Thermodynamics and Green Processing Laboratory, Department of Chemical Engineering, Sogang University

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Measurement of Solubility for

Disperse Dyestuffs in SC-CO 2 by Using in situ Apparatus

Kwang Jae Lee, Han Seok Kim and Ki-Pung Yoo

Thermodynamics and Green Processing Laboratory, Department of Chemical Engineering, Sogang University

Kwang Jae Lee, Han Seok Kim and Ki-Pung Yoo

Thermodynamics and Green Processing Laboratory, Department of Chemical Engineering, Sogang University

(2004.01.29)

Thermodynamics /Green Processing Laboratory

(2)

▶ Development of experimental apparatus and technique for measuring of solubility in

supercritical carbon dioxide

▶ Measurement and correlation of solubility for dyestuffs in supercritical carbon dioxide

▶ Criteria of optimum conditions for SFD

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OBJECTIVES

(3)

Dynamic method

- Continuous flow method - Circulated batch method

Static method

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BACKGROUND

▶ Classification of the experimental technique

(4)

Advantage

● to be surely the simplest experimental technique

● easy to operate

● small leakage available

Disadvantage

● a complete equilibrium cannot be achieved

● clogging of expansion valve 1) dry ice formation

2) dye particle precipitation

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Dynamic method - continuous flow method

CO2 tank

PT PT

Gas booster

Reservoir

Air bath

Equilibrium cell Cold trap Mass flow meter

Heating mantle

TE

Expansion Valve

BACKGROUND

(5)

Advantage

● a complete equilibrium state can be achieved

● no clogging

Disadvantage

● the results are strongly influenced by a small leakage from the cell

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Dynamic method - circulated batch method BACKGROUND

(6)

Advantage

● easy to make equilibrium state

● no clogging

● a small leakage available

Disadvantage

● fixed path length

- cannot measure the high solubility of solution

● high cost

Thermodynamics /Green Processing Laboratory

Static method BACKGROUND

(7)

Advantage

● can measure the solubility with in situ UV-Visible

spectroscopy

● a complete equilibrium state can be achieved

● no clogging

● flexible path length

- enable to measure over a

concentration range of several orders of magnitude

● low cost

Disadvantage

● need solvent for calibration

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Equilibrium cell

ISCO 260D

Syringe pump

Magnetic stirrer

Air oven

TE

Optical fiber

Optical fiber

Pressure gauge

UV-Vis.

Spectroscopy

PEEK Tube Optical

Fiber

EXPERIMENTAL

▶ House made apparatus used in this work

(8)

EXPERIMENTAL

▶ in situ Solubility measurement system

(9)

Thermodynamics /Green Processing Laboratory

EXPERIMENTAL

▶ The UV-Visible spectra of DY114

Wave length (nm)

360 380 400 420 440 460

Absorbance

0.0 0.1 0.2 0.3 0.4 0.5

Wave length (nm)

360 380 400 420 440 460

Absorbance

0.0 0.1 0.2 0.3 0.4 0.5

As time elapsing

(10)

Type Dyestuff Formula Tm Mw

E type (mild)

C.I. Disperse Red 60

(anthraquinone) 187 ℃ 331.32

C.I. Disperse Blue 56

(anthraquinone) 199 ℃ 365.18

C.I. Disperse Yellow 54

(quinoline) 270 ℃ 289.28

O

NH2 O

OH O

O

NH2 O

OH Br OH

NH2

O

O OH N

● Dyestuffs used in this work (E-type)

Thermodynamics /Green Processing Laboratory

▶ Materials EXPERIMENTAL

(11)

Type Dyestuff Formula Tm Mw

C.I. Disperse Red 360

(mono-azoic) 146 ℃ 424.43

S type (thick)

C.I. Disperse Blue 79.1

(mono-azoic) 146 ℃ 530

C.I. Disperse Yellow 114

(mono-azoic) 205 ℃ 424.43

N N N

CH2CH2CN CH2CH2O CN

O2N

N N N

CH2CH2OCOCH3 CH2CH2OCOCH3 Br

O2N

NO2 NHCOCH3 OCH3

S O O O N N

N H3C

CH3 O HO

CN

EXPERIMENTAL

Dyestuffs used in this work (S-type)

Thermodynamics /Green Processing Laboratory

(12)

Solvent Formula Mw ρ T

C

(K)

P

C

(MPa)

T

b

(K)

Dipm.

