September 3, 2008

New Analytic Apparatus for experimental

determinations of VLE and Saturation Densities

Luis A. Galicia-Luna* and Octavio Elizalde-Solis

Instituto Politécnico Nacional, ESIQIE, Laboratorio de Termodinámica, Edif. Z-6, 1er piso, UPALM Zacatenco,

07738, Lindavista, México, D. F.; México.

Colloquium to promote experimental work in Thermophysical Properties for Scientific

Research and Industry

In Honor of the 60th Birthday of Prof. Dominique Richon

September 3 - 4, 2009 at Mines ParisTech, Paris, FRANCE

www.termo.esiqie.ipn.mx

Outline

– Motivation

– Background

– Experimental

• Apparatus

• Methodology

– Results

– Conclusions

– Future work

Objectives

– To develop an experimental apparatus by means of an on-

line static-analytic apparatus for measuring VLE and

saturation densities.

– Obtaining experimental data: P, T, xi, yi, liquid, and vapor

densities

MotivationData: VLE and saturation densities of mixtures

EoS

Background

The equilibrium cell comprises two symmetrical titanium holders for

sapphire windows, two cap holding one or three RolsiTM sampler

according to temperature study

Cell 1: 40 MPa, 473 K, 50 cc

Cell 2: 60 Mpa, 673, 100 cc

Background

T/K300 350 400 450 500 550

p/M

Pa

4

6

8

10

12

14

16

(P, T) projection of the critical curve for the

systems carbon dioxide + 2-butanol:

Stevens et al. [28] and This work

2

4

6

8

10

12

14

16

18

20

0.0

0.2

0.4

0.6

0.8

1.0

1.2

320

340

360

380

400

420

P/M

Pa

x (CO 2

)

T/K

Vapor-liquid equilibria near critical point and critical pointsfor the CO

2+1-Pentanol systems at different temperatures

332.08 K

343.69 K

374.93 K

414.23 K

426.86 K

T2

T1PS

Air Bath

Vle cell

Agilent

GC 6890

mixture ISCO

pump

CO

2

New Apparatus

VLE and Saturation Densities on-line static-analytic

Rolsi sampler

Densimeter

recirculating

pump

Methodology

1. Sensors and Detector Calibration

- Temperature probes PT 100, Hart Sci. 1529

- Pressure transducer 30 MPa, Druck

- TCD detector (HPLC)

2. Cell Loading

3. Setting up Experimental Conditions

- Experimental uncertainty

Pressure: 0.04% Temperature: 0.02 K

4. VLE and saturation densities

PRESIÓN, MASA y TEMPERATURA Para calibrar, se cuenta con:

•Balanza Comparadora SARTORIUS MODIFICADA de 1200 grs con precisión de 0.1 mgr. •Sistema de calibración, de temperaturas Modelo F300S (Automatic Systems, patrón secundario +-0.005 °C).

•Sistema de calibración de presión hasta 140 MPa Desgranges & Huot Modelo 5304 (balanza de pesos muertos +-0.005 %).

Studied Systems in This Work– This work

– 2 – Propanol 99.5 mol %, SIGMA M2028

– (CH3)2CHOH, MW = 60.10

– 400 ppm H2O

– CAS: [67-63-0]

– Yaginuma et al, 1997

– 99.9 mol % Wako Pure Chemicals

– Carbon Dioxide

– 99.995 mol %, AIR PRODUCTS-INFRA

– Carbon Dioxide, Nihon Sanso Co. Ltd

– 99.9 mol %

*Densities of Carbon Dioxide + 2-Propanol at 313.15 K and Pressures to 9.8 MPa,

Rikio Yaginuma, Takashi Nakajima, Hiroyuki Tanaka, and Masahiro Kato, J. Chem. Eng. Data 1997, 42, 814-816

Coulometer 831 KF

water content

0

10

20

30

40

50

60

70

80

90

0.0 0.2 0.4 0.6 0.8 1.0

P /

ba

r

x,y (CO2)

CO2 + 1-Propanol

313.60 K - Suzuki

313.15 K - Sang-Do

311.00 K - Chylinski

313.15 K -Yaginuma

315.00 K - Teja

313.40 - Suzuki

313.15 K - Secuianu

313.11 K - Este trabajo

0

20

40

60

80

100

120

140

160

0 200 400 600 800 1000

P /

ba

r

Density (kg/m3)

Saturation densities of CO2 + 1-propanol

313.15 K -Yaguinuma

313.11 K - Este trabajo

363.02 K - Junio 2009

Saturation density for Carbon Dioxide (1) + 2-Propanol (2) at 313 K

(kg/m3)

0 200 400 600 800 1000

P(M

Pa

)

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

313.15 K, buble point

313.15, dew point

312.72 K, This work

Experimental uncertainty: T = 0.02 K

P = 0.01 MPa

x, y < 1 % and r = 0.2 (kg/m3)

Densities of Carbon Dioxide + 2-Propanol at 313.15 K and Pressures to 9.8 MPa,

Rikio Yaginuma, Takashi Nakajima, Hiroyuki Tanaka, and Masahiro Kato, J. Chem. Eng. Data 1997, 42, 814-816

Saturation density for Carbon Dioxide (1) + 2-Propanol (2) at 333.75 K

(kg/m3)

0 200 400 600 800 1000

P(M

Pa)

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

Experimental uncertainty: T = 0.02 K

P = 0.01 MPa

x, y < 1 % and r = 0.2 (kg/m3)

Vapor-Liquid Equilibrium Data for the System Carbon Dioxide(1) + 2-Propanol (2)

x (CO2)

0.0 0.2 0.4 0.6 0.8 1.0

P(M

Pa

)

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

333.70 K *

333.75 K this work

* New Apparatus for the Fast Determination of High-Pressure Vapor-Liquid Equilibria of Mixtures and of

Accurate Critical Pressures

Luis A. Galicia-Luna* , A. Ortega-Rodriguez and D. Richon, J. Chem. Eng. Data 2000, 45, 265-271

Conclusions

• The new experimental apparatus based

on the static-analytic method with on-

line sampling is suitable to measure VLE

and saturation densities.

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