70
Hydrothermal Conversion of Lignocellulosic Biomass to Biofuels and Valuable Chemicals Updated on April 30, 2012
Hydrothermal Conversion of Lignocellulosic
Biomass to Biofuels and Valuable Chemicals
Updated on April 30, 2012
Hydrothermal Conversion HTC 101
Biomass
Water
Heating
Hydrothermal Conversion
• At 200- 400 oC, 4-20MPa. water is still liquid.
• At this state, water can catalyze both acidic and basic reactions because
self-dissociation of water to H+ and OH- is enhanced.
SubcriticalFluids
05
10152025303540
0 100 200 300 400 500 600
Temperature (oC)
Pres
sure
(MPa
)
Liqu
id
Supercritical fluid
Vapor phase
• When the temperature of water is close to supercritical point (374 oC), the phase boundary between liquid and gas disappears, and then all
reactions are enhanced by the homogenous media. • Due to these special catalytic properties of hot water, biomass HTC to
bio-oil calls a great interest, but still not well studied.
Phase Behavior of Water
Ionic Product (IP)
Density
Dielectric Constant (ε)
Dens
ity
(kg/m
3)
800
1000
600
400
200
0
0 100 200 300 400 500 600Temperature (oC)
IP ε
-10
-12
-14
-16
-18
-20
-22
-240
20
40
60
80
100V
IIIVI
VII
LiquidI
VaporSolid
200 300 400 500 600Temperature (K)
700
Pres
sure
(MPa
)
101
100
102
10-1
10-2
10-3
10-4
103
104
10-5
Critical Point (374oC)
Triple Point
• Critical Point at 374oC• In the subcritical region, ionic reactions are enhanced, while in the
supercritical region – free radical reactions are enhanced.
Advantages of Hydrothermal Conversion of Lignocellulosic Biomass to biofuel
Lignocellulosic biomass Most abundant feedstock Low cost feedstock compared, can be zero for waste biomass like wood
residue, manure, etc. High yield crops (e.g. energy crops) identified
Wet feedstock without predrying A thermochemical process that does not need to separate
cellulose from lignin Can produces biogas and biooil depending on conditions
Comparison of HTC with other technologies
Technologies Conditions Time Main Products
Notes
Aerobic treatment Ambient T and P > 20 days CO2, Nitrate, N2O
No bioenergy
Anaerobic treatment Ambient T and P ~15 days CH4, CO2 Slowly
Gasification/pyrolyis 400~600 oC Several minutes
CH4, H2, CO, CO2
Predrying required
HTC 250 to 350 oC 0 to 60 min Bio-oil and CH4 & H2
Without predrying
Hydrothermal Conversion of Cattle Manure to Biofuels
Much cattle manure in Canada
0 500 1000 1500 2000 2500 3000 3500
Central Oldman - Belly (AB)
Little Bow (AB)
Lower Red Deer - Matzhiwin (AB)
Lower Oldman (AB)
Headwaters Battle (AB)
Lower Bow - Crowfoot (AB)
Upper Red Deer - Blindman (AB)
Central Oldman - Willow (AB)
(kg/ha)
• In Canada, cattle manure production: 0.5 million tons per day [1].• Meanwhile, more cattle manure is produced in per hectare land.
Statistics Canada, Cattle Statistics, 2007.
Air Pollution from Cattle Manure
1380
1430
1480
1530
1580
1990 2004 20053600
4100
4600
5100
5600
N2O
CH4
CH4 and N2O emission from cattle manure in Canada .
• Toxic gas---Ammonia
• Greenhouse gases--- CH4 & N2O
2%
29%
41%
20%
4%4%
Ammonia emission sourcesin Canada, 2005
(Environment Canada, Ammonia, 2009).
(kt C
O2eq
)
Year
Cattle manure
National Inventory Report, 1990-2005: Greenhouse Gas Sources and
Sinks in Canada. Environment Canada, 2007.
