1. The Green Conversion of N-acetyl-D-Glucosamine into
Platform Chemicals and Biochar
Greg Curtis and Dr. Francesca Kerton
Centre 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
Nega5ve
When
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.
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
O
HO
NHR
HO
NHR
OH
R = COCH3, Chitin
R = H, Chitosan
O
OHO
5-HMF
O
O
3A5AF
NH
O
LA
Chromogen I and III
GA
O
OH
O
HO
OH
OH
OH
OH
NH2
O
O O
HO
HO
H
OH
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: NaCl
1 : 1 - 2 NAG : B(OH)3
180 oC - 220 oC
Water
10 - 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
66.8
63.3
43.2
31.6
34.5
48.9
3A5AF%mol 5Ac3NH2F%mol 5-HMF%mol LA%mol
3NH2F%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 OH
O
HO OHBaker's Yeast
Water
3 days
25 oC
5-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
B
O
HO
O
B
O
B
O
B
HO OH
OH
Boric Acid Metaboric Acid Trimer of Metaboric Acid
>170 oC
H2O
H2O
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.
“When
all
the
trees
have
been
cut
down,
when
all
the
animals
have
been
hunted,
when
all
the
waters
are
polluted,
when
all
the
air
is
unsafe
to
breathe,
only
then
will
you
discover
you
cannot
eat
money.”