Solubility of naphthaline in supercritical binary solvent propane + n-butane mixture

Journal Pre-proof Solubility of Naphthaline in Supercritical Binary Solvent Propane+n-Butane Mixture V.F. Khairutdinov, F.M. Gumerov, Z.I. Zaripov, I. Sh. Khabriev, L. Yu. Yarullin, I.M. Abdulagatov

PII:

S0896-8446(19)30386-9

DOI:

https://doi.org/10.1016/j.supflu.2019.104628

Reference:

SUPFLU 104628

To appear in: Received Date:

29 June 2019

Revised Date:

14 August 2019

Accepted Date:

9 September 2019

Please cite this article as: Khairutdinov VF, Gumerov FM, Zaripov ZI, Khabriev IS, Yarullin LY, Abdulagatov IM, Solubility of Naphthaline in Supercritical Binary Solvent Propane+n-Butane Mixture, The Journal of Supercritical Fluids (2019), doi: https://doi.org/10.1016/j.supflu.2019.104628

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Solubility of Naphthaline in Supercritical Binary Solvent Propane+n-Butane Mixture V.F. Khairutdinova, F.M. Gumerova, Z.I. Zaripova, I.Sh. Khabrieva, L.Yu. Yarullina, I.M. Abdulagatov b,c,* a

Kazan National Research Technological University, Kazan, Russian Federation

b

Department of Physical and Organic Chemistry, Dagestan State University, Makhachkala,

Russian Federation c

Federation Corresponding author. E-mail: [email protected]

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*

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Graphical abstract

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Geothermal Research Institute of the Russian Academy of Sciences, Makhachkala, Russian

Highlights

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 -VLE phase diagram of naphthalene+propane+n-butane ternary mixture near the critical point;  -Solubility of naphthalene in the supercritical binary propane + n-butane solvent mixture;  -Critical curve properties data for binary (propane+n-butane, naphthalene+propane, naphthalene +n-butane) and ternary (naphthalene+propane+n-butane) mixtures

ABSTRACT

Solubility of naphthalene in supercritical solvent mixture (0.527 propane+0.473 n-butane mole

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fraction) was measured at three constant temperatures of 403 K, 423 K, and 443 K over the pressure range from (1.08 to 6.21) MPa. The measurements were made using high-temperature

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and high-pressure optical cell. The combined expanded uncertainty of the temperature, pressure,

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and concentration measurements at 95 % confidence level with a coverage factor of k = 2 is estimated to be 0.15 K, 0.05 %, and 3 %, respectively. For validation of the performance and

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reliability of the new high-pressure VLE apparatus the critical point parameters of pure component of (propane) and binary mixture (0.609 propane+0.391 n-butane mole fraction) for

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which reliable literature data are available have been made. The measured values of VLE properties for ternary mixture of naphthalene + SC (propane/n-butane) were compared with the

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values predicted from GERG model for natural gas main constituents and other natural gas component containing mixtures.

*

Keywords: Critical point; critical curve; naphthalene+propane+n-butane mixture; phase diagram; supercritical solvent, VLE measurements.

1. Introduction Crude oil is one of the most important primary energy sources. However, detailed analysis of the thermodynamic characteristics of the system, involved in the processes of the recovery of waste unused materials (oil sludge), which are forming during crude oil recovery and environmental pollutions, are required [1]. As well-known, supercritical fluids have a large range of potential in the various industrial applications such as environmental, mechanical, chemical,

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biological, and geothermal industries [2-9]. For example, in oil and gas industry supercritical fluids can be applied to enhanced oil recovery (EOR) [10-15]. EOR processes can be used to recover trapped heavy oil left in reservoirs after primary and secondary recovery methods (in

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tertiary oil recovery). Supercritical carbon dioxide has been used as a miscible flooding agent to miscible displacement of hydrocarbons from underground reservoirs, therefore, can help to

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accelerate recovery of heavy hydrocarbons and stimulation fluids from oil and gas reservoirs. Supercritical fluids are needed to make EOR economical in harsh environments. In compare with

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other technologies, supercritical fluid technology has more advantages and has also been identified as a safe, practical and economically attractive. This technique is the most technically

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feasible approach with minimum environmental impacts. The composition (solubility), phase behavior (VLE, PTxy phase diagram) of the main oil sludge components (heavy hydrocarbons)

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under supercritical extraction processes are key inputs to development of the technology