Water pollution from cattle manure
• Pollutants---- Ammonia, Nitrate, and Phosphorus
• Water pollution---- Eutrophication [5]
Cattle manureAmmonia
NitratePhosphorus
Surface water
Underground water
Eutrophication
Daniel, T. C.; Sharpley, A. N.; Lemunyon, J. L.,
Agriculture Phosphorus and Eutrophication:
A Symposium Overview. Journal of
Environmental Quality 1998, 27: 251-257
Soil pollution from cattle manure• Soil pollution--- Acidification
Cattle manure
AmmoniaInorganic acid
Ammonium salts [ (NH4)2SO4 ]
Rain
Soil
(NH4)2SO4 + O2 H2SO4 + HNO3
Acidified soil
Soil
Breemen, N. V.; Burrough, P. A.; Velthorst, E. J.; Van Dobben, H. F.; Wit,T. D.; Ridder, T.;
Reijnders, B. H. F. R., Soil Acidification from Atmospheric Ammonium Sulphate in Forest
Canopy through Fall. Nature 1982, 299:548-550.
Overall Objectives of the Research Program
Cattle manure waste
Hydrothermal conversion
To produce bioenergy(biogas and bio-oil)
To reduce pollution and odor
• Literatures have shown that swine manure, wood and grass can be converted to bio-oil by hydrothermal conversion (HTC) [7-8].
• NO report on cattle manure in public literature
Overall Experimental Procedures
Gases Liquid products Solids
Extraction
Bio-oil
Yields Compositions
Compositions(H2, CO, CO2, <C5)
Micro-GC
GC/MSGC/FID
Cattle manure
Aqueous solutions
Glucose/Cellulose
1.8 L reactor
7
70 mL tubular reactor(260~340 oC) (275~320 oC)
Aqueous solutions (with catalysts)
Yields
Hydrothermal Gasification of Cellulose and Cattle Manure
Effects of Alkalinity and Phase Behaviour
Cellulose• Cellulose (a polymer of glucose) is the most abundant biopolymer
globally, accounting for 1.5 x 1012 tonnes of annually available biomass. (Klemm et al, 2005)
Glucose (C6H12O6)
2 2 2 6 12 6
6 12 6 2 2 2
2 2 2
6 6 66 12 6
12 12 6
CO H O O C H OC H O H O H CO
H O H O
+Photosynthesis
Steam Reforming
Hydrothermal Gasification
Effects
Catalysts Physical effectsHeating Speed Gas Yield
Supercritical > Subcritical
Alkali salts(Control pH)
Pt group metals(Steam Reforming)
Cellulose Decomposition
OHO
O HO H
O H O H
OHO H
OO H
O H O H
O O H
OH O H
OHOH
Fructose - C6H12O6
O
O HOH O H
O HO H
D-Glucose - C6H12O6
OOOH
Furfural Alcohol (5-HMF) C6H6O3
OH
O
O H
O H
Erythrose - C4H8O4
OOH
Glycolaldehyde - C2H4O2
+
OOH
Glycolaldehyde - C2H4O2
OHO H
O
Glycolic Acid - C2H4O3
O H
OH O
Glyceraldehyde - C3H6O3
Dihydroxyacetone - C3H6O3O
OH O HO
O
Pyruvaldehyde - C3H4O2
O H
O
O H
Lactic Acid - C3H6O3
OOO
+Furfural - C5H4O2Formaldehyde - CH2O
OHO
O H
O H
OH
O
O
+
Levulinic Acid - C5H8O3
O H
OFormic Acid - CH2O2
O HOH
O H
1,2,4 Benzenetriol - C6H6O3
O H - : A lka li C ata lyzed reaction
H + : Acid C ata lyzed reaction
LD : Low density reaciton
H D : H igh density reaction
-H 2O
+H 2O
R A
R A
R A
-H 2O
+H 2O
LBVET
LBVET
LBVET
O O
O H
Acetaldehyde - C2H4O Acetic Acid - C2H4O2
Acrylic Acid - C3H4O2 Propionic Acid - C2H4O
O H
O
O H
O
O H
OO
Formic Acid - CH2O2Formaldehyde - CH2O
O H -
O H -O H -
O H -
H +
H +
H +
H +
LD
H D
H D
H D
LD
Pathway I
Pathway II
Pathway III
All Intermediates Not Equal
0
0.2
0.4
0.6
0.8
1
1.2
Gram
s Gas
ified
Per
Gra
m F
eeds
tock
Results by Knezivic et al (2009) show not all intermediates gasified as easily…
Research Objectives and Overview
• Determine effects of alkali salt (Na2CO3) concentration on the gasification of cellulose in the presence of a Platinum group metal
• Determine effect of headspace fraction on the hydrothermal gasification of cellulose in the presence of a Platinum group metal
• Effect of alkali and a Pt group metal on the hydrothermal gasification of a mixed biomass, cattle manure.
