Optimization and improvement of

bio-ethanol production processes

Dr. Kang Qian

Prof. Jan Baeyens

Date: 17/03/2017
Contents
• 1. Characteristics and worldwide potential
• 2. The uses of bio-ethanol
• 3. Bio-ethanol production
• 4. Traditional process routes
• 5. Process improvements
• 6. General conclusions
 1.1 Ethanol and its characteristics

Ethanol Bio-ethanol
(C2H5OH)

Primary Properties of Ethanol Flash points of ethanol-water mixtures

Boiling Point 351.37 K
Flash Point 289.6 K Industrial Production
Auto-ignition temperature 698 K C 2 H 4  H 20   CH 3CH 2OH
H 3 PO4 
Heat of combustion 26,800 kJ/kg

Fermentation C6 H 12 O6  2CH 3CH 2 OH  2CO2 for glucose and fructose

C12 H 22 O11  H 2 O  4CH 3CH 2 OH  4CO2 for sucrose
1.2 The recognized potential of bio-ethanol

Literature (2000-2017) concerning bio-ethanol SCOPUS with keywords

(■ Bio-ethanol General; ● Fuel-Application; ◆ Environment and Economics;
▼ Simulation and Separation; ▲ Membrane Technology; ★ Very High Gravity (VHG))
1.3 The different “generations” of bio-ethanol
production
Food-based Vs. Non-food
Corn, Wheat, Cassava, Fair ethanol yield: 3 to 10
Sugarcane Sweet ton raw material/ ton bio-
(mostly Brazil, sorghum ethanol
USA, China) (mostly China)
Biomass Very low ethanol yield
(although improving),
through: (1) aggressive
Algae pretreatment; (2) selected
bacterial/yeast strains; (3)
enzymatic hydrolysis.

》10 ton raw material/ ton

bio-ethanol
Contents
• 1. Characteristics and worldwide potential
• 2. The uses of bio-ethanol
• 3. Bio-ethanol production
• 4. Traditional process routes
• 5. Process improvements
• 6. General conclusions
 Engine fuel and fuel additive
Common ethanol-petrol mixtures
Code Composition Countries Comments
max. 5% anhydrous ethanol, Western Europe,
E5
min. 95% petrol India
max. 10% anhydrous ethanol, USA, Europe, China,
E10
min. 90% petrol India, South Africa
Blends for regular cars
max. 15% anhydrous ethanol, USA, cars >2000,
E15
min. 85% petrol South Africa
max. 25% anhydrous ethanol,
E25 Brazil
min. 75% petrol
max. 85% anhydrous ethanol,
E85 USA, Europe
min. 15% petrol
Flex-Fuel vehicles
hydrous ethanol (~ 5.3 wt%
E100 Brazil
water)

Fuel and feedstock in chemicals' synthesis

Conversion pathways of ethanol to different

organic chemicals
Contents

• 1. Characteristics and worldwide potential

• 2. The uses of bio-ethanol
• 3. Bio-ethanol production
• 4. Traditional process routes
• 5. Process improvements
• 6. General conclusions
"Generations" of bio-ethanol production

Sugar-based
mostly Hexoses

Cellulosic/algal-based

Hexoses
Pretreatment needed
Pentoses
Saccharification+ Fermentation
Contents

• 1. Characteristics and worldwide potential

• 2. The uses of bio-ethanol
• 3. Bio-ethanol production
• 4. Traditional process routes
• 5. Process improvements
• 6. General conclusions
4.1 Intergrated saccharification/fermentation processes
versus two-step processes
Mass balance of the first generation Cofco process of
cassava-based bio-ethanol
Contents

• 1. Characteristics and worldwide potential

• 2. The uses of bio-ethanol
• 3. Bio-ethanol production
• 4. Traditional process routes
• 5. Process improvements
• 6. General conclusions
5.1 Energy intergration within the current
production processes

After
Before

Production
Energy Stream
Mass Stream

Steam
Steam
Before: 2.5 kg steam/kg ethanol
After: ~ 1.8 kg steam/kg ethanol
 5.2 The use of VHG fermentation
• In traditional starch fermentation, Saccharomyces Cerevisiae is used as yeast
and the ethanol concentrations ~12 vol% are acceptable to avoid inhibition;

• The use of specific yeasts or bacteria, such as Zymomonas mobilis, with

higher inhibition levels, opened the way to very high concentration
fermentation, referred to as very high gravity (VHG) fermentation.

