MixAlco:

Biofuels from Biomass

Professor Mark Holtzapple
Department of Chemical Engineering
Texas A&M University
Presentation by
Scott L. Wellington, PhD
Research Advisor
Shell International E&P

Biofuels

CO2

Examples of Biomass
Fuels and
Chemicals

forest residues & trees

municipal solid waste
grass clippings
sewage sludge
agricultural residues
animal manure
energy crops
most of these are lignocellulose.

Nature Converts Cellulose

into Organic Acids, i.e.,
animal rumen
- cattle
- sheep
- deer
- elephants

anaerobic sewage digestors

swamps
termite guts

Why are Organic

Acids Favored?
C6H12O6 2 C2H5OH + 2 CO2
glucose
ethanol

G = - 48.6 kcal/mol

C6H12O6 3 C2H3OOH
glucose
acetic acid

G = - 61.8 kcal/mol

The actual stoichiometry is complex: Briefly

5 C6 H12 O6 6 acetate + 2 propionate + butyrate + 5 CO2 + 3 CH 4 + 6 H2 O
(67 mol%) (22 mol%) (11 mol%)

Conversion of City Yard,

Crop and Forrest Waste

Research Statistics
Year started = early 1991
Time spent = 13 years
Labor = ~110 personyears
Funding, over $2.3 mill

Researchers
Faculty
Mark Holtzapple
Richard Davison

Post Docs
Praveen Vadlani
Vincent Chang
Xu Li
Cesar Granda

Masters
Murlidahar Nagwani

PhD
Nan Sheng Chang

Chang Ming Lee

Champion Lee
Seth Adleson
Robert Rapier
William Kaar
David Gaskin
Hiroshi Shirage
Wilbelto Adorno-Gomez
Shelly Williamson
Maria Almendarez
Ramasubramania Narayan
Patricia O'Dowd
Hung-Wen Yeh
Manohar Vishwanathappa

Shushien Chang
Mitch Loescher
Kyle Ross
Susan Domke
Salvador Aldrett-Lee
Cateryna Aiello-Mazzarri
Wenning Chan
Piyarat Thanakoses
Xu Li
Guillermo Coward-Kelly
Li Zhu
Se Hoon Kim
Frank Agbogbo
Zihong Fu
Jonathan O'Dwyer

Aerobic Compost Pretreatment

then Anaerobic Fermentation
Tarp Cover

Air

Biomass
Pretreat - pH Control (Lime, Calcium Carbonate), air
Then Anaerobic Fermentation

Gravel

Vapor-Compression Dewatering
Compressor

Work

Fermentor
Broth
Solution of
Organic Acids

Distilled Water
Filter
Carboxylate Salt Crystals

Thermal Conversion
Stoichiometry (One Option)
O

O
H3 CCOCaOCCH3 3 CCCH3 + CaCO3
Calcium Acetate
O

Acetone

H3 CCH2 COCaOCCH2CH3 3CCH2 CCH2 CH3 + CaCO3

Calcium Propionate
O

Diethyl Ketone
O

H3 CCH2 CH2COCaOCCH2 CH2 CH3 3 CCH2 CH2 CCH2 CH2CH3 + CaCO3

Calcium Butyrate

Dipropyl Ketone

Ketone Hydrogenation Option

Catalyst = 200 g/L Raney nickel

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

H2

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

MixAlco Process:
1) Compost
Pretreatment
&
Fermentation

Biomass

Pretreat
Lime
Lime Kiln

2) Dewater
&
Collect
Carboxylate
Salts

Ferment

3) Heat to
Form Ketones:
Many Process
Options and
Products

Dewater

Thermal
Conversion

4) Hydrotreat
to Alcohols
Mixed
Alcohol
Fuels
Mixed
Ketones

Hydrogenate

Water

Calcium Carbonate

Hydrogen

Typical Product Spectrum at

Different Fermentation Temperatures

40oC
C2 Acetic
C3 Propionic
C4 Butyric
C5 Valeric
C6 Caproic
C7 Heptanoic

41 wt %
15 wt %
21 wt %
8 wt %
12 wt %
3 wt %
100 wt %

55oC
80 wt %
4 wt %
15 wt %
<1 wt %
<1 wt %
<1 wt %
100 wt %

Energy Content
Energy
(MJ/L) (Btu/gal)
Gasoline

34.9

125,000

Mixed Alcohols

29.0

104,000

Ethanol

23.4

84,300

Properties of Fuel Oxygenates

Blending Reid
Vapor Pressure
@38oC (kPa)

