Production of Biofuel Using Supercritical Fluid Media · Supercritical Fluid Technology:-Biofuel -...

Production of Biofuel Using Production of Biofuel Using Supercritical Fluid MediaSupercritical Fluid Media

Prof. Farid Gumerov Prof. Farizan GabitovProf. Zufar Zaripov A.P. Rustem Usmanov

Kazan State Technological University, Kazan, Russia

Department Thermophysics and Supercritical Fluid Technology

Kazan

Kazan Kazan -- "Third Capital" of Russia"Third Capital" of Russia

Medieval KazanKazan on the map of Russia

Founded in 11th century !

Kazan State Technological Kazan State Technological University (KSTU). Russian National University (KSTU). Russian National Research Center.Research Center.

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

Department Thermophysics and Supercritical Fluid Technology Supercritical Research involving:

Russia in Biofuel Market Russia in Biofuel Market

97%

3%

В МИРЕ

Russia

World

Russia

97%

Only 3%

Advantages of SCF

Extraction with Supercritical Fluids (SCF)- Experimental Setup - Extraction Algae Oil with Supercritical CO2

(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

Outline:Outline:

2

3

;Re

νβν

lgtGr

lw

⋅⋅∆⋅=

⋅=

Advantages of SCFAdvantages of SCF

No Catalyst Needed High Heat and Mass transfer Characteristics of the Process

viscosity

жидкости СКФ

5000

100-500


Diffusioncoefficient

3,2

30-300

Solubility Parameter


8-10 8-10

Liquid SCF Liquid SCFLiquid SCF

Advantages of SCFAdvantages of SCF

Viscosity Diffusion coefficient

Solubility Parameter

Supercritical Fluid Chromatography System From Thar Technologies Inc. (U.S.A)

Supercritical Extraction Supercritical Extraction Experimental Setup Experimental Setup


Flow Extraction Process

Potential oil plantsPotential 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)

Specific energy content (MWh/ha)

Soya 446 4

Sunflower 952 9

Rapeseed/canola 1190 11

Castor bean 1413 13

Jatropha 1892 18

Coconuts 2689 25

Palm oil 5950 55

Triadica sebifera 6527 61

Algae (10 g/m2, 15% triacylglycerides content)

11204 104

Algae (50 g/m2, 50% triacylglycerides content)

100000 931


Arable lands required to grow various oil crops for substitution of fossil diesel by biodiesel fuel

Cotton Soya Mustard Sunflower

AlgaeOil palmJatrophaRapeseed/canola


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.

Algae Sample PreparationAlgae Sample Preparation

Dry powder

VacuumVacuum dryingdrying of Algae of Algae

vacuum drying

vacuumimpulsedrying


Algae Extract

Remains after extraction

Chromatography Column Replaced to Extractor

Extraction at T = 40-60 °C, P = 30 - 40 MPa

Supercritical Fluid Extraction Supercritical Fluid Extraction ConditionsConditions

Extracting Fluids: - Pure SCF CO2, - Modified CO2 with polar co-solvent

(Methanol, Ethanol, Acetone etc.)

Temperature T = (1-1.2) Tc

Pressure P = (1-5) Pc

Transesterification Using SCF Transesterification Using SCF Methanol Methanol

0 100 200 300 400 500 600 7000

10

20

30

40

Methanol

Pre

ssur

e (M

Pa)

Density (kg·m-3)

512.6 K

600 K

550 K

570 K

630 K

530 K

CP

0 5 10 15 20 25 30 35 40 45 5015

25

35

45

55

65

75

85

95

Methanol

Vis

cosi

ty (µP

a·s)

Pressure (MPa)

512.6 K

530 K 550 K

570 K 600 K

Methanol PVT Properties Viscosity vs. Pressure

Methanol – Low cost for pure material Well know supercritical propertiesMost chemically active alcohol

Flow Diagram of Biofuel Production with Flow Diagram of Biofuel Production with Conventional and Supercritical MethodConventional 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

Advantages of Transesterification Advantages of Transesterification Using SCF MethanolUsing SCF Methanol

Длительность реакции, мин

4-20

60-1800

Каталитическая СКФ

Стоимость конструкционного материала, руб/кг

28

440


Степень конверсии, %

98

60-97


High reaction rate

Reduction in cost

High conversion rate

Reaction duration, min

Catalytic SCF

Catalytic SCF

Catalytic SCF

Cost difference, rub/kg

Conversion rate, %

Laboratory Experimental Setup for Laboratory Experimental Setup for Continuous Biodiesel ProductionContinuous 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.

