Production of Biofuel Using Supercritical Fluid Media

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1 Production of Biofuel Using Supercritical Fluid Media Prof. Farid Gumerov Prof. Zufar Zaripov Prof. Farizan Gabitov A.P. Rustem Usmanov Kazan State Technological University, Kazan, Russia Department Thermophysics and Supercritical Fluid Technology

2 Kazan - "Third Capital" of Russia Kazan on the map of Russia Medieval Kazan Kazan Founded in 11 th century!

3 Kazan State Technological University (KSTU). Russian National Research Center. Department Thermophysics and Supercritical Fluid Technology Supercritical Research involving: Thermophysical properties of Complex Fluids. Supercritical Fluid Technology: -Biofuel - Synthesis of nanoparticles - Synthesis of a catalyst and its regeneration - Treatment of the raw plant materials - Extraction of residual petroleum from a oil well

4 Russia in Biofuel Market 97% В World МИРЕ Russia 3% Only 3%

5 Outline: Advantages of SCF Extraction with Supercritical Fluids (SCF) - Experimental Setup - Extraction Algae Oil with Supercritical CO 2 (Preliminary Result) Transesterification of a Vegetable Oil to Biofuel Using Supercritical Fluid Media - Methanol as SCF - Laboratory and Pilot Experimental Setups Experimental Results for Palm and Rapeseed Oils Conclusions SCF Extraction Economics

6 Advantages of SCF Re = w l ν ; Gr = β t ν g 2 l 3

7 Advantages of SCF Viscosity viscosity Solubility Parameter Solubility Parameter Diffusion coefficient Diffusionco efficient 3, жидкости Liquid SCF СКФ жидкости Liquid SCF СКФ Liquid SCF жидкости СКФ No Catalyst Needed High Heat and Mass transfer Characteristics of the Process

8 Supercritical Extraction Experimental Setup Supercritical Fluid Chromatography System From Thar Technologies Inc. (U.S.A)

9 Supercritical Extraction Experimental Setup Flow Extraction Process

10 Potential oil plants Oil plants, oil content and energy (average energy content in oil is assumed 35.5 kj/g) Crop Specific annual oil yield (L/ha) Soya Sunflower Rapeseed/canola Castor bean Jatropha Coconuts Palm oil Triadica sebifera Algae (10 g/m 2, 15% triacylglycerides content) Algae (50 g/m 2, 50% triacylglycerides content) Specific energy content (MWh/ha)

11 Potential oil plants Arable lands required to grow various oil crops for substitution of fossil diesel by biodiesel fuel Cotton Soya Rapeseed/canola Jatropha Mustard Oil palm Sunflower Algae

12 Potential oil plants Three scenarios of substituting half of fossil diesel fuel by biofuel in USA by 2022 Corn Soya Algae Lands that will need to be allocated for respective crops to satisfy 50% of demand for biodiesel fuel in USA.

13 Algae Sample Preparation Dry powder

14 Vacuum drying of Algae vacuum drying vacuum impulse drying

15 Supercritical Extraction Experimental Setup Chromatography Column Replaced to Extractor Algae Extract Remains after extraction Extraction at T = C, P = MPa

16 Supercritical Fluid Extraction Conditions Extracting Fluids: - Pure SCF CO 2, - Modified CO 2 with polar co-solvent (Methanol, Ethanol, Acetone etc.) Temperature T = (1-1.2) T c Pressure P = (1-5) P c

17 Transesterification Using SCF Methanol 40 Methanol PVT Properties Viscosity vs. Pressure Methanol 85 Methanol Pressure (MPa) K 600 K 570 K 550 K 530 K Viscosity (µpa s) K 530 K 550 K 570 K 600 K K 35 CP Density (kg m -3 ) Pressure (MPa) Methanol Low cost for pure material Well know supercritical properties Most chemically active alcohol

18 Flow Diagram of Biofuel Production with Conventional and Supercritical Method Conventional Method Supercritical Method Considerably less number of process steps No necessity of separation of catalyst and saponification products from reaction products

19 Advantages of Transesterification Using SCF Methanol Reaction Длительность duration, реакции, мин min Стоимость конструкционного материала, руб/кг Cost difference, rub/kg Каталитическая Catalytic СКФ SCF Степень конверсии, % Conversion rate, % Catalytic Каталитическая SCF СКФ 28 Каталитическая Catalytic СКФ SCF High reaction rate Reduction in cost High conversion rate

20 Laboratory Experimental Setup for Continuous Biodiesel Production 1 alcohol reservoir; 2 continuous type reactor; 3 reservoir for raw material; 4 thermostatic delaying vessel; 5 cooler; 6 gravitational -dynamic separator; 7 vacuum pump; 8 and 9 dosing pump; 10 heat-exchanger; 11, 12, and 13 high pressure valves; 14, 15, and 16 valves; 17 and 18 pressure regulators; 19 and 20-level meters; 21-temperature sensor; 22 and 23 pressure sensors.