Experimental Setup I
• Two batch reactors were constructed from SS 316 tubing. The reactor volume was 69mL.
• Reactors heated by Muffle Furnace
• Gas composition determined by micro gas chromatography (micro-GC)
• Liquid phase composition determined by gas chromatography with a flame ionization detector (GC-FID)
Effects of Alkalinity with 5% Pt/Al2O3 catalyst
Effects of Residence Time
0
1
2
3
4
5
6
0
1
2
3
4
5
6
•Sodium Carbonate (alkaline pH) increase both carbon dioxide and hydrogen production
Acetic Acid and Methane
• As more acetic acid was produced, increasing amounts of methane were found in the solution.
• Highest yields of acetic acid (and methane) were found in 0.1M sodium carbonate solution.
Liquid Phase Analysis
Furfu
ral A
lcoh
ol (1
2.3m
M)
Unk
now
n (A
rea=
305.
4)
0M Na2CO3
60,000
50,000
40,000
30,000
20,000
10,000
0
uV
30,000
24,000
18,000
12,000
6,000
0
uV
Unk
now
n In
term
edia
te (A
rea-
641
.8)
But
yric
Aci
d (0
.3m
M)
n-C
apro
ic A
cid
(0.6
mM
)
Lact
ic A
cid
(0.3
mM
)
Unk
now
n In
term
edia
te (A
rea=
806.
9)
Acet
ic A
cid
(0.3
6mM
)P
ropi
onic
Aci
d (0
.21m
M)
50 mM Na2CO3
Ace
tic A
cid
(11.
6 m
M)
Lact
ic A
cid
(9.5
mM
)
Dih
ydro
xyac
eton
e (2
8.3m
M)
181614121086420
50,000
40,000
30,000
20,000
10,000
0
Retention Time (minutes)
uV
25,000
20,000
15,000
10,000
5,000
0
uV
Ace
tic A
cid
(1.5
mM
)P
ropo
ioni
c A
cid
(0.2
mM
)B
utyr
ic A
cid
(0.4
mM
)
Dih
ydro
xyac
eton
e (7
7.4m
M)
Lact
ic A
cid
(4.3
mM
)
Pro
pion
ic A
cid
(2.1
mM
)
But
yric
Aci
d (1
.8m
M) 100 mM Na2CO3
500 mM Na2CO3
181614121086420
Retention Time (minutes)
0M Na2CO3 – More Furfural Alcohol (HMF)
500 mM Na2CO3 – More Dihydroxyacetone and Lactic Acid
Alkalinity Effects with 5% Pt/SiO2
Similar but more variable results were obtained using a 5% Pt/SiO2 catalyst.
Alkalinity Effects with 1% Pt/Al2O3
With a higher loading of 1% Pt/Al2O3, carbon monoxide became an important product under low alkalinity.
Effect of Headspace Fraction
• As headspace fraction increased, hydrogen increased. • Magnitude of increase was dampened when sodium carbonate was added.
Liquid Phase Analysis
15,000
12,000
9,000
6,000
3,000
0
Aceto
ne
Unkn
own I
nterm
ediat
e
Aceti
c Acid
(2.8
mM)
Prop
ionic
Acid
(0.33
mM)
Butyr
ic Ac
id (1.
1 mM)
Dihy
droxy
aceto
ne (4
mM)
Lacti
c acid
(0.65
mM)
Levu
linic
Acid
(0.13
mM)
HMF (
1.67 m
M)
1,400
1,000
600
200
-200
-600
-1,000
-1,400
Aceto
ne Unkn
own I
nterm
ediat
e
Aceti
c Acid
(2.6
mM)
Prop
ionic
Acid
(0.5 m
M)Bu
tyric
Acid
(0.7 m
M)
Dihy
droxy
aceto
ne (0
.2 mM
)La
ctic a
cid ( N
D)
HMF (
0.1 m
M)
181614121086420
100,000
80,000
60,000
40,000
20,000
0
Unkn
own I
nterm
ediat
e
Aceti
c Acid
(2.9
mM)
Prop
ionic
Acid
(0.6 m
M)
Butyr
ic Ac
id (0.