Pilot Installation Transesterification Pilot Installation Transesterification Using SCF MethanolUsing SCF Methanol

Emul

sion

Biodiesel Fuel

Schematic of the Pilot InstallationSchematic of the Pilot Installation

High pressure pump

Nanodispersed emulsion

Vegetable Oil

Methanol

Ultrasonic emulsifier

High Pressure Reactor

SeparatorHeater

Advantages of Sonication Prior Advantages of Sonication Prior Transesterification Process Transesterification Process

Possibility of mixing of a non mixing fluids.High stability: no separation during transesterification process.

Vegetable oil/methanol mixture ultrasonication

Average grain size, µm

1min 2min 3min

Ultrasonic dispersion of emulsions

1min2min

3min

Laboratory Scale Experimental Laboratory Scale Experimental Setup Setup (Thermostated in Liquid Tin (Sn))(Thermostated in Liquid Tin (Sn))

Extraction CellGeneral Schematic

Laboratory Scale Experimental Laboratory Scale Experimental Setup Setup (Thermostated in Furnace)(Thermostated in Furnace)

Extraction CellGeneral Schematic

Experimental Results for Experimental Results for Palm Oil Palm Oil

refined Not refined

0.070 0.077 0.084 0.09135

45

55

65

75

85

95

t=295 oC

Con

vers

ion

yiel

d (%

)

Volume concentration of oil

(a)

0.12 0.14 0.16 0.18 0.2020

30

40

50

60

70

t=335 oC


(b)Time: 10min

Conversion of fatty acids to methyl ethers

Experimental Results for Experimental Results for Palm OilPalm Oil

0.15 0.21 0.27 0.33 0.3930

40

50

60

70

80

90

t=369 oC

Con

vers

ion

yiel

d (%

)


(a)

0.12 0.14 0.16 0.1815

30

45

60

75

t=320 oC


(b)refined Not refined Time: 10min


Not refined

Time: 10min

285 295 305 315 32530

45

60

75

90Cvol=0.09

Con

vers

ion

yiel

d (%

)

Temperature (oC)

(a)

300 315 330 345 36045

60

75

90 Cvol=0.12

Temperature (oC)

(b)

335 345 355 365 37520

35

50

65

80

95

Cvol=0.18

Con

vers

ion

yiel

d (%

)

Temperature (oC)

(c)

Wt. fraction of fatty acidsin methanol mixture


Not refined, Time: 10min

150 200 250 300 35050

60

70

80

90

Cvol=0.18

Con

vers

ion

yiel

d (%

)

Pressure (atm)

Conversion Yield vs. Pressure

t = 335 °C

280 295 310 325 340 35540

55

70

85

100

Cvol = 0.13

Con

vers

ion

yiel

d (%

)

Temperature (oC)

τ = 10 min

Effect of ultrasonic treatment

Not sonicated

Experimental Results for Pilot SetupExperimental Results for Pilot Setup

240 260 280 300 320 340 360 38050

60

70

80

90

100

Con

vers

ion

yiel

d (%

)

Temperature (oC)

Conversion Yield vs. Temperature

250 270 290 310 330 350 3700

15

30

45

60

75

90 Cvol = 0.8

Con

vers

ion

yiel

d (%

)

Temperature (oC)

τ = 10 min

Rapeseed Oil and Methanol Palm Oil and Ethanol

М

АЦП

Р 3003

Р 3003

ПК

М

1 2 3 4

56 78

М

АЦП

Р 3003

Р 3003

ПК

М

1 2 3 4

56 78

12

3

4

5 678

9

10

127

Research of Process Research of Process Transesterification Transesterification

2,0

3,0

4,0

5,0

6,0

7,0

8,0

50 100 150 200 250 300 350

123

СР, k

J/(k

gК

)

Тemperature (0C)

2,0

3,0

4,0

5,0

6,0

7,0

8,0

50 100 150 200 250 300 350

123

СР, k

J/(k

gК

)

Тemperature (0C)

Rapeseed Oil and Ethanol Palm Oil and Ethanol

Thermal Effects of Process Thermal Effects of Process Transesterification Transesterification

Conclusions: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.

SCF Extraction EconomicsSCF Extraction Economics(Preliminary Estimation)(Preliminary Estimation)

For Industrial Installation with yield of 4000 Liter/day (968 Ton/year).

Cost (8 RUB/L): $ 0.99 per GallonPrice of Mix Biofuel (10%) + Gasoline

Analog of Euro-4: (15.5 RUB/L) or $ 1.9 per Gallon (Including Glycerol sale).

Thanks for your AttentionThanks for your Attention!!

Production of Biofuel Using Supercritical Fluid Media · Supercritical Fluid Technology:-Biofuel -...

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