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The Green Conversion of N-acetyl-D-Glucosamine into Platform Chemicals and Biochar
Greg Curtis and Dr. Francesca KertonCentre for Green Chemistry & Catalysis, Memorial University of Newfoundland,
St. John’s, Canada
Climate Change and Biorefineries
The global temperature is increasing due to the build up of GHGs that are emi7ed from human ac8vi8es. Without a significant shi= towards industrial sustainability the global biosphere will become increasingly inhospitable to human ac8vity.
The 21st century will see the rise of the biorefinery for waste u8liza8on and the sustainable produc8on of fuels, materials and energy. An ocean-‐based biorefinery focuses on the u8liza8on of fishery wastes and seaweeds. Chi8n is obtained from crustaceans and holds great poten8al as a biorefining feedstock.
Why Waste U5liza5on is Necessary for Sustainability
.
Aqueous Dehydra5on of N-‐acetyl-‐D-‐glucosamine with B(OH)3 and NaCl
Acknowledgments & References
Conclusions-‐ 75.4 mol% / 90.6% selec8vity yield for 3A5AF : 220 oC, 7.5 wt% NAG, 10 minutes and 1:2 mole ra8os (rela8ve to NAG) of NaCl and B(OH)3. -‐ 67.8 mol% / 95.7% selec8vity a=er the 3rd cycle of water with addi8on boric acid at : 220 oC, 7.5 wt% NAG and 10 minutes. -‐ 69.5 mol% / 86.5% selec8vity yield for 5-‐HMF : 220 oC, 7.5 wt% NAG, 40 min and 2:2 mole ra8o (rela8ve to NAG) of NaCl & B(OH)3.-‐ Biochar has poten8al to be carbon nega8ve and improve soil nutri8on.
Results from Conversion of NAG to 3A5AF & 5-‐HMF in Subcri5cal water
Products were extracted in ethyl acetate and then analyzed on by GC-‐MS. The reac8on pressure was within the range of 200 -‐ 450 psi.
By adjus8ng the molar ra8os of addi8ves, a selec8vity of 90.6% with a molar yield of 75.40% for 3A5AF and an 85.6% selec8vity for 5-‐HMF with a molar yield of 69.5% were obtained under op8mal condi8ons.
Biochar as Carbon Nega5veWhen biochar is produced at 400 oC or below there tends to be a higher reten8on of func8onal groups (ketones, aldehydes, carboxylic acids and alcohols) than when pyrolysis temperatures are used (>800 oC) (2). These preliminary studies have shown that the biochar produced at the lower temperature can have a great affinity at retaining fer8lizer nutrients. Biochar has soil and atmospheric benefits that are green.
The waste generated in the fishery plants in Atlan8c Canada is es8mated to be 418, 000 t/yr (1). Newfoundland alone produces 39,000 t/yr shellfish waste (northern shrimp and snow crab) with a chi8n content of 20-‐25 wt%. The waste is typically dumped in the sea and presents a green opportunity.
Subcri8cal water is non-‐toxic, inexpensive and versa8le as a reac8on solvent. Biochar is a common by-‐product in the hydrothermal processing of carbohydrates. The environmental impact of this process is reduced when u8lizing the biochar as a valuable product.
Recycling the water phase was one of the main goals of this research. For the addi8ve-‐free reac8ons, 200 mol% of NaCl and B(OH)3 rela8ve to NAG were used in the first cycle. Only fresh NAG was added to the 2nd and 3rd runs of the reac8on with no addi8onal water nor NaCl/B(OH)3 were added.
Recycling the reac8on water was beneficial to 3A5AF selec8vity and yield. NaCl decreased the produc8on of 3A5AF but B(OH)3 significantly increased it. The boost in yields and selec8vity is more striking at 220 oC and provides incen8ve to extend the number of produc8ve cycles.