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recovery of oil sludge and minimize their environmental impact [1]. The supercritical fluids and fluid mixtures and heavy (solid) hydrocarbons mixtures exhibit complex phase behaviors during oil sludge recovery processes. A deeper understanding of the phase behavior (VLE, PTxy relation) of multicomponent systems containing supercritical fluids can lead to marked improvements in industrial applications of the supercritical technologies. In our previous publications [16-18] we have successfully used supercritical binary mixture of propane+n-butane for heavy hydrocarbons extractions from dry oil sludge, oil

emulsions, and oil–bearing sand. In order to modeling and optimization of the extraction processes parameters (for increasing of the efficiency of the extraction processes) with supercritical propane+n-butane binary mixture the accurate VLE data for heavy hydrocarbon + SC (propane+n-butane) mixture are required. In the work [18] we have experimentally studied the kinetics of the process of extraction treatment of the water (0.5 to 30 mass %), sulfur (4.5 mass %) and salt (0.02 mg NaCl/cm3) containing oil emulsions with supercritical propane+nbutane mixture at temperatures from (358 to 413) K over the pressure range between (10 and 15) MPa. The high extraction yield of oil product up to 93 mass % was achieved. Also, at the same

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time the deasphalteneization of the oil emulsion sample was performed. The density and kinematic viscosity of the extracted oil product at 298 K was 877.5 kg∙m-3 and 374.1 mm3∙s-1, respectively. Water and sulfur contents were decreased up to 2.3 % and 2.5 %, approximately 13

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and 2 times, respectively. The salts and asphaltenes content were decreased almost two times.

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The efficiency of deasphalthenization processes with supercritical (propane+n-butane) mixture depends on phase behavior of the heavy hydrocarbons with the supercritical mixture agent

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(propane+n-butane) generated during the refining, i.e., details of the phase behavior (VLE, PTxy) of heavy hydrocarbon (crude oil sludge) near the critical point of the solvent mixture should be

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known. To increase of the efficiency of the extraction process, i.e., in order to reach the maximum level of desulfurization, dehydration and deasphalteneization of the extracted oil

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product accurate, the VLE data for the system of water+SC (propane+n-butane), sulfur+ SC(propane+n-butane), and naphthalene (as a representative of the heavy oil component)+

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SC(propane+n-butane) are required. In the present work we have studied VLE properties of the naphthalene in supercritical mixture of (propane+n-butane). The VLE properties (PTxy data) of the light and heavy hydrocarbon mixtures under pressure, and their thermodynamic properties are key input parameters to develop production technologies for oil sludge (oil waste) refining. Naphthalene is an aromatic hydrocarbon which is one of the main components of the petroleum sludge. Since naphthalene is a typical component of petroleum sludge makes a good

choice for a model system to study phase equilibrium in the system of naphthalene+ SC (propane+n-butane). The role of the supercritical solvent in the extraction processes is very important to yield high efficiency. The correct choses of the supercritical solvent is considerable affecting on the efficiency of the extraction process. As well-known carbon dioxide often used as a supercritical agent (supercritical solvent) in various extraction processes [10-16]. However, in case of crude oil sludge refining (treatment with supercritical solvent) supercritical СО2 is not best appropriate supercritical solvent. As a rule in oil industry (petro-chemistry) the light nalkanes, like ethane, propane, n-butane and their mixtures as a main byproduct of natural oil gas

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can be used as a more suitable supercritical solvents. The chemical affinity to oil and relative low critical parameters (especially the critical pressure) are the advantages of these type solvents. Another advantage of the SC mixture solvent is the manipulating of the concentration of the SC

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solvent mixture allows adjust the extraction parameters (critical parameters of the SC solvent

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mixture).

The literature search based on the TRC/NIST archive (TDE search result) and own search

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results is revealed that in total 6 critical lines data sources [19-24] are listed in the NIST Source Data Archive [25] for binary propane+n-butane mixture. All these reported critical temperature

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and pressure data for the binary mixture of (propane+n-butane) from NIST/TRC Data Base [26] were used (see below) to compare and confirmation of the correct operation and reliability of the

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present experimental apparatus for solubility measurements of the ternary mixture of naphthalene + propane+n-butane.

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Previously VLE properties of naphthalene in pure supercritical fluids such as carbon

dioxide, methane, ethane, ethylene, xenon, and their mixtures were studied by several authors [28-43]. For example, Tsekhanskaya et al. [29] reported experimental solubility data of naphthalene in SC СО2 at three temperatures 308.15, 318.15, and 328.15 K for the pressures up to 33.4 MPa. The authors found sensitivity of solubility on the solvent density changes near the critical point. There are very limited reported VLE data for binary mixture components

(naphthalene+propane and naphthalene +n-butane) of the ternary system naphthalene + propane +n-butane under study. However, the binary mixture of propane+n-butane was very well-studied by many authors. In total, 15 VLE data sources [20,22,25,44-55] are listed in the NIST SOURCE Data Archive [26] for binary propane+n-butane mixture. Smith and Wormald [28] studied the solubility of naphthalene in two binary supercritical solvent mixtures (0.4 carbon dioxide+0.6 ethane) and (0.85 carbon dioxide+0.15 propane) over the temperature range from (308 to 338) K and at pressure up to 26 MPa. The uncertainty of the measurements was 3 %. The binary mixture of propane+naphthalene has been studied previously by Tobaly et al. [56] and Peters et al. [57].

