.00%14.00%16.00%
0 20 40 60 80 100
Cel
lulo
se L
oss
(%)
Wei
ght L
oss,
H
emic
ellu
lose
Los
s (%
)
Time (min)
Weight Loss Hemicellulose Loss Cellulose Loss
)180162(*
4.15Mannose)
180162(*cos Cellulose −= eGlu
CelluloseMannoseeGluGalactoseXyloseArabinose −++++= )180162(*)cos()
150132(*)( oseHemicellul
6
The profile of weight , hemicellulose and cellulose loss versus extraction time
Yoon, S. H. and van Heiningen, A. , Journal of Industrial and Engineering Chemistry ,16 (1), 74-80, 2010BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
7
Composition of pre-hydrolysate
Xyl2, 2.4 Gal2, 2.1
Man2, 9.1
Man, 0.6
Ara, 1.4Gal, 0.7Glu, 0.4
Xyl, 1.1
Ara2, 0.1
Glu2, 1.4
0.01.0
2.03.0
4.05.0
6.07.0
8.09.0
10.0S
ugar
s C
once
ntra
tion
(g/L
)
0.4
0.2
0.1
0.3
0.8
0.00.10.20.30.40.50.60.70.8
Acetic acid Acetyl group Levulinic acid HMF Furfural
Oth
er C
ompo
unds
(g/L
)
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Three stage pre-extraction process
8
Water
Fresh Wood Chip
First StagePre-hydrolysate I
Second StagePre-hydrolysate II
Third StagePre-hydrolysate III
Make-up Water
Make-up Water
Fresh Wood Chip
Fresh Wood Chip
Extracted Wood Chip
Extracted Wood Chip
Extracted Wood Chip
FirstStage
I
SecondStage
II
ThirdStage
III
Fresh Wood Chip
Water
Extracted Wood Chip
Screw ReactorPre-hydrolysate
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
9
Composition of pre-hydrolysate III after three-stage pre-extraction
Gal2, 3.9
Man2, 15.5
Man, 0.6Ara, 1.4Gal, 0.7Glu, 0.4
Xyl, 1.1Xyl2, 2.7
Ara2, 0.1
Glu2, 3.0
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0S
ugar
s C
once
ntra
tion
(g/L
)
1.4
1.0
0.20.5
2.6
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Acetic acid Acetyl group Levulinic acid HMF Furfural
Oth
er C
ompo
unds
(g/L
)
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Average composition of Woody biomass and main derived hydrolysis products
10J.R.M. Almeida, T. Modig, A. Petersson, B. Hahn-Hägerdal, G. Liden and M.F. Gorwa-Grauslund, J Chem Technol Biotechnol 82 (4) (2007), pp. 340–349
3. De-toxification of Pre-hydrolysate
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
De-toxification test
0.00.40.81.21.62.02.42.83.2
200 250 300 350 400 450wavelength (nm)
Abs
orba
nce
untreated25 °C60 °C
11Vanillin(230nm) Furfural(278nm) HMF(284nm) p-Coumaric acid (308nm) Ferulic Acid (322nm) 4-hydroxyacetophenone (340nm)
UV-Vis Absorbance Changed During De-toxification Test
Overliming: Pre-hydrolysate III was added CaO to pH=10.0 , 25 °C or 60 °C for half hour, centrifuge, then adjust supernatant pH to 5.0 by adding 70% sulfuric acid.
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Composition change after de-toxification test
020
4060
80100
TotalSugar
Mannose+
Glucose
AceticAcid
Levulinicacid
HMF Furfural TotalSolublePhenolic
%
untreated 25 °C 60 °C
12
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
4. Separate hydrolysis and fermentation (SHF) of pre-hydrolysate
0%
20%
40%
60%
80%
100%
Cellulase β-Glucosidase Xylanase Pectinase
48h
enzy
mat
ic d
iges
tibili
ty/%
Glucose Xylose Galactose Mannose
13Enzyme Loading: 25mg protein enzymes / g-mannose oligomer50 °C, pH=4.8BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Fermentation of pre-hydrolysate III by Saccharomyces cerevisiae
14
SHF conditionEnzymatic Hydrolysis:: 25mg protein Pectinase/ g-mannose oligomer and 50°C.Fermentation Conditions : 32°C, Saccharomyces cerevisiae D5A
0
2
4
6
8
10
12
0 20 40 60 80 100Time (h)
Etha
nol C
onc.
