BioSep™: A New Ethanol Recovery

Technology for Small Scale Rural

Production of Ethanol from Biomass
Yu (Ivy) Huang, Ph.D.
Membrane Technology & Research, Inc.
1360 Willow Road, Suite 103
Menlo Park, California

&
Leland M. Vane, Ph.D.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio

AICHE
San Francisco, California
November 2006

1
 Ethanol production is growing globally

Brazil > 50% sugar cane crop 40% non-diesel fuel

USA currently, 15% corn crop 2% non-diesel fuel

> 1/3 oil displacement by 2025

EU 6% biofuel by 2010
20 - 30% replacement of oil by 2030

China Launched a program to use ethanol as a fuel

2
 How much ethanol can we produce?

Current:
¾Oil consumption: 873 MM gal/day, 58% import
¾Ethanol production: 12 MM gal/day

Forecast for 2025:

¾Oil consumption from import: 870 MM gal/day
¾The President’s goal: replace 75% import from Mideast − 100 MM gal/day

40,000

35,000

30,000

Total annual 25,000

ethanol production
(MM gal/y) 20,000

15,000

10,000

5,000

0
1970 1980 1990 2000 2010 2020 2030

3
 Conventional Bioethanol Process

MOL
Ethanol
SIEVE

Biomaterial

FERMENTATION DISTILLATION
COLUMN

Water

4
 Ethanol from Biomass

Two competing driving forces:

¾ Ethanol concentration/purification by distillation/molecular sieve
is only economical at > 40-50 MM gal/year
Æ driver for central production
¾ Transport of biomass over long distances is costly and energy
inefficient
Æ driver for distributed production in rural areas
(with added benefits for rural economies)

Can this problem be solved?

The solution is membranes (of course).

5
 MTR BioSep Process
MOL Ethanol
Biomass SIEVE

FERMENTATION DISTILLATION

Water

Water
PERVAPORATION
(dehydration)
Ethanol
FERMENTATION
PERVAPORATION DEPHLEGMATION
(ethanol concentration)

6
 Applications of BioSep Process

¾ Small biomass waste streams generated in the production of

-- beer, wine, and juice
-- cane and beet sugar
-- potatoes, yams, and other root crops
-- cheese, soft drinks, confectionery and packaged foods

¾ Replace molecular sieve in conventional corn to ethanol

plant

¾ Replace distillation in conventional corn to ethanol plant

7
 What is pervaporation?

Pervaporation = Permeation + Evaporation

To vacuum system
permeate

βmem
βevap Saturated vapor

feed Liquid feed residue

y1 /(1 − y1 )
Separation factor β = β evap ⋅ β mem =
x1 /(1 − x1 )
Not limited by thermodynamic vapor-liquid equilibrium (VLE)

8
 Pervaporation Applications

¾ Dehydration of organic solvents

‹ Primarily dehydration of ethanol and iso-propanol
‹ First commercial plant in the world was put into operation
in Brazil in 1984.
‹ Commercial application of inorganic membranes
‹ Needs improvements to be competitive with molecular
sieves in large scale applications

¾ Removal and recovery of organic solvents from water

‹ Commercially successful applications are hard to find

9
 Pervaporation using Ethanol-Permeable
and Water-Permeable Membranes

Ethanol removal from 5-10 wt% Water removal from 90 wt%

ethanol/water mixture ethanol/water mixture

10
Fractional condensation (dephlegmation)
improves separation

Vapor enters at the bottom

Vapor is partially condensed

at the top

Condensate trickles down,

creates a counter-current effect

Achieves 4 to 6 theoretical
stages of separation

11
 Significant increase in
separation performance ….

12
 MTR BioSep Process
2 0.5 wt% ethanol
to recycle or waste

4
Water-
90 - 95 wt% permeable
Ethanol-
ethanol pervaporation
1 permeable membrane
pervaporation
Filtered biomass feed 99+ wt%
membrane 6
(10 wt% ethanol) ethanol

30-40 wt%
3 ethanol Dephlegmator
vapor 20 wt%
5 ethanol
vapor

7 5 wt% ethanol recycle

Pervaporation-dephlegmation Dehydration

13
 Ethanol Permeable Membranes
5 MM gal/year plant, feed ethanol concentration = 10wt%
15 30

25

10 20

Total Energy consumption

Total energy
membrane area for distillation 15
consumption
2
(Thousand m ) (million Btu/hr)
5 10

0 0
0 10 20 30 40 50

EtOH/H O separation factor, β

2

Solution: zeolite mixed-matrix membrane

14
Mixed-matrix Membranes

Effects of zeolite loadings

30 5

20
3
Ethanol/water
separation factor, Ethanol/water
β selectivity, β
mem
2
10

0 0
0 20 40 60 80 100
Zeolite loading (wt%)

15
Ethanol Dehydration Membranes

100

MTR-2
Celfa
80

60
Permeate water
concentration
(wt%)
40

MTR-2
20
o
Temperature = 100 C

0
0 20 40 60 80 100
Feed water concentration (wt%)

16
Package membranes into spiral-wound modules

17
 Conclusions
• Pervaporation offers alternative to distillation for ethanol
recovery
‹ Higher selectivity membranes will yield energy savings

‹ Membranes scale down better than distillation

• Pervaporation offers alternative to molecular sieves for water

removal
‹ Chemical and thermal stable membranes developed

‹ Systems commercially available

• Synergies achievable through use of pervaporation for both

ethanol recovery and dehydration
‹ Combined with dephlegmation condensation

18
 Acknowledgments

• U.S. Department of Energy

• U.S. Department of Agriculture
• Jennifer Ly, Tiem Aldajani, Karl Amo of MTR
• Vasudevan Namboodiri, Travis Bowen of EPA

19
 Questions?

2020
Liquid Separation Group MTR Confidential