12
3. An efficient method to break down the crystallinity of chitin needs to be
identified. This would allow the enzymes easier access to the reactive groups
within the biopolymer.
n
O
OH
OHO
NHR
HONHR
OH
R = COCH3, ChitinR = H, Chitosan
OOHO
5-HMF
OO
3A5AF
NHO
LA
Chromogen I and III
GA
O
OHO
HOOH
OH
OH
OH
NH2
O
O OHO
HO HOH
HO
HO
NHAcNHAc
Figure 20.3 Materials and chemicals accessible from waste crustacean shells
As biopolymers, chitin and chitosan have been used in many areas including
catalysis,31 medicine,32 and the food industry.33 Interestingly, in terms of developing
sustainable processes, chitosan was recently shown to be an excellent flocculating
agent in the dewatering of green algae for future use as a feedstock for biofuel
production.34 Not only was it superior in terms of life cycle assessment, it also
afforded a superior technical performance compared with alum and other
conventional flocculants.
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1 : 0.5 - 2 NAG: NaCl1 : 1 - 2 NAG : B(OH)3
180 oC - 220 oC Water10 - 60 Minutes
NAG
3A5AF
OO
O
O
NH2
OH
NH2
5AcNH2F
3NH2F5HMF
O
O
7.5 wt% 10 min
5.0 wt% 10 min
3.75 wt% 10 min
7.5 wt% 20 min
5.0 wt% 20 min
3.75 wt% 20 min
7.5 wt% 40 min
5.0 wt% 40 min
3.75 wt% 40 min
0 25 50 75 100
17.6
71.7
86.5
14.6
6.6
3.5
4.5
2.9
21.5
82.4
28.3
13.5
85.4
93.4
87.8
91.9
97.1
74.2
3A5AF 5Ac3NH2F 5-HMF LA 3NH2F
NAG Concentration and Time Influence on Selectivity a Yields 1:2:2, NAG: NaCl: B(OH)3 at 220 oC
7.5 wt% 10 min
5.0 wt% 10 min
3.75 wt% 10 min
7.5 wt% 20 min
5.0 wt% 20 min
3.75 wt% 20 min
7.5 wt% 40 min
5.0 wt% 40 min
3.75 wt% 40 min
0 23 45 68 90
6.8
31.4
69.5
8.2
6.7
3.8
1.7
1.3
10.0
23.4
9.1
10.2
35.2
70.0
69.1
25.8
32.1
25.2
3A5AF 5Ac3NH2F 5-HMF LA
7.5 wt% 10 min
5.0 wt% 10 min
3.75 wt% 10 min
7.5 wt% 20 min
5.0 wt% 20 min
3.75 wt% 20 min
7.5 wt% 40 min
5.0 wt% 40min
3.75 wt% 40 min
0 25 50 75 100
69.9
79.1
84.5
76.3
80.0
90.2
84.0
85.9
90.6
3A5AF 5Ac3NH2F 5-HMF LA 3NH2F
NAG Concentration and Time Influence on Selectivity a Yields 1:1:2 NAG: NaCl: B(OH)3 at 220 oC
7.5 wt% 10 min
5.0 wt% 10 min
3.75 wt% 10 min
7.5 wt% 20 min
5.0 wt% 20 min
3.75 wt% 20 min
7.5 wt% 40 min
5.0 wt% 40 min
3.75 wt% 40 min
0 22.5 45.0 67.5 90.0
3.27
17.72
47.98
10.39
43.20
71.03
36.03
62.81
75.40
3A5AF 5Ac3NH2F 5-HMF LA
1st
2nd + NaCl
3rd + NaCl
1st
2nd + B(OH)3
3rd + B(OH)3
0 0.25 0.50 0.75 1.00
94.6%
97.8%
84.5%
86.5%
82.0%
98.5%
%3A5AF %5Ac3NH2F %5-HMF %LA %3NH2F
0
17.5
35.0
52.5
70.0
1st 2nd + NaCl 3rd + NaCl 1st 2nd + B(OH)3 3rd + B(OH)3
66.863.3
43.2
31.634.5
48.9
3A5AF%mol 5Ac3NH2F%mol 5-HMF%mol LA%mol3NH2F%mol
1st
2nd + NaCl
3rd + NaCl
1st
2nd + B(OH)3
3rd + B(OH)3
0 25 50 75 100
53.3
48.9
38.6
27.6
31.8
36.9
18.3
18.6
43.3
34.5
35.6
49.2
28.4
32.5
18.1
37.9
32.6