(g/L
)
untreated60 °C25 °C
0
1
2
3
4
5
0 20 40 60 80 100Time (h)
Glu
cose
Con
c. (g
/L)
untreated60 °C25 °C
02
46
810
1214
16
0 20 40 60 80 100Time (h)
Man
nose
Con
c. (g
/L)
untreated60 °C25 °C
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
2694
20
246
146
4485
1141 55 76 63
050
100150200250300
Total Sugars(g/L)
Glu+Mann (g/L) EthanolConc.(g/L)
Yield (%)
III IV (2.2 ×) V (5.9 ×)
15
Laboratory Scale: Rotary evaporator.-Total sugar concentration Increase. -Furfural and acetic acid are removed up to 90%. Industry Scale: Steam- Stripping or Flash Tank and Multiple-effect Evaporator (Kraft mill).
5. Increasing the ethanol concentration
a. concentrated pre-hydrolysate
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
16
Kraft Paper Mill Sludges as a Feedstock
• 4.1 to 5 million tons sludge per year in U.S.- Incineration (greenhouse gas emission, low energy efficiency)- Landfill (greenhouse gas emission, limited land availability)
• Low/ Negative Cost ( 0 to 50$ per ton disposal cost)
• High Carbohydrate and Low Lignin Content (Kraft pulping process removes most of lignin and hemicellulose)
• Easily Digested by Cellulase (No need for expensive pretreatment)
b. mixing pre-hydrolysate
with paper sludge
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
17
Composition of various sludges
Primary Sludge is from Boise paper mill, Jackson, AL.
Kang,L., Wang,W., Lee, Y.Y., 2010. Appl. Biochem. Biotechnol. 161(1-8), 53-66.BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Fermentation of pre-hydrolysate IIIwith paper sludge
Maximum Ethanol Yield (%) Maximum Ethanol Conc. (g/L)
Pre-hydrolysate III with paper sludge 71.5 (120h) 31.5
Pre-hydrolysate only 82.6 (48h) 10.3
Paper sludge only 73.4 (120h) 27.8
18
Enzyme Loading: Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan)+ 25mg protein Pectinase/ g-mannose oligomerSolid Loading:15 g total solid /100ml work volumeSSF Conditions : 36°C, Saccharomyces cerevisiae D5A
0
5
10
15
20
25
30
35
0 24 48 72 96 120Time (h)
Etha
nol C
onc.
(g/L
)
Paper Sludge onlyPaper Sludge with Pre-hydrolysatePre-hydrolysate only
0%10%20%30%40%50%60%70%80%90%
0 24 48 72 96 120Time (h)
Etha
nil Y
ield
(%)
Paper Sludge onlyPaper Sludge with Pre-hydrolysatePre-hydrolysate only
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Fermentation of pre-hydrolysate with de-ashed sludge
Maximum Ethanol Yield (%) Maximum Ethanol Conc. (g/L)
Pre-hydrolysate III with de-ashed sludge 71.3 (120h) 40.1
De-ashed sludge only 75.2 (120h) 35.0
19
Enzyme Loading: Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan)+ 25mg protein Pectinase/ g-mannose oligomerSolid Loading:15 g total solid /100ml work volumeSSF Conditions : 36°C, Saccharomyces cerevisiae D5A
05
1015202530354045
0 24 48 72 96 120Time (h)
Etha
nol C
onc.
(g/L
)
De-ashed sludge with pre-hydrolysate III
De-ashed sludge only
0%
10%
20%
30%
40%
50%
60%
70%
80%
0 24 48 72 96 120Time (h)
Etha
nol Y
ield
(%)
De-ashed sludge with pre-hydrolysate III
De-ashed sludge only
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
Conclusion
• Combining pre-hydrolysate with sludge can more than double ethanol production
• Hemicellulose pre-hydrolysate can be converted to ethanol through de-toxification, enzymatic hydrolysis and fermentation processes.
• The fermentation of concentrated pre-hydrolysate can increase the ethanol concentration.
• The fermentation performance of the mixture of pre-hydrolysate with sludges has high efficiency and more practical. 20
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011
21
Acknowledgments
Vekanta Ramesh PallapoluUrvi KothariSuan ShiAllen SmithSung-Hoon YoonGopal Krishnagopalan
Alabama Center for Paper and Bioresource Engineering Boise Cascade, LLC Genencor International
BioPro Expo & Marketplace / Atlanta, GA / March 14-16, 2011