MixAlco:

Biofuels and Chemicals

from Biomass

Mark Holtzapple
Department of Chemical Engineering
Texas A&M University
College Station, TX
 Biofuels address
Energy shortage
Global warming
Biofuels
CO2
 Lets envision an
ideal biofuel process
Feedstock

CO2
 Multiple Feedstocks

trees municipal solid waste

grass sewage sludge
agricultural residues animal manure
energy crops
 U.S. Biodegradable Wastes

Amount Alcohol Potential

Waste (million tonne/year) (billion gal/year)
Municipal Solid Waste 78 10
Sewage Sludge 10.9 1.4
Industrial Biosludge 3 0.4
Recycled Paper Fines 4.3 0.5
Agricultural Residues 400 52
Forestry Residues 330 43
Manure 220 28
Total 1,046 135
U.S. Gasoline Consumption = 130 billion gal/year
U.S. Diesel Consumption = 40 billion gal/year
 High-Productivity Feedstocks

30
Dry tons/(acreyr)
Productivity

20

3.4
Corn grain Sweet sorghum Energy cane
 Sweet Sorghum

Grows in ~35 US states

Energy Cane
Energy Cane
 High Agricultural Income

1090
Gross Income
$/(acreyr)

730

340

Corn grain Sweet sorghum Energy cane

($2.40/bu) ($40/tonne) ($40/tonne)
 Low Environmental Impact

Environmental
cost per
Corn Sweet Energy
unit of biomass Grain Sorghum Cane
Water High Low Low
Fertilizer High Low Low
Pesticides High Low Low
Herbicides High Low Low
Soil erosion High Low Low
Aquatic Biomass Water Hyacinth
Aquatic Biomass Water Hyacinth
 Aquatic vs Terrestrial Feedstocks
100

70
Dry tons/(acreyr)
Productivity

30
20
3.4
Corn grain Sweet sorghum Energy cane Hyacinth Hyacinth
CO2 Enrich
Process

CO2
 Ideal Process Properties

No sterility
No genetically modified organisms (GMOs)
Adaptable
No pure cultures
Low capital
No enzymes
High product yields
No vitamin addition
Co-products not required
Fuel

CO2
 Fuel Properties
Ethanol MTBE Mixed
Alcohols

Octane high high high

Volatility high low low
Pipeline shipping no yes yes
Energy content low high high
Heat of vaporization high low low
Ground water damage no yes no
Is there an ideal biofuel
technology?

CO2
 MixAlco Process Version 1

Mixed
Alcohol
Fuels

Carboxylate
Mixed
Salts Ketones
Thermal
Biomass Pretreat Ferment Dewater Hydrogenate
Conversion

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Pretreatment

Mixed
Alcohol
Fuels

Carboxylate Mixed
Salts Ketones
Thermal
Biomass Pretreat Ferment Dewater Hydrogenate
Conversion

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Lime Treatment

T = 100oC
t=1h
Lime loading = 0.1 g Ca(OH)2/g biomass
Water loading = 5 to 15 g H2O/g biomass
 In situ Digestion

Weigh ~ 2 g of biomass
Place biomass in tea bag
Place tea bags in porous sack
Place porous sacks in cattle rumen
Incubate
Remove porous sack
Wash tea bags
Dry
Weigh residue
 In-Situ Digestion

1.0
(g digested/g fed)
48-h Digestion

0.8
0.6
0.4
0.2 Untreated
0.0 Lime-treated
Sugar- African Sorghum Tobacco
cane millet straw stalks
bagasse straw
Pretreatment Vessels
 Advanced Lime Treatment

Air Biomass + Lime

Gravel
Building the Pile

~100 ft
Building the Pile
Building the Pile

Crew directing the flow

 Lignin Removal
No Air Air
30 30 30 30
Lignin Content (g lignin/100 g bagasse)

Lignin Content (g lignin/100 g bagasse)

25 25 25 25
Lignin Content in Treated Bagasse
(g lignin/100 g treated bagasse)

Lignin Content in Treated Bagasse

20 20

(g lignin/100 g of bagasse)
25oC 20 20

15 15 50oC 15 15
57oC 25oC
10 10 10 10
50oC
55 55
57oC
00 00
0 50 100 150 200 250 300 0 50 100 150 200 250 300
50 100 150 200 250 300 50 100 Tim150
e(days) 200 250 300
Time(days)
Time (days) Time (days)
 Mixed-Acid Fermentation

Lime Treatment: 2 weeks, 25oC

Terrestrial Inoculum

60
Total acid concentration (g/L)

50 Air VSLR
18 14 11 (g/(Ld))
40 8
LRT
30 4 (days)

20
No Air 2
20.5
15
10 10
5
0
0 0.2 0.4 0.6 0.8 1
Conversion
 Fermentation

Mixed
Alcohol
Fuels
Carboxylate
Mixed
Salts
Thermal Ketones
Biomass Pretreat Ferment Dewater Hydrogenate
Conversion

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Environments where organic
acids naturally form
animal rumen
- cattle
- sheep
- deer
- elephants
anaerobic sewage digestors
swamps
termite guts
 Why are organic acids favored?

