efecte de cosolventa, ferestre de miscibilitate si … · 2015-10-08 · (module crimix). in order...

EFECTE DE COSOLVENTA, EFECTE DE COSOLVENTA, FERESTRE DE MISCIBILITATE FERESTRE DE MISCIBILITATE SI DISCONTINUITATI ALE SI DISCONTINUITATI ALE SUPRAFETEI CRITICE IN SUPRAFETEI CRITICE IN ECHILIBRE DE FAZE LA ECHILIBRE DE FAZE LA PRESIUNI INALTEPRESIUNI INALTE

ID_1088 ID_1088 20072007--20102010

Copyright, 2009 © D.Geana

D.Geana Catedra

Chimie

Fizica

Aplicata

Universitatea

Politehnica

Bucharest

Echipa proiectuluiEchipa proiectului

•• Prof.dr.ing. Dan Petre Geana Prof.dr.ing. Dan Petre Geana –– directordirector

•• Prof.dr.ing. Viorel FeroiuProf.dr.ing. Viorel Feroiu

•• Sef lucrari dr.ing. Catinca SecuianuSef lucrari dr.ing. Catinca Secuianu

•• Sef lucrari dr.ing. Adrian CrisciuSef lucrari dr.ing. Adrian Crisciu

•• Doctorand ing. Mirela IonitaDoctorand ing. Mirela Ionita

•• Doctorand ing. Alina ConstantinDoctorand ing. Alina Constantin

Indicator performanta (publicatie Indicator performanta (publicatie ISI) 2009ISI) 2009

Indicator performanta (publicatie ISI) Indicator performanta (publicatie ISI) 20092009

Indicator performanta (publicatie BID) Indicator performanta (publicatie BID) 20092009

Indicator performanta (publicatie ISI) Indicator performanta (publicatie ISI) 20092009

Indicator performanta (publicatie ISI) Indicator performanta (publicatie ISI) 2009, Energy2009, Energy & Fuels, & Fuels, 23 (6), pp 23 (6), pp 30683068––30773077. Colaborare internationala . Colaborare internationala Syracuse University,USASyracuse University,USA

European Symp. on Applied European Symp. on Applied Thermodynamics (ESAT) 2009Thermodynamics (ESAT) 2009

RICCCE 2009 (Abstract)RICCCE 2009 (Abstract)MISCIBILITY WINDOWS AND HOLES IN THE

CRITICAL SURFACE IN TERNARY SYSTEM

CARBON DIOXIDE+1-HEPTANOL+N-PENTADECANE

Dan Geană

"Politehnica" University of Bucharest, Faculty of Applied Chemistry and Material Science,

Bucharest, Romania

During recent years some special phase equilibrium phenomena, such as cosolvency and

related effects, have been considered. Carbon dioxide binaries exhibiting gas–gas like fluid

phase behavior can be combined to give a ternary system, which might show large

cosolvency effects and, as a consequence, two-phase liquid–gas holes in the three-phase

liquid–liquid–gas surface and/or one-phase miscibility windows surrounded by

heterogeneous states.

Experimental measurements are available at high pressure for the ternary system CO2 +

1-heptanol + n-pentadecane. The ternary system shows two-phase liquid–gas holes in the

critical surface and/or one-phase miscibility windows.

The modeling of miscibility windows and holes in the critical surface was made with a

database and calculation program, developed in our laboratory, for phase equilibrium

(PHEQ) data management and applications, with equations of state. The software package

PHEQ was extended for calculations of critical lines in binary and ternary mixtures

(module CRIMIX). In order to model the occurrence of a hole in the critical surface and

miscibility windows, the equation of state Soave-Redlich-Kwong (SRK) with two

parameters conventional mixing rule (2PCMR) was used. A quasy-binary representation of

the ternary systems was used, calculating the critical lines and the three-phase lines at

constant reduced mass fractions of n-pentadecane. The calculated miscibility windows and

holes in the critical surface are in satisfactory agreement with the available experimental

data.

RICCCE 2009 (Abstract)RICCCE 2009 (Abstract)

PHASE EQUILIBRIA IN THE TERNARY SYSTEM

CARBON DIOXIDE + 1-HEXANOL + PENTADECANE

Catinca Secuianu, Viorel Feroiu, and Dan Geană "Politehnica" University of Bucharest, Faculty of Applied Chemistry and Material Science, Bucharest,

Romania

Investigation of fluid multiphase behaviour is of considerable interest to experimental

and theoretical applications. Ternary mixtures can be used as model systems for some

important applications such as supercritical fluid extraction (SFE) and supercritical fluid

chromatography (SFC). The model mixtures of interest consist of one supercritical

solvent plus two low-volatile substances or one low-volatile substance plus mixtures of

two supercritical solvents or of a supercritical solvent with a moderator1-4.

Previously our research group have investigated the phase equilibria of the carbon

dioxide + 1-heptanol + pentadecane mixture5.

In this paper we present new VLE data measured with a high-pressure phase

equilibrium apparatus of the static-analytical type, using a sampling-analyzing process

for determining the composition of the different coexisting phases of the carbon dioxide

+ 1-hexanol + n-pentadecane ternary system.

The new data were obtained using a sampling-analyzing system, constituted of two

ROLSITM capillary samplers6 connected altogether on-line with a gas chromatograph.

The experimental data obtained in our measurements and available literature data were

modelled using cubic equations of state, coupled with different mixing rules.