8 mM)
Lacti
c acid
(1.3
mM)
Levu
linic
Acid
(0.55
mM)
HMF (
21.0
mM)
Retention Time (min)
80,000
70,000
60,000
50,000
40,000
30,000
20,000
10,000
0
Aceto
neMe
thano
l
Aceti
c Acid
(1.0
mM)
Butyr
ic Ac
id (0.
59 m
M)
Lacti
c acid
(1.36
mM)
HMF (
16.3
mM)
Unkn
own I
nterm
ediat
e
78.3 % headspace fraction
(15 mL slurry, 0 M Na2CO3)
92.8 % headspace fraction
(5 mL slurry, 0 M Na2CO3)
49.3 % headspace fraction
(35 mL slurry, 0 M Na2CO3)
63.8 % headspace fraction
(25 mL slurry, 0 M Na2CO3)
181614121086420
Retention Time (min)
• HMF suppressed as the headspace fraction increased
• At highest headspace fraction, butyric acid most abundant
Experimental Setup II• 1.8 L batch reactor (SS316), Parr Instrument Company• Gas composition was analyzed by micro-GC
Controller (A)
Reac
tor (B
)
Cond
ense
r (C)Micro-GC (D)
Solenoid Valve
Tap Water
Cooli
ng Lo
op
To Fumehood
A
B
C
D
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
No Catalyst NaOH RuCl3 NaOH and RuCl3
mm
ol g
as/g
ram
volat
ile m
anur
e
Catalytic Conditions
Carbon Dioxide
Carbon Monoxide
Hydrogen
Cattle Manure Test Results
Experiments with Cattle Manure show synergy between the RuCl3 and the basic NaOH catalysts
Discussion – Effects of Alkalinity
• Three Distinct Regions of Alkalinity1. Region I – HMF suppression2. Region II – Change to Basic Solution pH3. Region III – Formation of Bicarbonates from Carbon Dioxide
• Peak in Hydrogen when using Pt/SiO2 catalyst occurred at higher alkalinity (200 mM as opposed to 75mM)
• Liquid Phase changes from HMF (0M Na2CO3) , to lactic acid and dihydroxyacetone
• Methane likely to be related to the decarboxylation of acetic acid • Significant interaction between RuCl3 and NaOH catalysts
Discussion – Effects of Headspace Fraction
• Higher headspace fractions (vapour fractions) enhanced gas production, the effect was most significant without the addition of sodium carbonate
• In general, decreasing headspace fraction resulted in a decreased concentration of detected chemicals.
• Under the most successful conditions (92.8% headspace fraction, no Na2CO3), butyric acid relatively significant chemical in the liquid phase.
Conclusions
• More facile pathways for gasification available under high headspace fraction, without the addition of alkali salt sodium carbonate.
• Acetic Acid appears to be a likely source for produced Methane• Decomposition of Cellulose through HMF produces little gas• Decomposition pathway has large impact on gasification yield and
composition
Hydrothermal Conversion of Cattle Manure to Biooil
Laboratory ProcedureCattle manure
HTC reaction system (1.8L; 310 oC ;15min)
+ water
Liquid Products
Extraction
Separation
CHCl3CH2Cl2 C4H10O
Evaporation
Bio-oil Bio-oil Bio-oil
Yields Heating values Structures
Comparison
Effects of solvents on bio-oil yields
C4H10O CHCl3 CH2Cl2
Bio-
oil yi
elds
(wt%
of vo
latile
conte
nt of
cattle
man
ure)
50
40
30
20
10
0
Solvents(Conditions: 125g of cattle manure, 500g of water, 0.5 mol of NaOH,
residence time of 15 min, and 0 psig initial pressure of CO)
Effects of solvents on elemental compositions of bio-oil
(Conditions: 125g of cattle manure, 500g of water, 0.5 mol of NaOH,residence time of 15 min, and 0 psig initial pressure of CO)
0%
20%
40%
60%
80%
100%
CH2Cl2 CHCl3 C4H10O Cattle manure
ONHC
Elem
ental
comp