Blending
Octane
(R + M)/2

Alcohols
214
124
97
62
34

Methanol (MeOH)
Ethanol (EtOH)
Isopropanol (IPA)
tert-Butanol (TBA)
Isobutanol (IBA)

108
115
106
100
102

Klass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic

Academic Press (1998).

Key Numbers
Conversion = 0.75

tonne digested
tonne fed

tonne acids
Selectivit y = 0.65
tonne fed
Yield = 0.75

tonne digested
tonne acids
tonne acids
0.65
= 0.49
tonne fed
tonne digested
tonne fed

Solid residue will be burned for process heat, sold as compost, or

landfilled.

U.S. Biodegradable Wastes

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

Fuels and Sugar from Energy Cane

Energy Cane Processing

Sugar

Energy
Cane

Extract

Biomass
Fiber

Sugar
Mill

Sugar

Residue
(Boiler Fuel)

MixAlco
Process

Alcohol
Fuel

Sweet Sorghum
Grows in ~35 US states
Yield = 2025 dry ton/(acreyr)

100% planted

345 mi

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

Land Area in United States

2 3

Effect of Automotive Efficiency

1
(Current)

302 mi

2 better

213 mi

3 better

174 mi

Land Area in United States

2 3

U.S. Biodegradable Wastes

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

Advantages of MixAlco
Approach

robust efficient nonsterile fermentation

natural occurring microorganisms
culture passed from one compost pile to another
no spoiled batches since natural process
inexpensive compost like pretreat & fermentation
no enzyme addition required
conventional plant operation and fuel distribution
flexible using organic residue wastes and/or crops
high performance bio-fuel or fuel additive products

The MixAlco Process is: - green - simple

- robust - widely applicable and - timely

Professor Holtapple
is the Recipient of
the Presidential
Green Chemistry
Award

MixAlco Process Next Steps

Convert Pilot Plant for Other Studies

3 Quarter 2005
Complete Design of Demonstration Plant
Year End 2004
Organize a Demonstration Project
Early 2004
Commercialize the Process
ASAP

Patents
5,865,898 5,962,307
5,693,296 5,874,263

Biomass

Pretreat

Ferment

5,969,189
5,986,133 6,262,313

Dewater

Thermal
Conversion

Mixed
Alcohol
Fuels
Mixed
Ketones

Hydrogenate

Lime
Lime Kiln

Hydrogen

Calcium Carbonate

6,043,392
6,395,926

Chemical Flowchart
Calcium
Magnesium
Acetate

Isobutylene
H2

Calcium
Acetate

B
I
O
M
A
S
S

Acetic
Acid
H2
Ethanol

Calcium
Propionate

n-Propanol
Calcium
Butyrate

Acetone

n-Butanol

Diisopropyl
Ether

H2
Diethyl Ketone

3-Pentanol

Propyl
Propionate

Butyric
Acid
H2

Isopropanol

Ethyl
Acetate

Propionic
Acid
H2

Isopropyl
Tertiary
Butyl
Ether

Dipropyl
Ketone
Butyl
Butyrate

H2

4-Heptanol

Centralized Processing

15.3 mi
50% of area
planted

MixAlco Process Version 2

Mixed
Alcohol
Fuels

Biomass

Pretreat

Ferment

Carboxylate
Salts
Dewater

Lime
Lime Kiln

Calcium Carbonate

Acid
Springing

Mixed
Acids

Hydrogenate

Hydrogen

Acid Springing
R3N

HAc
R3NHAc

Ca(Ac)2
H2O
CO2

CaCO3

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3

R3NHAc R3N

Carboxylic Acid Production

CO2
Biomass

Pretreat
CaO

Ferment

Carboxylate
Carboxylic Acid
Salt
Dewater
Springing
Springing
acetic acid
propionic acid
butyric acid

