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

(1)

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

OBJECTIVES

(3)

● Dynamic method

- Continuous flow method - Circulated batch method

● Static method

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

● 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

● 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

● 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

Equilibrium cell

ISCO 260D

Syringe pump

Magnetic stirrer

Air oven

TE

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)

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)

▶ 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)

(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

(13)

▶ 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

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

Wavelength (nm)

400 450 500 550 600 650 700

Absorbance

0.0 0.5 1.0 1.5 2.0 2.5

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

Wavelength (nm)

350 400 450 500 550

Absorbance

0.0 0.2 0.4 0.6 0.8 1.0 1.2

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

C. I. Disperse Blue 79.1

(16)

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

▶ Determination of ε for dye-acetone system

by using conventional UV-Visible spectroscopy

●

ε = slope of calibration curve / 10 mm

RESULTS

(17)

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Absorbance

0.0 0.5 1.0 1.5 2.0

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Absorbance

0.0 0.5 1.0 1.5 2.0

RESULTS

▶ Determination of ε for dye-benzene system

●

ε = slope of calibration curve / 10 mm

by using conventional UV-Visible spectroscopy

(18)

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

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

RESULTS

▶ Determination of ε for dye-ethanol system

●

ε = slope of calibration curve / 10 mm

by using conventional UV-Visible spectroscopy

(19)

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

(20)

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)

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

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

▶ 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

(24)

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

8 10 12 14 16 18 20

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

(26)

B

ln(xP/P _ref ) = A + c(ρ-ρ _ref )

▶ Model equation for correlating the solubility

RESULTS

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

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

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

(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.

CONCLUDING REMARKS

(29)

감 사 드 립 니 다.

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

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)

▶ 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

OBJECTIVES

● Dynamic method

- Continuous flow method - Circulated batch method

● Static method

BACKGROUND

▶ Classification of the experimental technique

Advantage

Disadvantage

● Dynamic method - continuous flow method

BACKGROUND

Advantage

● a complete equilibrium state can be achieved

● no clogging

Disadvantage

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

● Dynamic method - circulated batch method BACKGROUND

Advantage

Disadvantage

● Static method BACKGROUND

Advantage

Disadvantage

EXPERIMENTAL

▶ House made apparatus used in this work

EXPERIMENTAL

▶ in situ Solubility measurement system

EXPERIMENTAL

▶ The UV-Visible spectra of DY114

As time elapsing

Type Dyestuff Formula Tm Mw

● Dyestuffs used in this work (E-type)

▶ Materials EXPERIMENTAL

Type Dyestuff Formula Tm Mw

EXPERIMENTAL

● Dyestuffs used in this work (S-type)

Solvent Formula Mw ρ T

(K)

P

(MPa)

T

(K)

Dipm.

(debye)

EXPERIMENTAL

● Solvents used in this work

▶ 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

- negligible shifts in the position of absorption maxima

THEORY

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

RESULTS

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

RESULTS

▶ Determination of ε for dye-acetone system

by using conventional UV-Visible spectroscopy

ε = slope of calibration curve / 10 mm

RESULTS

RESULTS

▶ Determination of ε for dye-benzene system

ε = slope of calibration curve / 10 mm

by using conventional UV-Visible spectroscopy

RESULTS

▶ Determination of ε for dye-ethanol system

ε = slope of calibration curve / 10 mm

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

● Dynamic method - circulated batch method ^BACKGROUND

● Static method ^BACKGROUND

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

● Solubility data of DY54 in SC-CO ₂

● Solubility data of DY54 in SC-CO ₂

ln(xP/P _ref ) = A + c(ρ-ρ _ref )