References

1. H. Pöhler, A.L. Scheidgen, G.M. Schneider - Fluid Phase Equilib., 1996, 115, 165–177.

2. A.L. Scheidgen, G.M. Schneider - J. Chem. Thermodyn., 2000, 32, 1183–1201. 3. K. Gauter, C.J. Peters, A.L. Scheidgen, G.M. Schneider - Fluid Phase Equilib.,

2000, 171,127–149. 4. A.L. Scheidgen, G.M. Schneider - Fluid Phase Equilib., 2002, 194–197, 1009–

1028. 5. C. Secuianu, V. Feroiu, d. Geană - Fluid Phase Equilib., 2007, 261, 337-342. 6. P. Guilbot, A. Valtz, H.Legendre, D. Richon - Analusis 2000, 28, 426−431.

Instalatie pentru masuratori de Instalatie pentru masuratori de echilibre de faze la presiuni inalte,cu echilibre de faze la presiuni inalte,cu celula vizuala si analiza GC oncelula vizuala si analiza GC on--lineline

Detaliu:celula vizuala cu sistem Detaliu:celula vizuala cu sistem Rolsi de analiza GC onRolsi de analiza GC on--line a line a compozitiei fazelorcompozitiei fazelor

DiscontinuitateDiscontinuitate (hole) in (hole) in suprafatasuprafata criticacritica a a sistemuluisistemului CO2+hexanol+pentadecanCO2+hexanol+pentadecan

250 300 350 400

100

200

300

400

500

0.0

0.2

0.40.60.81.0

Hexanol Pentadecan W=0.33 W=0.5 W=0.67 W=0.79

P / b

ar

WCre

d

T /K

DiscontinuitateDiscontinuitate (hole) in (hole) in suprafatasuprafata criticacritica a a sistemuluisistemului CO2+hexanol+pentadecanCO2+hexanol+pentadecan

250 300 350 400

100

200

300

400

500

0.2

0.4

0.6

0.8

P / b

ar

WCre

d

T /K

SistemSistem CO2+Hexanol+C15;W=0.67 CO2+Hexanol+C15;W=0.67 SRK SRK EoSEoS vs. experimentvs. experiment

0

50

100

150

200

250

300

350

400

450

500

200 250 300 350 400 450 500 550 600 650 700

Temperature/K

Pres

sure

/bar

Discontinuitate LG in three-phase LLG line

SistemSistem CO2+Hexanol+C15;W=0.67 CO2+Hexanol+C15;W=0.67 SRK SRK EoSEoS vs. vs. experiment (detaliu)experiment (detaliu)

0

50

100

150

200

250

240 260 280 300 320 340 360 380 400

Temperature/K

Pres

sure

/bar

critical lineLLG lineCO2 P-T lineExp

ProiectiaProiectia PP--WcWc a a suprafeteisuprafetei criticecritice (LG hole)(LG hole)

30

40

50

60

70

80

90

0 0.2 0.4 0.6 0.8 1WC

red

P/ba

rLCEPUCEPDCEP

2 Faze (LG)Tip III

Tip III

Tip IVSuprafata critica

ProiectiaProiectia TT--WcWc a a suprafeteisuprafetei criticecritice (LG hole)(LG hole)

275

280

285

290

295

300

305

310

315

320

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

WCred

T/K

LCEPUCEPDCEP

Tip III

Tip III

Tip IV

2 Faze (LG)

Suprafata critica

SistemSistem pentadecan(1) + hexanol(2) + pentadecan(1) + hexanol(2) + CO2(3) la T=316 K CO2(3) la T=316 K sisi P=80 barP=80 bar SRK SRK EoSEoS vs. experimentvs. experiment

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

X(hexanol)

X(p

enta

deca

n)

ExpEoS

SistemSistem pentadecan(1) + hexanol(2) pentadecan(1) + hexanol(2) + CO2(3) la T=316 K + CO2(3) la T=316 K sisi P=105 barP=105 bar SRK SRK EoSEoS vs. experimentvs. experiment

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

X(hexanol)

X(p

enta

deca

n)

EoSExp

Cosolventa

RESURSA UMANARESURSA UMANA IMPLICAREA TINERILOR CERCETATORIIMPLICAREA TINERILOR CERCETATORI

•• 2 profesori2 profesori

•• 2 tineri sefi lucrari doctori cu experienta2 tineri sefi lucrari doctori cu experienta

•• 2 doctoranzi (1 fara frecventa, 1 cu 2 doctoranzi (1 fara frecventa, 1 cu frecventa fara bursa)frecventa fara bursa)

ConcluziiConcluzii--Criteriile de performanta 2009: 4 publicatii in Criteriile de performanta 2009: 4 publicatii in reviste ISI; 1 publicatie in revista recenzata in reviste ISI; 1 publicatie in revista recenzata in baze de date, 1 comunicare in volumul conferintei baze de date, 1 comunicare in volumul conferintei indexate ISI; 2 comunicari la conferinta indexate ISI; 2 comunicari la conferinta internationala.internationala.

-- Rezultate originale 2009: Evidentierea Rezultate originale 2009: Evidentierea experimentala a discontinuitatilor (holes) in experimentala a discontinuitatilor (holes) in suprafata critica; Modelarea suprafetei critice cu suprafata critica; Modelarea suprafetei critice cu ecuatii de stare; Determinari de conode in sistem ecuatii de stare; Determinari de conode in sistem ternar,efect de cosolventa; Modelarea efectului de ternar,efect de cosolventa; Modelarea efectului de cosolventa cu ecuatii de starecosolventa cu ecuatii de stare

-- 2 tineri cercetatori (sefi lucrari) doctori cu 2 tineri cercetatori (sefi lucrari) doctori cu experienta;2 tineri doctoranzi implicati in cercetariexperienta;2 tineri doctoranzi implicati in cercetari