21 Pilot Installation Transesterification Using SCF Methanol Biodiesel Fuel Emulsion

22 Schematic of the Pilot Installation Methanol Nanodispersed emulsion High Pressure Reactor Vegetable Oil Ultrasonic emulsifier High pressure pump Heater Separator

23 Advantages of Sonication Prior Transesterification Process Vegetable oil/methanol mixture ultrasonication Possibility of mixing of a non mixing fluids. High stability: no separation during transesterification process.

24 Ultrasonic dispersion of emulsions 1min 2min Average grain size, µm 3min 1min 2min 3min

25 Laboratory Scale Experimental Setup Setup (Thermostated in Liquid Tin (Sn)) General Schematic Extraction Cell

26 Laboratory Scale Experimental Setup (Thermostated in Furnace) General Schematic Extraction Cell

27 Experimental Results for Palm Oil 95 refined (a) 70 Not refined (b) Time: 10min 85 t=295 o C 60 t=335 o C Conversion yield (%) Conversion of fatty acids to methyl ethers Volume concentration of oil Volume concentration of oil

28 Experimental Results for Palm Oil refined (a) 75 Not refined (b) Time: 10min t=369 o C t=320 o C Conversion yield (%) Volume concentration of oil Volume concentration of oil

29 Experimental Results for Palm Oil Conversion yield (%) (a) C vol = (b) C vol =0.12 Not refined Time: 10min Temperature ( o C) Temperature ( o C) 95 (c) Conversion yield (%) C vol =0.18 Wt. fraction of fatty acids in methanol mixture Temperature ( o C)

30 Experimental Results for Palm Oil Conversion Yield vs. Pressure Effect of ultrasonic treatment C vol = 0.13 τ = 10 min 80 C vol = Conversion yield (%) 70 Conversion yield (%) t = 335 C 55 Not sonicated Pressure (atm) Temperature ( o C) Not refined, Time: 10min

31 Experimental Results for Pilot Setup Conversion Yield vs. Temperature C vol = 0.8 τ = 10 min Conversion yield (%) Conversion yield (%) Temperature ( o C) Temperature ( o C) Rapeseed Oil and Methanol Palm Oil and Ethanol

32 Research of Process Transesterification М ПК АЦП Р 3003 Р М

33 Thermal Effects of Process Transesterification С Р, kj/(kg К) 8,0 7,0 6,0 5,0 4,0 3,0 2, С Р, kj/(kg К) 8,0 7,0 6,0 5,0 4,0 3,0 2, Тemperature ( 0 C) Тemperature ( 0 C) Rapeseed Oil and Ethanol Palm Oil and Ethanol

34 Conclusions: Optimal conditions: 20 to 30 MPa and temperature 300 to 350 C. The optimal methanol to oil ratio strongly depends on preliminary treatment The ultrasonic treatment is considerable increasing the conversion yield The oil conversion into ethers is increasing with temperature and with excess of methanol. The very slight effect of pressure on the rapeseed oil conversion. The slightly increasing of conversion with pressure from 25 to 30 MPa. Further increase of pressure leads to decrease in conversion.

35 SCF Extraction Economics (Preliminary Estimation) For Industrial Installation with yield of 4000 Liter/day (968 Ton/year). Cost (8 RUB/L): $ 0.99 per Gallon Price of Mix Biofuel (10%) + Gasoline Analog of Euro-4: (15.5 RUB/L) or $ 1.9 per Gallon (Including Glycerol sale).

36 Thanks for your Attention!

Chuck Neece Director Research and Development FUMPA BioFuels

Chuck Neece Director Research and Development FUMPA BioFuels What is Biodiesel? Just give me the Facts! Biodiesel is Not! Just filtered grease or oil in your tank This would not be chemically changed to