ositio
ns (b
y mas
s)
Effects of solvents on heating values of bio-oil
Bio-oil Heating value( MJ/kg)
Standard derivation
Bio-oil (extracted by CH2Cl2) 36.08 2.06
Bio-oil (extracted by CHCl3) 35.55 0.99
Bio-oil (extracted by C4H10O) 36.56 0.18
Cattle manure 15.2 0.73
Effects of solvents on structures of bio-oil
0
1
2
3
4
5
150 200 250 300 350 400 450 500 550
C4H10O
CH2Cl2
CHCl3
UV-VIS analysis spectra of bio-oil extracted by different solvents(Conditions: 125g of cattle manure, 500mL of water, 6g of NaOH,
process gas of 0 psig of CO, and residence time of 15 min)
Wavelength (nm)
Abso
rban
ce
Effects of temperatures on bio-oil/bio-gas yields
(Conditions: 125g of cattle manure, 500g of water, 0.5 mol of NaOH,residence time of 15 min, and 0 psig initial pressure of N2)
Bio-
oil yi
elds
(wt%
of vo
latile
conte
nt of
cattle
man
ure)
Bio-gas (millimole)
0%
10%
20%
30%
40%
50%
250 270 290 310 330 350 3700
40
80
120
160
Temperatures (oC)
Bio-oil
Bio-gas
Effects of pressures on bio-oil yields
Figure 5. Effect of initial conversion pressure on biooil yield (Conditions: 125 g of cattle manure, 500 g of water, 0.5 mol of NaOH,
temperature of 310 oC, residence time of 15 min, and process gas of N2)
Bio-
oil yi
elds
(wt%
of vo
latile
conte
nt of
cattle
man
ure)
Pressure (psig)
0%
10%
20%
30%
40%
0 20 40 60 80 100 120
Effects of processing gases on bio-oil yields
Figure 6. Effect of process gasese on biooil yield (Conditions: 125g of cattle manure, 500g of water, 0.5 mol of NaOH,
temperature of 310 oC, and 0 psig process gas)
27.97%
38.49%44.72%
48.76%
0%
10%
20%
30%
40%
50%
60%
Air N2 H2 CO
Bio-
oil yi
elds
(wt%
of vo
latile
conte
nt of
cattle
man
ure)
Processing gases
Effects of mass ratios of cattle manure to water on bio-oil yields
Figure 7. Effect of cattle manure to water mass ratios on bio-oil yields (Conditions: T= 310 oC, 0.5 mol of NaOH, residence time of 15 min,
and 0 psig initial pressure of CO)
Yield
s of b
io-oil
and r
esidu
al so
lid(w
t% of
volat
ile co
ntent
of ca
ttle m
anur
e)Total bio-gas (moles)
Mass ratio of dry cattle manure to water
0%
20%
40%
60%
0.05 0.10 0.15 0.20 0.25 0.300.00
0.50
1.00
1.50
2.00
Bio-oil
Bio-gas
Residual solids
Effects of processing gas
High heating values of bio-oils
Energy types Heating value( MJ/kg)
Bio-oil from HTC290 oC 35.07
300 oC 36.10
310 oC 35.74325 oC 34.28
Bio-ethanol 29.8Coal 32.5Gasohol E85 33.1Bio-diesel 41
Bio-oil from cattle manure: Comparison with petro liquid fuels
HTC bio-oil
#87 Gasoline
Fossil diesel
• The main components of HTC bio-oil were carboxylic acids, aldehydes, and phenol derivatives.
• The main components of petroleum are alkanes.
GC analysis of HTC bio-oil and fossil liquid fuelsTime (min)
9
Bio-oil from cattle manure: Stability
• The color of HTC bio-oil became darker with time.
• More residual solids were formed over time.
• During storage, the concentrations of aromatic chemicals and phenol derivatives decreased, while aldehydes and ketones increased.
Fresh bio-oil 1 day 1 week
(It was stored at room temperature. HTC bio-oil was produced from cattle manure)
10
Hydrothermal Conversion of Cellulose to Biooil
Bio-oil from cellulose
• No alkanes were detected in HTC bio-oil from cellulose.
• The compositions of HTC bio-oils varied with the initial pH levels of aqueous reaction media.
