3th Forum Ha Noi 20-21 December 2012

Assc. Prof. Dr. Truong Vinh Chemical Engineering Department, Nong Lam University HCM city

Contents
i. ii. iii. iv. v. Introduction to biodiesel and algae. Introduction to ethanol plant. Introduction to algal-biodiesel from ethanol plant. Two-stage growing experiment in fresh water. Growing experiment in wastewater without stress treatment. vi. Photobioreactor development. vii. Discussion viii.Proposed growing model for large scale algal production based on two-stage growing methodology ix. Conclusion

INTRODUCTION TO BIODIESEL Why biodiesel ?

1. The resources of fossil fuel is expected to be reduced in the next decades. 2. Consumption of diesel is 6 times of petrol. Combustion of fossil diesel produces CO2 causing global warming: 240ppm to 345ppm during the 20th century. 3. Need to replace fossil fuel by other sources of energy: wind, solar, biodiesel. 4. Biodiesel is one of the renewable energy resources (wind, solar can not be used directly for transport). 5. Direct use of biodiesel in diesel engine is cleaner than fossil diesel: less emission of greenhouse gas such as CO, CO2, SO2, NOx.

INTRODUCTION TO ALGAE
Crop Corn Sugar cane Switch grass Wood residue Soybeans Rapeseed, canola Algae Used to produce Ethanol Ethanol Ethanol Ethanol, Biodiesel Biodiesel Biodiesel Biodiesel

Why microalgae ?

Less land used => No food competition problem Algae+CO2= Energy =>Less gas emission
Greenhouse gas emission (kg CO2/MJ produced)* 81-85 4-12 -24 N/A 49 37 -183 Estimated % crop land used 157-262 46-57 60-108 150-250 180-240 30 1-2

(Source: Martha Groom, University of Washington; * Emissions produced during the growing, harvesting, refining and burning)

Oil crops, waste cooking oil and animal fat : a potential renewable, carbon neutral fuels, available technology, food competition problem Microalgae: high productivity, less competition with feed crop, less CO2 emission => renewable resources of energy that has the potential to completely displace fossil diesel

1. INTRODUCTION TO ETHANOL PLANT

1. Name of company: Green Field Join Stock Company 2. Location: Quang Nam Province, Vietnam 3. Specification of the ethanol plant: Ethanol production: 100,000 ton/year Waste water release: 4000 m3/day Cooling water release: this river water used to cool the ethanol distillation equipment with the rate of 8000 m3/day at temperature of 60oC. CO2 resource: fermentation of cassava produced 20,000 ton CO2/year

2. INTRODUCTION TO algal-biodiesel from ethanol plant

Ethanol Plant Cheap CO2 source High Nutrition

Cassava => Fermentation => Ethanol + CO2 + Waste water + Residual

Microalgae => Photobioreactor => biodiesel + glycerine + chlorophyll + Waste

Growing System

Biodegradable Film

Food color Antioxidant

Fertilizer

Biodiesel Plant

3. Production Process of biodiesel from algae in two-stage growing system

Dried biomass
Drying Harvesting

Dry extraction

Wet biomass

Second stage of growing

First stage of growing

Treatments

Oil separation

Wet extraction

Oil refining

Biodiesel Reaction

Methanol Catalyst
Glycerin Purification

Product Separation

Algae growth in photobioreactor

Biodiesel Purification

Algae seed production

3.1 GROWING WITHOUT TREATMENT

Composition Protein Lipid Carbonhydrates Percentage 60.1 14.55 0.36 0.0013 0.0059 75.02

Chlorophylls
Carotenoids Total

Composition of algae grown without treatment is suitable for Functional Food

3.1 GROWING WITH TREATMENT

Methodology: Experiment 1: Growing in Basal medium for 7 days Transfering to new medium contained 15, 30, 45, and 60 % Basal nutrient. The control sample was the 100% Basal medium Continueing to grow for 7 days and harvest Experiment 2: Best result from experiment 1 was used with modification of Basal medium and variation of initial cell density

3.2 GROWING WITH TREATMENT: results of experiment 1

Effect of stress nutrient treatment on biomass and oil productivity after 7 days
.500 .450 .400 .350 Oil content, g/L .300 .250 .206 .200 .150 .100 .050 .000 15% nutrient 30% nutrient Crude oil, g/L 45% nutrient Refined lipid, g/L 60% nutrient Biomass, g/L Control .000 .500 1.000 .290 .394 .364 .316 .278 .276 .272 1.500 Biomass, g/L .403 2.000 .472 2.500