(debye)

Acetone CH3COCH3 58.08 0.792 508.2 4.71 329.65 2.9

Benzene C6H6 78.11 0.879 562.16 4.88 353.25 0.0

Ethanol CH3CH2OH 46.07 0.789 513.92 6.12 351.55 1.7

n-Hexane CH3(CH2)4CH3 86.17 0.659 507.6 3.04 342.15 0.0

Carbon dioxide CO2 44.01 0.713* 304.19 7.38 - 0.0

EXPERIMENTAL

Solvents used in this work

Thermodynamics /Green Processing Laboratory

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Beer-Lambert’s Law

A = εl C

A = absorbance of sample, l = path length

C = concentration of sample, ε = molar extinction coefficient

Calibration Solvent

Hexane : reference solvent

- polarity and extinction coefficient are similar to CO

2

- negligible shifts in the position of absorption maxima

Thermodynamics /Green Processing Laboratory

THEORY

(14)

▶ UV-Visible spectra of E-type dyestuffs in organic solvents

Wavelength (nm)

400 450 500 550 600 650

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0

Benzene Acetone Ethanol

Absorbance

0.5 1.0 1.5 2.0 2.5

Benzene Acetone Ethanol

Wavelength (nm)

400 450 500 550 600 650 700

Absorbance

0.0 0.5 1.0 1.5 2.0 2.5

Benzene Acetone Ethanol

C. I. Disperse Red 60

C. I. Disperse Yellow 54 C. I. Disperse Blue 56

RESULTS

(15)

▶ UV-Visible spectra of S-type dyestuffs in organic solvents

RESULTS

Wavelength (nm)

400 450 500 550 600 650 700

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

Benzene Acetone Ethanol

Wavelength (nm)

350 400 450 500 550

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Benzene Acetone Ethanol

C. I. Disperse Red 360

C. I. Disperse Yellow 114Wavelength (nm)

400 500 600 700 800

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Benzene Acetone Ethanol

C. I. Disperse Blue 79.1

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Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Absorbance

0.0 0.5 1.0 1.5 2.0 2.5

DR 60 y=42.42x DR 360 y=73.03x DB 79.1 y=65.49x DB 56 y=57.86x DY 114 y=84.87x DY 54 y=198.70x

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Absorbance

0.0 0.5 1.0 1.5 2.0 2.5

DR 60 y=42.42x DR 360 y=73.03x DB 79.1 y=65.49x DB 56 y=57.86x DY 114 y=84.87x DY 54 y=198.70x

Thermodynamics /Green Processing Laboratory

▶ Determination of ε for dye-acetone system

by using conventional UV-Visible spectroscopy

ε = slope of calibration curve / 10 mm

RESULTS

(17)

Thermodynamics /Green Processing Laboratory

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Absorbance

0.0 0.5 1.0 1.5 2.0

DR 60 y=41.04x DR 360 y=89.25x DB 79.1 y=64.14x DB 56 y=66.82x DY 114 y=97.84x DY 54 y=172.0x

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Absorbance

0.0 0.5 1.0 1.5 2.0

DR 60 y=41.04x DR 360 y=89.25x DB 79.1 y=64.14x DB 56 y=66.82x DY 114 y=97.84x DY 54 y=172.0x

RESULTS

▶ Determination of ε for dye-benzene system

ε = slope of calibration curve / 10 mm

by using conventional UV-Visible spectroscopy

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Thermodynamics /Green Processing Laboratory

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

DR 60 y=42.42x DR 360 y=18.14x DB 79.1 y=25.41x DB 56 y=55.53x DY 114 y=25.46x DY 54 y=153.67x

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

DR 60 y=42.42x DR 360 y=18.14x DB 79.1 y=25.41x DB 56 y=55.53x DY 114 y=25.46x DY 54 y=153.67x

RESULTS

▶ Determination of ε for dye-ethanol system

ε = slope of calibration curve / 10 mm

by using conventional UV-Visible spectroscopy

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Thermodynamics /Green Processing Laboratory

Dyestuff Solvent ε (mol/cm

2

) ×10

6

λ

max

(nm)

E type

DR60 Benzene 14.054 515

Acetone 13.597 515

Ethanol 14.060 517

DB56 Benzene 21.128 624

Acetone 24.403 657

Ethanol 20.742 625

DY54 Benzene 57.479 448

Acetone 49.755 441

Ethanol 44.455 442

▶ Molar extinction coefficient of E-type dyes

RESULTS

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Thermodynamics /Green Processing Laboratory

Dyestuff Solvent ε (mol/cm

2

) ×10

6

λ

max

(nm)

S type

DR360 Benzene 32.165 489

Acetone 39.310 504

Ethanol 7.991 498

DB79.1 Benzene 34.710 593

Acetone 33.992 581

Ethanol 13.467 575

DY114 Benzene 36.021 428

Acetone 41.526 420

Ethanol 10.804 415

▶ Molar extinction coefficient of S-type dyes

RESULTS

(21)