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Tobaly et al. [56] used a variable volume cell with two sapphire windows allowing the light beam through the analyzed fluid. The measurements were made at three temperatures 373, 415, and 443 K at pressures up to 9 MPa using high-pressure optical cell. The concentrations have

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been measured by spectroscopic method. The isothermal P-x coexistence curves were

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determined up to the mixture critical points. The cell can be rotated around the optical axis in order to stir the fluid toward equilibrium. The uncertainty of the concentrations is estimated to be

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1%. The experimental observation of the unusual behavior of the bubble curve of the propane + naphthalene mixture at 373 K by Tobaly et al [56] is probably due to existence of a critical

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endpoint around this temperature. The phase-behavior of binary propane-naphthalene mixture, according to study by Rijkers et al. [58], is close to Type-I in the Scott and Van Konynenburg

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[59] classification. However, as was showed by Peters et al. [57], phase-diagram of the propanenaphthalene mixture more likely to Type-II. No experimental VLE data were found in the

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literature for binary naphthalene+n-butane and ternary naphthalene +propane+ n-butane mixtures.

Various VLE models were applied in the literature for binary and ternary systems

containing supercritical light hydrocarbons (propane, ethane, n-butane) and heavy oil compounds (heavy hydrocarbons, naphthalene). The utilization of supercritical fluids (SCF) to separate high boiling point organics needs quantitative phase equilibria (PTxy) data and modeling [70]. The

phase equilibria and modeling for separating high boiling point organics from ionic liquids by supercritical (SC) CO2 and C3H8 have been studied by Liu et al. [70] thereof to take their advantage of low critical temperature. Polishuk et al. [71] developed model for simultaneous prediction of the critical and sub-critical phase behavior in mixtures using two predictive models based on global phase diagram approach and Soave–Redlich–Kwong equations of state. The models were applied to describe experimental VLE data for binary homologous series of nalkanes. A solid–liquid equilibrium model was developed on the basis of copolymer SAFT

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equation of state by Pan and Radosz [72]. This SLE model is demonstrated for hydrocarbon solutions containing totally and partially crystallizable solutes. The model was tested on the solubility data for naphthalene, normal-alkane, and polyethylene, this model is used in a

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sensitivity study to understand the effects of crystallizability, melting temperature, molecular

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weight, and pressure on solid–liquid and liquid–liquid transitions of polyethylene in subcritical and supercritical propane. Prikhod'ko and Vinogradova [73] reported the model for liquid-vapor

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equilibrium in systems including a light oil-gas component and aromatic and polyaromatic hydrocarbons. The hole lattice quasi-chemical group-contribution model was used by Prikhod'ko

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and Vinogradova [73] to simulate the vapor-liquid equilibrium in binary and ternary mixtures with aromatic (benzene, toluene) and polyaromatic (naphthalene, phenanthrene) hydrocarbons

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and light oil-gas components (carbon dioxide, hydrogen sulfide, nitrogen, methane, ethane, propane). Eighteen binary and two ternary systems are examined. New group parameters for

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these systems were estimated. Kunz et al. [68] and Kunz and Wagner [74] developed wide –range equation of state

(GERG model) to accurate calculate of the thermodynamic and VLE properties of natural gases and other mixtures of main natural gas components for industrial applications. The GERG- 2008 [74] multi-parameter fundamental equation of state (Helmholtz free energy as a function of T,,x) is considered as the reference model for the prediction of natural gas mixture properties.

The GERG fundamental equation of state for natural gas was adopted as an ISO Standard (ISO 20765-2) reference equation for natural gas applications [74]. GERG-2008 was successfully used by various authors to accurate predict of the thermodynamic and VLE properties of main components (binary, ternary, and multicomponent mixtures consisting up to 21 components) of the natural gas (see, for example Refs. [75-77]). GERG-2008 precisely describes the gas and liquid phase as well as the super-critical region and the VLE. In the present work we used (see below) the GERG model [68,74] for calculate VLE properties of the binary and ternary mixtures consisting propane, n-butane, and naphthalene.

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Also, there is great scientific interest in experimental study of the VLE and other thermodynamic properties of mixtures near the critical point one of the mixture’s components [60-63]. It is well-know that thermodynamic properties of the mixtures when solvent (pure or

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mixture) in the near-critical condition exhibits unusual behavior [60-63]. For example,

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singularity of the solute partial molar properties ( V 2  , H 2 , C P2 ) in the immediate vicinity of the solvent's critical point are of great theoretical interest, especially when solvent is the mixture.