3.2 GROWING WITH TREATMENT: results of experiment 2

Effect of initial cell density on the biomass and oil content at 30% nutrient stress treatment
70.000 60.000 53.522 Crude oil content, % 50.000 40.000 0.149 30.000 20.000 10.000 0.050 0.218 50.350 0.200 0.156 30.150 34.560 27.870 0.100 0.280 60.130 0.246 0.232 0.250 0.300

0.150

.000
3 8(0) 8(1) 8(2) Initial cell density, million/L 15 % du 25

0.000

8(0): Basal , 8(1): Modified 1 , 8(2): Modified 2

g du/L

Lipid Productivity, g/L

3.2 GROWING WITH TREATMENT: Conclusion

Nutrient stress treatment decreased the biomass but improved the oil content compared to the control.
At the treatment 30% of Basal nutrient (in equivalent to deprivation of 70% of nutrient), oil content was highest with crude oil of 0.47 g/L and refined oil of 0.36 g/L. At the treatment 30% of Basal medium, with additional of MgSO4 (Modified 1) and initial cell density of 8 106/mL, the oil content was 60%.

4. Growing experiment in wastewater without stress treatment

Nutrient in waste water of ethanol plant
Item N total P total K Ca Mg Na Fe Mn Cu Zn S Mo Co BOD5 COD Value 438.2 40.94 648 9.02 131.63 0.432 0.14 11.46 106 345

Unit
mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L

mg/L
mg/L mg/L mgO2/L mgO2/L

4. Growing experiment in wastewater without stress treatment

Experimental design: the waste water was dilute with variation of the ratio between waste water and fresh water/cooling water from 20% to 100% (v/v) as in shown the following table: Treatment Waste water Fresh water 20w 20 80 40W 40 60 60w 60 40 80w 80 20 100w 100 0

Growth condition: container 1.5 liter, fluorescent light with light intensity of 110 mol/m2s using 4 fluorescent lamps of 40W

4. Growing experiment in wastewater without stress treatment: results

250 Cell density, x106/mL 200 150 100 50 0 0 5 10 15 Growing time, day 20 100 w 80 w 60 w 40 w 20 w

4. Growing experiment in wastewater without stress treatment: oil content and biomass
The algae could not survive in the media that contained higher 60% of waste water. At 20% of waste water, the algae grew well and better than in normal Basal medium. The cell density was 230 million/mL after 14 days of growing. The productivity of algae grown in 20% waste was 3.5g/L with crude oil content of 57%

4. Growing experiment in wastewater without stress treatment: Using LED light

Experimental design:

The waste water /cooling water of 20% , 25% and 30% (v/v) was used as nutrients for algal growing
Two sources of light were compared: fluorescent light (4 lamps of 40W) and LED light (4 lamps of 21 W) Algae were grown in 1.5 liter bottles.

4. Growing experiment in wastewater without stress treatment: Using LED light

Results: No significant different between cell density of algae grown under fluorescent and LED light after 8 days (P>0.05)
Waste content Fluores LED ANOVA Source of Variation Sample Columns Interaction Within Total Cell density, million/mL 20% 25% 30% 54 85 73 70 82 72 63 85 71 65 59 55 df 1 2 2 6 11 MS 123.6492 235.1511 51.25278 103.6933 F P-value F crit 1.1925 0.3167 5.9874 2.2678 0.1847 5.1433 0.4943 0.6328 5.1433

SS 123.65 470.30 102.51 622.16 1318.617

4. Growing experiment in wastewater without stress treatment: Using LED light

Results: the algae growed best at 25% of waste water for both light sources => using LED light saved half of energy
90 80 Cell density, x106/mL 70 60 50 40 30 Fluoresence LED light

20
10 0 20% waste 25% waste 30% waste

4. Growing experiment in wastewater without stress treatment: benefit from waste and CO2
Nutrient saving Price, VND/L from using waste medium 24.75 24.75 NaNO3 3.575 8.25 MgSO4 7H2O

Basal medium NaNO3 CaCl2 2H2O MgSO4 7H2O 8.25 K2HPO4 8.25 KH2PO4 28.875 NaCl 0.275 Total 73.975