C6H12O6 2 C2H5OH + 2 CO2 G = -48.56 kcal/mol

glucose ethanol

C6H12O6 3 C2H3OOH G = -61.8 kcal/mol

glucose acetic acid

The actual stoichiometry is more complex

5 C6H12O6 6 acetate + 2 propionate + butyrate + 5 CO2 + 3 CH 4 + 6 H2O

(67 mol%) (22 mol%) (11 mol%)
Typical Product Spectrum
at Different Culture Temperatures

40oC 55oC
C2 Acetic 41 wt % 80 wt %
C3 Propionic 15 wt % 4 wt %
C4 Butyric 21 wt % 15 wt %
C5 Valeric 8 wt % <1 wt %
C6 Caproic 12 wt % <1 wt %
C7 Heptanoic 3 wt % <1 wt %
100 wt % 100 wt %
 Marine Inoculum

Marine Inoculum
90 Air
Total acid concentration (g/L)

80
70
60 LRT
50 (days)
40 Terrestrial Inoculum 20.5
30
No Air 15
20
10
10 VSLR (g/(Ld)) 18 14 11 8 5
0 4 2
0 0.2 0.4 0.6 0.8 1
Conversion
 Storage + Pretreatment
+ Fermentation

Tarp Cover

Air Biomass + Lime + Calcium Carbonate

Gravel
 Dewatering

Mixed
Alcohol
Fuels
Carboxylate
Mixed
Salts
Thermal Ketones
Biomass Pretreat Ferment Dewater Hydrogenate
Conversion

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Vapor-Compression Dewatering

Compressor

Work
Salt
Solution
(Fermentor
Broth)
Distilled Water
Filter
Salt Crystals
 Thermal Conversion

Mixed
Alcohol
Fuels
Carboxylate
Mixed
Salts
Thermal Ketones
Biomass Pretreat Ferment Dewater Hydrogenate
Conversion

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Thermal Conversion
Stoichiometry
O O O
H3CCOCaOCCH3 3CCCH3 + CaCO3
Calcium Acetate Acetone

O O O
H3CCH2COCaOCCH2CH3 3CCH2CCH2CH3 + CaCO3
Calcium Propionate Diethyl Ketone

O O O
H3CCH2CH2COCaOCCH2CH2CH3 3CCH2CH2CCH2CH2CH3 + CaCO3
Calcium Butyrate Dipropyl Ketone
Thermal Conversion Kinetics

45
40
35
30
t (min)

25
20 Conversion (%)
15
99
10
95
5 90
0
380 400 420 440 460 480 500
T (C)
 Hydrogenation

Mixed
Alcohol
Fuels
Carboxylate
Mixed
Salts
Thermal Ketones
Biomass Pretreat Ferment Dewater Hydrogenate
Conversion

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
Ketone Hydrogenation
Stoichiometry

O OH
H3CCCH3 + H2 H3CCCH3
H
Acetone Isopropanol

O OH
H3CCCH2CH3 + H2 H3CCCH2CH3
H
Methyl Ethyl Ketone 2-Butanol

O OH
H3CCH2CCH2CH3 + H2 H3CCH2CCH2CH3
H
Diethyl Ketone 3-Pentanol
 Ketone Hydrogenation

Catalyst = 200 g/L Raney nickel

Temperature = 130oC
Time = 35 min (@ P = 15 atm)
Liquid Ketones

H2
 MixAlco Process Version 2

Mixed
Alcohol
Fuels

Carboxylate
Mixed
Salts Acids
Acid
Biomass Pretreat Ferment Dewater Hydrogenate
Springing

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Acid Springing
R3 N HAc

Ca(Ac)2 R3NHAc

H2 O

CO2
CaCO3

R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3NHAc R3N
 MixAlco Process Version 2

Mixed
Alcohol
Fuels

Carboxylate
Mixed
Salts Acids
Acid
Biomass Pretreat Ferment Dewater Hydrogenate
Springing

Lime
Hydrogen
Calcium Carbonate
Lime Kiln
 Hydrogenation Stoichiometry

O O
H3CCOH + HOCH2CH2CH2CH2CH3 H3CCOCH2CH2CH2CH2CH3 + H2O
Heavy Alcohol Ester
O
H
H3CCOCH2CH2CH2CH2CH3 + 2 H2 H3CCOH + HOCH2CH2CH2CH2CH3
Ester H Heavy Alcohol