13.9
Biochar Water Phase Ethyl Acetate Extract
1st
2nd + NaCl
3rd + NaCl
1st
2nd + B(OH)3
3rd + B(OH)3
0 25 50 75 100
53.6
52.6
29.1
21.4
27.7
33.8
9.4
11.5
34.4
40.2
35.9
32.3
37.0
35.9
36.5
38.4
36.5
34.0
TGA of Biochar from 1:2:2 NAG:NaCl:B(OH)3 at 220 oCTGA of Biochar from 1:2 NAG:NaCl at 220 oC
Additive-free 180 oC
Additive-free 220 oC
1:2 NAG:NaCl 180 oC
1:2 NAG:NaCl 220 oC
2:2 B(OH)3:NaCl 180 oC
2:2 B(OH)3:NaCl 220 oC
1:2 NAG:B(OH)3 180 oC
1:2 NAG:B(OH)3 220 oC
0 17.5 35.0 52.5 70.0
0.98
1.28
0.48
0.39
0.21
0.17
0.01
0.01
26.79
27.35
30.32
29.42
28.94
31.68
25.11
24.82
8.35
7.71
6.37
7.08
8.60
7.53
7.47
8.20
59.03
57.33
57.10
57.06
55.80
54.34
61.90
61.65
C % H % N % O % B %
Elemental Composition with and without Additives
O
O OHO
HO OHBaker's Yeast
Water3 days25 oC5-HMF
Total Reactants (g)
= 384.75g
Total Product (g) Total Waste (g)
E-Factor (no
Biochar)
E-Factor (1g
Biochar)
E-Factor (2g
Biochar)
1st) 384.75g 1st 220 oC) 1.26g 3A5AF
383.49g 304.36 169.24 117.02
2nd 180 oC) 7.5g NAG, 4.19g B(OH)3
2nd 220 oC) 11.69g
2nd 180 oC) 3.58g 3A5AF
2nd 220 oC) 3.54g 3A5AF
2nd) 8.11g
2nd) 8.15g
2nd) 2.27
2nd) 2.30
2nd) 1.55
2nd) 1.58
2nd) 1.10
2nd) 1.11
3rd 180 oC) 7.5g NAG, 4.19g B(OH)3
3rd 220 oC) 11.69g
3rd 180 oC) 3.78g 3A5AF
3rd 220 oC) 3.84g 3A5AF
3rd) 7.91g
3rd) 7.85g
3rd) 2.09
3rd) 2.04
3rd) 1.45
3rd) 1.42
3rd) 1.02
3rd) 1.00
Product A.E at 65% A.E at 75% A.E at 85% A.E at 95%
100 mol% 3A5AF
49.1% 56.6% 64.2% 71.7%
100 mol% 5-HMF
37.1% 42.8% 48.5% 54.2%
Product A.E at 65% A.E at 75% A.E at 85% A.E at 95%
65 mol% 3A5AF
31.9% 36.8% 42.9% 45.6%
65 mol% 5-HMF
24.1% 27.8% 31.5% 35.2%
B
OH
HO OH
BOHO
O
BO
B
OB
HO OH
OH
Boric Acid Metaboric Acid Trimer of Metaboric Acid
>170 oC
H2OH2O
Successful proof-‐of-‐concept for the bio-‐reduc8on of 5-‐HMF
250 - 300 oC
H2O
O
B
O
B B
O
B
OO
OHHO
Tetraboric Acid
Recycling the reac8on water for 3 cycles at 180 oC with addi8onal NaCl or B(OH)3
The reac8ons were performed in a 300 mL batch reactor with a 7.5 wt% NAG solu8on. Boric acid is responsible for the dehydra8on of NAG and when combined with NaCl the yields are boosted. Depending on reac8on condi8ons the type of boric acid that is cataly8cally ac8ve may change. (Studies have begun to compare boric acid to borax (sodium tetraborate))
The funding was provided by NSERC of Canada, RDC NL, CFI, Hebron and Memorial University of Newfoundland. Acknowledging the Green Chemistry and Catalysis Group for their support in and out of the lab. 1) AMEC Earth & Environmental Limited, Management of Wastes from Atlan8c Seafood Processing Opera8ons, Report for Environment Canada Atlan8c Region, 2003. 2) D. Day, R. J. Evans, J. W. Lee, D. Reicosky., Energy, 2005. 30, 2558–2579.
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