Thermodynamics /Green Processing Laboratory

RESULTS

Density of CO2 (mol/L)

12 14 16 18 20 22

Mole fraction of DR60

0.1 1 10

Sung and Shim (1999) at 313.15 K

this work

Density of CO2 (mol/L)

12 14 16 18 20 22

Mole fraction of DR60

0.1 1 10

Sung and Shim (1999) at 313.15 K

this work

▶ Reliability of the experimental technique

(22)

Concentration (g/L)

0.001 0.002 0.003 0.004 0.005 0.006 0.007

Absorbance

0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Yellow 54 (447nm) y = 221.78x R2 = 0.9980

Concentration (g/L)

0.001 0.002 0.003 0.004 0.005 0.006 0.007

Absorbance

0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Yellow 54 (447nm) y = 221.78x R2 = 0.9980

by using in situ UV-Visible spectroscopy

Determination of ε for DY 54-hexane system

RESULTS

Thermodynamics /Green Processing Laboratory

▶ Measurement of the solubility for DY54 in SC-CO 2

(23)

Concentraton of benzene (g/L)

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035

Absorbance

0.0 0.5 1.0 1.5 2.0 2.5

JASCO : 10.00 mm DYEMAX : 6.74mm DYEMAX : 13.49 mm

Concentraton of benzene (g/L)

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035

Absorbance

0.0 0.5 1.0 1.5 2.0 2.5

JASCO : 10.00 mm DYEMAX : 6.74mm DYEMAX : 13.49 mm

Conventional UV in situ UV

Slope : molar extinction coeffi. × path length

Determination of path length

for in situ UV-Visible spectroscopy

RESULTS

Thermodynamics /Green Processing Laboratory

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Density of CO2 (mol/L)

8 10 12 14 16 18 20

Mole fraction of DY54

10-8 10-7 10-6 10-5 10-4

333.15 K 363.15 K 393.15 K

Density of CO2 (mol/L)

8 10 12 14 16 18 20

Mole fraction of DY54

10-8 10-7 10-6 10-5 10-4

333.15 K 363.15 K 393.15 K

Solubility data of DY54 in SC-CO 2

RESULTS

(25)

Temperature (K)

Pressure (MPa)

Density of CO2 (mol/L)

Solubility of dye (y fraction)

333.15

14.81 14.1191 4.4326e-8

17.67 15.7278 1.3171e-7

22.36 17.2315 7.1913e-7

25.01 17.8435 1.2860e-6

30.04 18.7392 1.8146e-6

363.15

21.53 13.0766 5.6917e-7

24.05 14.1784 1.0620e-6

29.42 15.8117 2.2720e-6

31.28 16.2426 2.4283e-6

393.15

21.57 9.9775 5.1743e-7

22.81 10.6129 8.8372e-7

26.60 12.2605 2.6317e-6

29.04 13.1108 4.2822e-6

Solubility data of DY54 in SC-CO 2

RESULTS

Thermodynamics /Green Processing Laboratory

(26)

B

ln(xP/P ref ) = A + c(ρ-ρ ref )

▶ Model equation for correlating the solubility

RESULTS

Thermodynamics /Green Processing Laboratory

where,

x : mole fraction of solubility, P : system pressure, P

ref

: standard pressure of 1 bar, ρ : solution density, ρ

ref

: reference density (700 kg/m

3

)

by Bartle et al., 1991

(27)

Density of CO2 (g/cm3)

0.0 0.2 0.4 0.6 0.8 1.0

Mole fraction of DY54

0 2x10-6 4x10-6 6x10-6 8x10-6 10x10-6

333.15 K 363.15 K 393.15 K Calculated data

Density of CO2 (g/cm3)

0.0 0.2 0.4 0.6 0.8 1.0

Mole fraction of DY54

0 2x10-6 4x10-6 6x10-6 8x10-6 10x10-6

333.15 K 363.15 K 393.15 K Calculated data

Correlation – empirical equation

RESULTS

Thermodynamics /Green Processing Laboratory

(28)

▶Molar extinction coefficient of dyestuffs in organic solvents were calculated from the slope of linear calibration curves of absorbance.

▶Molar extinction coefficient for carbon dioxide was determined by using standard solution of C. I. Disperse Yellow 54.

▶Solubility of the dye C. I. Disperse Yellow 54 in supercritical carbon dioxide have been measured in the temperature range from (333.15 to 393.15) K and at pressure from (14.81 to 30.04) MPa.

▶Solubility data of the C. I. Disperse Yellow 54 in supercritical carbon dioxide were correlated in terms of the density (g/cm

3

) of carbon dioxide using an empirical equation of Bartle et al.

Thermodynamics /Green Processing Laboratory

CONCLUDING REMARKS

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