Heat duty of the distillation when using VHG fermentation

VHG conditions
15 vol% 19 vol%
C1501 C1502 C1503-1 C1503-2 C1501 C1502 C1503-1 C1503-2
Reboiler
5343 15094 18163 4163 10062 14512
duty (kW)
Condenser
2264 14356 18144 2266 9412 14186
duty (kW)

After: ~ 0.94 kg steam/kg ethanol

5.3 The development of hybrid (pervaporation) systems
5.3.1 “Drying” of Ethanol

Current molecular sieve dehydration of azeotropic ethanol-H2O mixtures

Mass and energy balance of the molecular sieve process
Mass balance
Feed water concentration (wt%) 5.6
Product water concentration(wt%) 0.8
Total feed flow rate (kg/h) 27,160
Feed ethanol flow rate (kg/h) 25,638
Product mass flow rate (kg/h) 25,845
Water absorption (kg/h) 1,314
Energy balance
Evaporator heat Product heat (kJ/kg) 868

Heat content of steam (kJ/kg) 2,061

Absorption column Steam consumption (kJ/h) 23,563,127

Absorption column Steam consumption (kg/h) 11,434

Regeneration column Steam consumption (kJ/h) 1,452,207

Regeneration column Steam consumption (kg/h) 705

Total steam (kg/h) 12,139

(kg steam/kg ethanol) 0.48
Novel approach: Schematic diagram of the process and lab
Test Cell Unit

Membrane Area : ~ 117 m2

5.3.2 Hybrid pervaporation operation of the bio-ethanol
fermentation

FFIRST COLUMN  0.75FFEED  FRETENTATE  165000 kg / h

FRETENTATE  47080 kg / h
FPREMEATE  7920 kg / h

Membrane Area : ~ 1095 m2

Summary results of the Cofco distillation process

System Steam Consumption (kg steam/kg ethanol)
Basic 2.50
Integrating reboilers and condensers 1.18
VHG (15%) 1.17
VHG (19%) 0.94
Pervaporation 1.13
5.3.3 Cross-flow microfiltration of bio-ethanol
fermentation broth
• Bio-ethanol fermentation broth consists of mainly water
and ethanol, together with solid residues of un-reacted
feedstock and additives (mostly yeast).

• The current mechanical separation (belt filter or centrifuge)

can only remove + 10 µm particles representing about
90% of the total solids content.

• The sintered metal fiber (SFM) fleeces are highly efficient

for microfiltration and the removal of suspended solids
largely exceeds 99%.
  > 99% retention of > 1 μm particles
 flux: 5 to 10 m3/m2h at TMP of 1.5 bar

 protection of heat exchangers, pumps

 no need of 1st separation column
 very small MF unit needed: 30 m2

Size analysis of broth solids

5.4 Intergrated novel production process

Fig.5 Schematics of the processes for bio-ethanol production

(a) As currently applied; (b) With potential membrane applications
(DDGS: Distillers Dried Grains with Solubles; 1+2+3: cellulosic materials; 2+3: starch or carbohydrate rich
materials)
Contents

• 1. Characteristics and worldwide potential

• 2. The uses of bio-ethanol
• 3. Bio-ethanol production
• 4. Traditional process routes
• 5. Process improvements
• 6. General conclusions
General Conclusions

 Implementing the energy-pinch approach enables to integrate recycle

condenser and reboiler heat duties;
Steam duty: 2.50 to 1.8 kg steam/kg bio-ethanol

 VHG (19%) reduces the steam consumption to 0.94 kg steam/kg bio-

ethanol, whilst operation in a hybrid mode (pervaporation of 33 % of the
fermenter broth) achieves similar savings;
Membrane dehydration can save 0.5 kg steam/kg bio-ethanol, in
replacing molecular sieves
Microfiltration can reduce fouling of heat exchangers, pumps,….

 Aneconomic analysis reveals that the factory-gate price of cassava-

based bio-ethanol could be reduced from ~820 €/ton to ~730 €/ton.
Sugarcane- and corn-based bio-ethanol remain about 30 to 50 % more
expensive, due to the higher raw material cost.
Thank you for your attention!