O
H
H3CCOH + 2 H2 H3CCOH + H2O
H
Acetic Acid Ethanol
 Hydrogenation

Water Mixed Alcohols

Carboxylic Esters Alcohols

Acids

H2

Heavy Alcohols
 Chemical Flowchart
Isopropyl
Calcium Tertiary
Magnesium Isobutylene Butyl
Acetate Ether
H2
Calcium Acetone Isopropanol
Acetic
Diisopropyl
Acetate Acid
Ether
H2 Ethyl
B Acetate
I Ethanol

O H2
M Calcium Propionic
Diethyl Ketone 3-Pentanol
Propionate Acid
A
S H2 Propyl
S n-Propanol Propionate

Calcium Butyric H2
Dipropyl
Butyrate Acid 4-Heptanol
Ketone
H2
Butyl
n-Butanol Butyrate
 Properties of Fuel Oxygenates
Blending Reid Blending
Vapor Pressure Octane
@38oC (kPa) (R + M)/2
Alcohols
214 Methanol (MeOH) 108
124 Ethanol (EtOH) 115
97 Isopropanol (IPA) 106
62 tert-Butanol (TBA) 100
34 Isobutanol (IBA) 102
Ethers
55 Methy tertiary butyl ether (MTBE) 110
34 Di-isopropyl ether (DIPE) 105
17 Isopropyl tertiary butyl ether (IPTBE) 113
Klass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press (1998).
 Energy Content
Energy
(MJ/L) (Btu/gal)
Gasoline 34.9 125,000
Mixed Alcohols 29.0 104,000
Version 1

Mixed Alcohols 26.5 95,000

Version 2

Ethanol 23.4 84,300

 Mixed Ketone Selling Price
Version 1 (15% ROI)

1.00 Capacity
2 10 (tonne/h)
0.80
Ketone Selling Price ($/gal)

40
160
800
0.60

0.40

0.20

0.00
-40 -20 0 20 40
Biomass Cost ($/tonne)
 Mixed Alcohol Selling Price
Version 1 (15% ROI)

1.00 2 10 Capacity
(tonne/h)
40
Alcohol Selling Price ($/gal)

0.80 160
800

0.60

0.40

0.20

0.00
-40 -20 0 20 40
Biomass Cost ($/tonne)
 Mixed Acid Selling Price
Version 2 (15% ROI)

0.10 2 Capacity
(tonne/h)
0.08 10
Acid Selling Price ($/lb)

40
0.06 160
800
0.04

0.02

0.00
-40 -20 0 20 40
Biomass Cost ($/tonne)
 Mixed Alcohol Selling Price
Version 2 (15% ROI)

1.00 2 Capacity
(tonne/h)
10
Alcohol Selling Price ($/gal)

0.80
40
160
0.60 800

0.40

0.20

0.00
-40 -20 0 20 40
Biomass Cost ($/tonne)
Fuels and Sugar from Energy Cane
 Productivity in Puerto Rico
(dry ton/(acreyr))
30

14.6 21 70%
Biomass
60% 8.8 Fiber

9 30%
40% 5.8 Sugar
Conventional
Sugarcane Energy Cane
Source: Alex Alexander, The Energy Cane Alternative, Sugar Series 6, Elsevier
 Energy Cane Processing

Sugar
Mill Sugar
Sugar
Energy Residue
Cane Extract (Boiler Fuel)

Biomass MixAlco Alcohol

Fiber
Process Fuel
 Some Potential Commodity Products
from Sugar

Food acidulants
Citric, gluconic, succinic acids
Biodegradable polymers
Polyhydroxyalcoanates
Polylactic acid
Synthetic rubber precursors
2,3-butanediol, a precursor to butadiene
Fiber precursors
1,3-propanediol, a component of DuPont's Sorona
Centralized Processing

15.3 mi
50% of area
planted
 Supply US Gasoline Consumption

130 109 gal gas 1.2 gal alc plantyr

Plants = 6
= 248 plants
yr gal gas 629 10 gal alc

366 mi2
Area = 248 plants = 90,900 mi2
plant

100% planted 302 mi

 Effect of Automotive Efficiency

1 better 302 mi
(Current)

2 better 213 mi

3 better 174 mi
Land required in Brazil

1 2 3
 Sweet Sorghum

Grows in ~35 US states

Yield = 2025 dry ton/(acreyr)

345 mi
1 100% planted

William Rooney, Soil and Crop Sciences, Texas A&M University

Land Area in United States

1 2 3
StarRotor Test Stand
Projected Engine Efficiency
engine = 49 55%
(75 100 miles/gallon)
 Conclusions
The technology is
- green
- profitable
- world-wide
- simple
Many potential products
- ketones
- alcohols
- organic acids
 Conclusions

Near-term applications
- waste chemicals
Mid-term applications
- waste fuels
Far-term applications
- crops fuels
Thank you for your
time and attention