GC analysis of HTC bio-oils produced from cellulose at pH=3, 7 and 14
• At pH<7: HMF and levulinic acid
• At pH=7: HMF, acetic acid and lactic acid
• At pH>7: Carboxylic acids
Time (min)
pH=3
pH=7
pH=14
pH value changes vs. initial pH level
• Reaction pathways of HTC changed during alkaline HTC
Cellulose
Carboxylic acids
Final pH<7
Cellulose
Carboxylic acids
Final pH>7
Weak alkaline solutions
Strong alkaline solutions
A Zone B Zone A B
Bio-oil: HMF+
carboxylic acids
Bio-oil: carboxylic acids
Comparison of initial and final pH levels of alkaline HTC of cellulose to bio-oil
12
13.5
Hydrothermal Conversion of Cellulose, Glucose to Alkanes
Motivation: Previous bio-oil from cattle manure or cellulose is not “oil”
HTC bio-oil Catalytic HTC bio-oil
Compositions Acids, aldehyes, aromatic chemicals
Alkanes(Petroleum)
Chemical stability Unstable Stable
Separation Organic solvent extraction Voluntary separation from aqueous solutions
Use as a liquid fuel Upgrading needed Directly used by car engine
• Need to improve the quality of HTC bio-oil by catalytic HTC13
0%
5%
10%
15%
20%
25%
Vacuum 0 100 200 300
0.00
0.20
0.40
0.60
0.80
1.00
Vacuum 0 100 200 300
CH4 C2H6
C3H8 C4H10
• Alkane yields increased with increasing H2 pressure.• More heavy gaseous alkanes (C3H8, C4H10) were produced with higher H2 pressure. • The chemical composition was the same as that of liquefied petroleum gas (LPG)
Alka
ne yi
elds (
%)
Initial H2 pressure (psi) Initial H2 pressure (psi)
Alka
ne (m
mol)
Alkanes from CHTC of glucose with hydrogen
0.5 g glucose, 3 g water, 0.5 g Pt/Al2O3, 1.5 h reaction time
and at 265 oC.
• C5-9 liquid alkanes were detected in liquid products
0.5 g glucose, 3 g water, 0.5 g Pt/Al2O3, 265 oC, 1.5 h reaction time and initial 100 psi of H2.
But, much more C1-4 alkanes were formed than C5-9 alkanes.
GC analysis of C5-9 alkanes in liquid phase
• Problems with CHTC of glucose to alkanes
Alkanes from CHTC of glucose (cont…)
• Few liquid alkanes were formed from glucose.
• External H2 was required for CHTC.
Glucose (C6)
Gaseous alkanes (C< 5)CHTC
H2 is required for hydrogenation reaction
16
Alkanes from CHTC of cellulose (cont.)
A new reaction process was proposed to produce liquid alkanes from cellulose with in situ H2
in situ H2
Alkane precursors(e.g. HMF)
Alkanes
Steam reforming
CHTC (Aqueous phase reforming-APR)
In-situ-H2-APR
Cellulose(a polymer of glucose)
Illustration of In-situ-H2-APR process
Before conversion at room temperatures
Water
N2
Cellulose
During conversion at high temperatures
(300 oC)
Steam
in situ H2 produced by steam reforming of cellulose in steam phase.
Alkane precursors produced by CHTC of cellulose in liquid water
phase.
Heating the reactor
Reactor
in situ H2 + Alkane precursors Alkane bio-oil(liquid alkanes)
(1)
(2)
(3)
(catalyzed by pH>7)
(catalyzed by pH<7)
Factor 1:v/v (water/reactor)
Factor 2: pH
• Effects of volumetric ratios of input water to reactor
Results: Alkanes from CHTC of cellulose
• Too little or too much water inhibited alkane bio-oil formation.
• The alkane bio-oil mainly consisted of nonane, octane and heptane.
Pyrolysis without water Conventional HTC using much water
In-situ-H2-APR
19
3 g cellulose, 300 oC And 15 min reaction time
Effects of pH levels of aqueous reaction media
Results: Alkanes from CHTC of cellulose
Alkane bio-oil yields were further increased by weak alkaline conditions.
pH/reaction pathway changes mainly led to this improvement.