CaCO3

Lime Kiln
CO2

Required Area
Scale = 800 tonne/h
Feedstock yield = 30 ton/(acreyr)
800 tonne 8000 h 1.1 ton acreyr
Area =

= 235,000 acre
h
yr
tonne
30

= 366 mi2

Feedstock
Yard Clippings
1000 wet ton 0.5 dry ton tonne 280 d
yr
dry tonne

= 16
d
wet ton 1.1 ton
yr
8000 h
h

Sewage Sludge
650 wet ton 0.3 dry ton tonne 365 d
yr
dry tonne

=8
d
wet ton 1.1 ton
yr
8000 h
h
tonne
Total = 24
h

Key Assumptions
tonne digested
Conversion = 0.83
tonne fed

(High because of sugar)

tonne acids
Selectivit y = 0.65
tonne fed
Yield = 0.83

tonne digested
tonne acids
tonne acids
0.65
= 0.54
tonne fed
tonne digested
tonne fed

0.54 tonne acids 0.54 tonne alcohol

tonne alcohols
Product =

= 0.29
tonne fed
tonne acids
tonne fed

Production Rate
800 tonne fed 0.29 tonne alcohols
tonne alcohols
Production Rate =

= 233
h
tonne fed
h

= 297,000 L/h
= 78,600 gal/h
= 44,900 bbl/d
= 629 mill gal/yr

Plant Capacity
Plant Capacity
City Population
(tonne/h) (mill gal/yr)
2
1.1
40,000
10
5.6
200,000
Base
40
22.3
800,000
Case
160
89.3
3,200,000
800
446.7
16,000,000

What is lignocellulose?

Cellulose
Hemicellulose
Lignin

- glucose polymer
- xylose polymer
- aromatic polymer

Hydrogenation
Mixed Alcohols

Water

Carboxylic
Acids

Esters

Alcohols

H2
Heavy Alcohols

48-h Digestion
(g digested/g fed)

In-Situ Digestion
1.0
0.8
0.6
0.4
Untreated
Lime -treated

0.2
0.0
Sugar- African Sorghum Tobacco
cane
millet straw
stalks
bagasse straw

Land required in Brazil

2 3

Supply US Gasoline Consumption

130 109 gal gas 1.2 gal alc
plantyr
Plants =

= 248 plants
yr
gal gas
629 10 6 gal alc

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

100% planted

302 mi

Expected Product Yields

(mesophilic 40oC)
Total Acid = 24

tonne biomass 8000 h 0.49 tonne acid 2200 lb

mill lb

= 207
h
yr
tonne biomass
tonne
yr

Plant Production

US Production

C2 = 207

mill lb total acid 0.41 lb C2

mill lb

= 85
yr
lb total acid
yr

3700

mill lb
yr

(2.3%)

C3 = 207

mill lb total acid 0.15 lb C3

mill lb

= 31
yr
lb total acid
yr

250

mill lb
yr

(12.4%)

mill lb total acid 0 .44 lb C4 +

mill lb
+
C4 = 207

= 91
yr

lb total acid

yr

Expected Product Yields

(thermophilic 55oC)
Total Acid = 24

tonne biomass 8000 h 0.49 tonne acid 2200 lb

mill lb

= 207
h
yr
tonne biomass
tonne
yr

Plant Production

US Production

C2 = 207

mill lb total acid 0.80 lb C2

mill lb

= 166
yr
lb total acid
yr

3700

mill lb
yr

(4.5%)

C3 = 207

mill lb total acid 0.04 lb C3

mill lb

= 8 .3
yr
lb total acid
yr

250

mill lb
yr

(3.3%)

mill lb total acid 0.16 lb C4 +

mill lb
+
C4 = 207

= 33
yr

lb total acid

yr

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

Affordable Fermentors
Above-ground stainless steel

$380/m3

Above-ground carbon steel

$125/m3

Above-ground concrete

$ 69/m3

In-ground plastic

$ 12/m3

Heat Requirements
Btu
lb water removed

Single-effect evaporator
Triple-effect evaporator
Amine dewatering

1000
333
60