Year of BOD experiment (mgO2/L) before/ After growing 2009 81/7.9

COD (mgO2/L) before/ After growing 260/78

2012
33 45%

106/80

345/100

Contribution of CO2 and nutritent in waste water on cost saving to produce biomass Saving from CO2 Saving from nutrient of waste water 39.9 1.5

5. PHOTOBIOREACTOR DEVELOPMENT
Purpose: Cheap price: plastic material for tube Contamination control: closed system Low operation cost: minimal pump energy

5.1 Photobioreactor parameters

Table 2: Summary of characteristics of different developed PBRS for experiments

Parameters
Tube diameter (D) of solar receiver (mm) Total length of solar receiver (m) Length of tube (m) Total area occupied (m2) Volume of culture (liter) Air lift column height (m) Tank height from tube (m) Velocity of culture (m/s)

LCP170D70 70 44.0 2.0 4.0 168 0.45 1 0.01

LCP400D140 140 26.0 3.5 5.7 400 0.7 1.4 7.5

LCP400D170 170 17.6 3.0 4.9 400 0.7 1.4 8

LCP400D210 210 11.5 3.0 3.6 400 0.7 1.4 8.5

5.2 Photobioreactors
Contamination control Simple construction
LCP400-D170 81 liter/m2

LCP400-D140 70 liter/m2

Treatment system

5.2 Photobioreactors
Contamination control Simple construction

LCP2500-D170: 2.5 m3 Width x Length = 2.5 m x 15 m 81 liter/m2

5.3 GROWING IN PBRS

The growing of algae Chlorella vulgaris in PBR LCP-170 Initial number of cell was 106 cell/ml 60 50 Cell density, 106/mL

40
30 20 10 0 0 100 200 300 400 Growing time, (h) 500 600

Figure 4: Algae density and OD of Chlorella vulgaris as function of growing time

5.4 DISCUSSION
Comparison of biomass cost produced from PBRs of different tube sizes of experimental systems with and without treatment
D, mm Biomass, g/L Crude Oil, mg/L CD, x106 cell/mL Specific volume, L/m2 210 0.336 36.6 27 89.3 170 0.35 70.9 47.5 81.1 140 0.41 80 38 70.0 70 0.67 80.4 125 40.4
The cost of oil reduced by 4 times with stress treatment

Capacity, g oil/m2
VND/g oil (without treatment) VND/g oil (with treatment)

3.27
423

5.75
425 107.6

5.60
447

3.25
1153

a)Microalgae is renewable resource of energy that has the potential to displace fossil diesel b)Technology should be improved to reduce cost by improving of algae strain, growing methodology. c)Wet extraction or solar drying should be considered to reduce the production cost d)Growing in waste water using CO2 of ethanol plant provided high productivity and reduced production cost e)Growth methodology in PBR should be combined with stress treatment (two stage growing) to optimize the biodiesel production from microalgae.

Methodology: Two-stage growing technology: First stageGrowing => Second stage-Treatment Strategy: Using sun energy as sustainable resource for algalbiodiesel production : Combination between direct sun light and solar panels as electrical source for LED light in order to

stabilize the light source during the year.

Solar panel

LED light

Plastic house

First stage

Sun drying

Cultivationoutdoor

Sun drying

15m

Plastic house

Cultivationindoor Plastic house

Plastic house 17m

Harvest - Seed culti.

Harvest - Seed culti. 15m

Harvest - Seed culti.

Treatment

Treatment

Treatment

Second stage

Treatment

Treatment

Treatment

Harvest - Seed cultivation.

Harvest - Seed cultivation

Harvest - Seed cultivation

 Initial results of project EEP-3-V-053 indicated that waste water of ethanol can be used as nutrient for algal growth to produce biodiesel with a contribution to cost saving of 1.5%. Using the available CO2 source produced from ethanol plant decreased the production cost by 40%. Autotrophic growth of algae for biodiesel is sustainable because it uses sun as energy. However, sun energy is not stable for algal growing due to the weather change during the year Therefore, solar panel is propose to stablise the light source LED light is expected to use to reduce the investment of the solar panels. Two stage growing method can be used to enhance the oil content. Energy used in extraction of oil from algae is reduced significantly by either wet extraction method or sun drying/solar drying. The improvement of other technologies such as plastic material for tubes of PBR, efficiency of LED light, solar panel, etc, is important

Contact adress: Truong Vinh Chemical Engineering Department Nona Lam University, Ho Chi Minh city, Vietnam tv@hcmuaf.edu.vn 0903862721