Measurement of Solubility for Disperse Dyestuffs in SC-CO2 ... · Measurement of Solubility for...

Measurement of Solubility forDisperse Dyestuffs in SC-CO2 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

▶ 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● to be surely the simplest

experimental technique● easy to operate● small leakage available

Disadvantage● a complete equilibrium

cannot be achieved● clogging of expansion valve1) dry ice formation2) dye particle precipitation


● Dynamic method - continuous flow method

CO2tank

PT PT

Gas booster

Reservoir

Air bath

Equilibrium cell Cold trap

Massflowmeter

Heatingmantle

TE

ExpansionValve

BACKGROUND

Advantage● a complete equilibrium

state can be achieved● no clogging

Disadvantage● the results are strongly

influenced by a smallleakage from the cell


● Dynamic method - circulated batch methodBACKGROUND

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 methodBACKGROUND

Advantage● can measure the solubility with

in situ UV-Visible spectroscopy

● a complete equilibriumstate can be achieved

● no clogging● flexible path length

- enable to measure over aconcentration range of severalorders of magnitude

● low cost

Disadvantage● need solvent for calibration


Equilibriumcell

ISCO 260D

Syringe pump

Magneticstirrer

Air ovenTE

Optical fiber

Optical fiberPressuregauge

UV-Vis.Spectroscopy

PEEKTube

OpticalFiber

EXPERIMENTAL▶ House made apparatus used in this work


EXPERIMENTAL

▶ in situ Solubility measurement system


EXPERIMENTAL

▶ The UV-Visible spectra of DY114

Wave length (nm)

360 380 400 420 440 460

Abso

rban

ce

0.0

0.1

0.2

0.3

0.4

0.5

Wave length (nm)

360 380 400 420 440 460

Abso

rban

ce

0.0

0.1

0.2

0.3

0.4

0.5

As time elapsing

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

NH2O

OH

O

O

NH2O

OH

Br

OH

NH2

O

O

OH

N

● Dyestuffs used in this work (E-type)


▶ MaterialsEXPERIMENTAL

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 NCH2CH2CN

CH2CH2O

CN

O2N

N N NCH2CH2OCOCH3

CH2CH2OCOCH3

Br

O2N

NO2 NHCOCH3

OCH3

S OO

N NON

H3C

CH3

O

HO

CN

EXPERIMENTAL

● Dyestuffs used in this work (S-type)


Solvent Formula Mw ρ TC(K)

PC(MPa)

Tb(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


▶Beer-Lambert’s Law

A = εl C

A = absorbance of sample, l = path lengthC = concentration of sample, ε = molar extinction coefficient

▶ Calibration SolventHexane : reference solvent- polarity and extinction coefficient are similar to CO2- negligible shifts in the position of absorption maxima


THEORY

▶ UV-Visible spectra of E-type dyestuffsin organic solvents

Wavelength (nm)

400 450 500 550 600 650

Abs

orba

nce

0.0

0.2

0.4

0.6

0.8

1.0

BenzeneAcetoneEthanol

Wavelength (nm)

360 380 400 420 440 460 480 500 520

Abs

orba

nce

0.0

0.5

1.0

1.5

2.0

2.5


Wavelength (nm)

400 450 500 550 600 650 700

Abs

orba

nce

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 56RESULTS

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

Wavelength (nm)

400 450 500 550 600 650 700

Abs

orba

nce

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

Abs

orba

nce

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

Abs

orba

nce

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4


C. I. Disperse Blue 79.1

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Abs

orba

nce

0.0

0.5

1.0

1.5

2.0

2.5

DR 60 y=42.42xDR 360 y=73.03xDB 79.1 y=65.49xDB 56 y=57.86xDY 114 y=84.87xDY 54 y=198.70x

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Abs

orba

nce

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


Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Abs

orba

nce

0.0

0.5

1.0

1.5

2.0


Concentration (g/L)

0.00 0.01 0.02 0.03 0.04

Abs

orba

nce

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



Concentration (g/L)

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

Abs

orba

nce

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=18.14xDB 79.1 y=25.41xDB 56 y=55.53xDY 114 y=25.46xDY 54 y=153.67x

Concentration (g/L)

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

Abs

orba

nce

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=18.14xDB 79.1 y=25.41xDB 56 y=55.53xDY 114 y=25.46xDY 54 y=153.67x

RESULTS

▶ Determination of ε for dye-ethanol system● ε = slope of calibration curve / 10 mm



Dyestuff Solvent ε (mol/cm2) ×106 λmax (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 dyesRESULTS


Dyestuff Solvent ε (mol/cm2) ×106 λmax (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 dyesRESULTS


RESULTS

Density of CO2 (mol/L)

12 14 16 18 20 22

Mol

e fra

ctio

n of

DR

60

0.1

1

10

Sung and Shim (1999)at 313.15 K this work


12 14 16 18 20 22

Mol

e fra

ctio

n of

DR

60

0.1

1

10

Sung and Shim (1999)at 313.15 K this work

▶ Reliability of the experimental technique

Concentration (g/L)

0.001 0.002 0.003 0.004 0.005 0.006 0.007

Abs

orba

nce

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

Abs

orba

nce

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-CO2

Concentraton of benzene (g/L)

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035

Abs

orba

nce

0.0

0.5

1.0

1.5

2.0

2.5

JASCO : 10.00 mm DYEMAX : 6.74mmDYEMAX : 13.49 mm

Concentraton of benzene (g/L)

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035

Abs

orba

nce

0.0

0.5

1.0

1.5

2.0

2.5

JASCO : 10.00 mm DYEMAX : 6.74mmDYEMAX : 13.49 mm

Conventional UV

in situ UV

Slope : molar extinction coeffi.× path length

● Determination of path lengthfor in situ UV-Visible spectroscopy

RESULTS



8 10 12 14 16 18 20

Mol

e fra

ctio

n of

DY

54

10-8

10-7

10-6

10-5

10-4

333.15 K363.15 K393.15 K


8 10 12 14 16 18 20

Mol

e fra

ctio

n of

DY

54

10-8

10-7

10-6

10-5

10-4

333.15 K363.15 K393.15 K

● Solubility data of DY54 in SC-CO2

RESULTS


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-CO2

RESULTS


B

ln(xP/Pref) = A + c(ρ-ρref)

▶ Model equation for correlating the solubility RESULTS


where, x : mole fraction of solubility, P : system pressure, Pref : standard pressure of 1 bar, ρ : solution density, ρref : reference density (700 kg/m3 )

by Bartle et al., 1991

Density of CO2 (g/cm3)

0.0 0.2 0.4 0.6 0.8 1.0

Mol

e fra

ctio

n of

DY5

4

0

2x10-6

4x10-6

6x10-6

8x10-6

10x10-6

333.15 K363.15 K393.15 KCalculated data

Density of CO2 (g/cm3)

0.0 0.2 0.4 0.6 0.8 1.0

Mol

e fra

ctio

n of

DY5

4

0

2x10-6

4x10-6

6x10-6

8x10-6

10x10-6

333.15 K363.15 K393.15 KCalculated data

● Correlation – empirical equationRESULTS


▶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 usingstandard solution of C. I. Disperse Yellow 54.

▶Solubility of the dye C. I. Disperse Yellow 54 in supercritical carbondioxide have been measured in the temperature range from (333.15 to393.15) K and at pressure from (14.81 to 30.04) MPa.

▶Solubility data of the C. I. Disperse Yellow 54 in supercritical carbondioxide were correlated in terms of the density (g/cm3) of carbon dioxideusing an empirical equation of Bartle et al.


CONCLUDING REMARKS

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