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. Why microalgae ? INTRODUCTION TO ALGAE Less land used => No food competition problem Algae+CO2= Energy =>Less gas emission Crop Corn Sugar cane Switch grass Wood residue Soybeans Rapeseed, canola Algae Used to produce Ethanol Ethanol Ethanol Ethanol, Biodiesel Biodiesel Biodiesel Biodiesel Greenhouse gas emission (kg CO2/MJ produced)* 81-85 4-12 -24 N/A Estimated % crop land used 157-262 46-57 60-108 150-250 49 37 -183 180-240 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 Biodiesel Plant Fertilizer 3. Production Process of biodiesel from algae in two-stage growing system Dry extraction Oil separation Harvesting Drying Second stage of growing Dried biomass Wet biomass Wet extraction Treatments Biodiesel Reaction Product Separation Biodiesel Purification Methanol Catalyst Glycerin Purification First stage of growing Oil refining Algae growth in photobioreactor Algae seed production 3.1 GROWING WITHOUT TREATMENT Composition Percentage Protein 60.1 Lipid 14.55 Carbonhydrates 0.36 Chlorophylls 0.0013 Carotenoids 0.0059 Total 75.02 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 2.500 .472 .450 Oil content, g/L .350 .300 2.000 .364 .316 .290 .278 .276 .272 1.500 .250 .206 .200 1.000 .150 .100 .500 .050 .000 .000 15% nutrient 30% nutrient 45% nutrient Crude oil, g/L Refined lipid, g/L 60% nutrient Biomass, g/L Control Biomass, g/L .400 .403 .394 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 60.130 60.000 0.246 50.000 0.250 0.232 0.218 50.350 0.200 40.000 0.156 0.149 30.150 30.000 34.560 0.150 27.870 0.100 20.000 0.050 10.000 0 .000 3 8(0) 8(1) 0 0 0.000 8(2) 15 25 Initial cell density, million/L 8(0): Basal , 8(1): Modified 1 , 8(2): Modified 2 % dầu g dầu/L Lipid Productivity, g/L 53.522 Crude oil content, % 0.300 0.280 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 Unit mg/L mg/L mg/L mg/L mg/L mg/L 0.432 0.14 11.46 106 345 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 20w 40W 60w 80w 100w Waste water 20 40 60 80 100 Fresh water 80 60 40 20 0 Growth condition: container 1.5 liter, fluorescent light with light intensity of 110 μmol/m2s using 4 fluorescent lamps of 40W 4. Growing experiment in wastewater without stress treatment: results Cell density, x106/mL 250 200 100 w 150 80 w 60 w 100 40 w 20 w 50 0 0 5 10 15 Growing time, day 20 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 SS 123.65 470.30 102.51 622.16 df 1 2 2 6 1318.617 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 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 Cell density, x106/mL 80 70 60 50 Fluoresence 40 LED light 30 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 Basal medium NaNO3 CaCl2 • 2H2O MgSO4 • 7H2O 8.25 K2HPO4 8.25 KH2PO4 28.875 NaCl 0.275 Total 73.975 8.25 MgSO4 • 7H2O 33 Year of BOD experiment (mgO2/L) before/ After growing COD (mgO2/L) before/ After growing 2009 81/7.9 260/78 2012 106/80 345/100 45% 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 LCP170D70 LCP400D140 LCP400D170 LCP400D210 70 140 170 210 44.0 26.0 17.6 11.5 2.0 3.5 3.0 3.0 Total area occupied (m2) 4.0 5.7 4.9 3.6 Volume of culture (liter) 168 400 400 400 Air lift column height (m) 0.45 0.7 0.7 0.7 Tank height from tube (m) 1 1.4 1.4 1.4 0.01 7.5 8 8.5 Parameters Tube diameter (D) of solar receiver (mm) Total length of solar receiver (m) Length of tube (m) Velocity of culture (m/s) 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 Cell density, 106/mL 50 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 210 170 140 70 Biomass, g/L 0.336 0.35 0.41 0.67 Crude Oil, mg/L 36.6 70.9 80 80.4 CD, x106 cell/mL 27 47.5 38 125 Specific volume, L/m2 89.3 81.1 70.0 40.4 Capacity, g oil/m2 3.27 5.75 5.60 3.25 VND/g oil (without treatment) 423 425 447 1153 VND/g oil (with treatment) 107.6 The cost of oil reduced by 4 times with stress treatment 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 First stage LED light Sun drying Plastic house Plastic house Cultivationoutdoor Cultivationindoor Sun drying Plastic house 17m Plastic house Harvest - Seed culti. Harvest - Seed culti. 15m 15m Harvest - Seed culti. Second stage Treatment Treatment Harvest - Seed cultivation. Treatment Treatment Harvest - Seed cultivation Treatment Treatment 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