Initial pH>7
Final pH<7
pH=7
in situ H2(catalyzed by
pH>7)
Alkane precursors(catalyzed by
pH<7)
In-situ-H2-APR of cellulose to alkane bio-oil under weak alkaline conditions
20
Control: pH=7
pH=7.5
ConversionTime
Possible explanation to petroleum formation
Observations Petroleum formed in sea
Bio-oil formed by In-situ-H2-APR
Oil Main components
alkanes alkanes
Associated with natural gas?
Yes Yes (syngas)
Environ-ment
Metals Ni, Fe, V, Cu Pt, Ni (catalysts)Inorganic chemicals
SiO2/Al2O3 (the main components of earth crust)
SiO2/Al2O3
(catalyst supports)pH 7.5-8.4 (sea) 7.5 (aqueous media)
Steam Geothermal heating External heatingLiquid water Yes Yes
• In-situ-H2-APR: a possible explanation for petroleum formation
Conclusions
1. HTC bio-oil was different from petroleum, in terms of chemical composition.
2. HTC bio-oil compositions were unstable and changed with time.
3. But, by CHTC (especially, In-situ-H2-APR), alkane bio-oils were produced from glucose and cellulose. Their compositions are quite same as liquefied petroleum gas and gasoline, respectively.
4. Via catalytic HTC, therefore, a quick production of petroleum from renewable/carbon-neutral biomass would become feasible.
Other Slides
Absorb CO2 and solar energyThree types of biomass: • Lignocellulosic and starch-based
plants (e.g. Wood, grass, livestock manure)
• Triglyceride-producing plants: e.g. canola, soybeans, sunflower, safflower
• Algae are another source of triglycerides as well as carbonhydrates and lignin.
Biomass is Biological Material Derived from Living Organisms Recently
Jatropha
Rapseed
Miscanthus
• World has ~ 800 million vehicles, and adds 50 million vehicles per year
• Biomass is the only renewable source for renewable transportation fuel.
• Biofuel is the solution before electrical car becomes affordable and reliable.
• Biofuel may remain important since other sectors demands electricity rather than fuel.
Transportation Energy Needs to Remain Liquid to Fit in
Existing Tanks and Be Transportable
Henry Ford originally designed the Ford Model T to run completely on ethanol. But then crude oil became more cheaply available.
Dehydration
Hydrotreating Renewable diesel
FermentationCatalysis
Pyrolysis and Liquefaction
Gasification
BioOil(Including tars, acids, chars,
alcohols, aldehydes, esters,
ketones and aromatic)
SynGas(CO + H2)
Extraction
Hydrolysis SugarGlucose(C6),
xylose(C5), sucrose and so on
Edible oil
Anaerobic Digestion
VFA(Acetate, propionate, Butyrate and so on )
Fischer-Tropsch FT diesel, Alkans, Jet fuelDMF, MtOH, Mixedalcohol
Refining Boiler oil, Diesel
Fermentation Ethanol, Butanol
Furfural, MTHF, HMF
Transesterification Biodiesel
FermentationBiogas
(Methane)
• Syngas and Sugar platform : two actively researched field for the liquid fuel
Commercial
Pilot
Pilot
Commercial
Commercial
Ethanol
Platforms for Biofuel Production[3]Oi
ly bio
mass
Ligno
cellu
losic
Biom
ass
CanadaCanadian Renewable Fuels Association (CRFA)
Bio-oil Feedstock Pretreatment Use as liquid fuelBio-ethanol Food crops
(e.g. Corn, wheat)Not required 1. Needing to be mixed with
petroleum before use2. Not used in cold weather
(low vapour pressure of ethanol)
Bio-diesel Food crops(e.g. Canola oil)
Predryingbiomass
1. Not used in cold weather(gelling at low temperatures < -10 oC)
Challenges to existing biofuels Mostly from edible biomass
High cost: 90% of $$$ goes to separation Mixed with petroleum gasoline
New Generation Biofuels: Cellulosic Feedstock…
Switchgrass Wheat Straw Hybrid Poplar Corn Stalks
Sustainable Production of Biofuels: An Integrated Biomass Production System
CO2H2O
AirNutrients
Energy
Separation
Edible for feed and
food
Transport
ConversionEnergy
Non-edible
Fuel
Utilization
Energy
Nutrients
CO2
H2O
CO2
H2O