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Phase behavior of the complex multicomponent hydrocarbon mixtures are considerable affecting by the interaction between pure component molecules with different size, shape, and physical-

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chemical nature. Therefore, measured phase behavior data (PTxy) are great important for modeling of the VLE properties multicomponent mixtures with SC binary mixture solvent.

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In the present paper we have reported VLE data of ternary mixture of naphthalene +propane+ n-butane, i.e., we studied VLE properties of naphthalene in the supercritical binary

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solvent (propane + n-butane). The solubilities of solid naphthalene in the binary supercritical solvent mixture of (0.527 propane+0.473n-butane mole fraction) over the temperature range from (403 to 443) K at pressures up to 6.21 MPa have been measured. Additionally we have measured the critical parameters of pure propane and (0.609 propane+0.391 n-butane mole fraction) mixture in order to confirm the correct operation and accuracy of the experimental apparatus.

2. Experimental 2.1. Materials Ready to use mixed propane+butane solvent with fixed composition of 0.527 mole fraction of propane and 0.473 mole fraction of n-butane was provided by ООО «UralOrgSynthesis» Company (Production # ГОСТУ 20448-90). A mixture of 0.527 propane + 0.473 n-butane mole fraction was selected for practical reasons. Ready to use mixture with a composition of 0.527 propane + 0.473 n-butane mole fraction is commercially available for domestic consumption. The mixture is an affordable, cheap and commercially available solvent. Based on these

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considerations, a commercial ready to use propane-butane mixture with a composition of 0.527 propane + 0.473 n-butane mole fraction was selected in this work. The propane sample (CAS # 74-98-6, C3H8, product number ТУ 2632-181-44493179-2014, M =44.096 g·mol-1) used in this

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work was supplied by chemical reagents production company OOO MONITORING (Moscow,

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Russia). The purity of propane was 99.8 mass %. The naphthalene sample (CAS # Naphthalene 91-20-3, product number ТУ 6-09-40-3245-90 and Reference # 16106-82) used in this work

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supplied by ООО “REACHIM” Company. N-butane sample with purity of 99.75 mass % was provided by OOO “MONITORING” (Moscow). The purity of Naphthalene was 99.0 mass %.

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No further purification was attempted. Table 1 lists the commercial sources, purities, water content, and analysis method of the samples used in the present work.

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2.2. Apparatus and procedures

Experimental technique and procedure used for vapor-liquid equilibrium (VLE, PTxy)

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properties measurement were described in our previous publication Khairutdinov et al. [78]. VLE measurements were performed using high-pressure optical cell. A schematic diagram of the apparatus is presented in Fig. 1. The main part of the VLE apparatus is a high-pressure optical cell (see Fig. 2). The apparatus consists of units for creating, regulating, and measuring of the pressure, sampling, equilibrium cell, and unit for temperature controlling, vacuuming and rotating units, and some analytical part. The stainless steel-flanged sapphire cell operates up to

50 MPa and the maximum operating temperature is limited by 450.15 К. The body and cover of the cell were made from stainless still (12Х18Н10Т). Between the cover and body of the optical cell the sapphire windows were installed. The working volume of the optical cell was 117 cm3. The cell temperature was measured using a chromel -alumel thermocouples. The thermocouples were calibrated with PRT-10. The combined expanded uncertainty of the temperature measurements (at 95 % confidence level, a coverage factor of k = 2) is 0.15 K (standard uncertainty is 0.075 K). The cell pressure was measured with a dead weight pressure gauge. The combined expanded uncertainty of the pressure measurements was 0.05 % (standard uncertainty

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is 0.025 %).

In order to perform static experiment with the present instrument one third of the optical cell was filled with the propane+n-butane mixture. The entire optical cell has been evacuated

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using a vacuum pump. Then the optical cell was heated up to desired experimental temperature

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using electrical heater and propane + n-butane mixture was pumped (transferred) from the cylinder -1 (Fig. 1) to the cell-4 using high-pressure pump-3 (Thar Technology, Supercritical 24)

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until required pressure will reach. Copper jacket-5 was used for smooth controlling of the temperature and uniformly heating of the cell. The cell was completely isolated using thermal

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insulation material-6. Phase equilibria study is requiring to identify the equilibrium condition before composition analyses is performing. How long is taking before equilibrium condition is

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reaching depends on method of stirring and operation condition. In order to reach the equilibrium condition in the two-phase system the sample under study was vigorously stirred for 30 minute

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using rotating system. The cell was rotated to stir the mixture toward equilibrium. As a rule the equilibrium condition is defining as the condition at which all measuring properties remain constant or their fluctuations are within the experimental uncertainty. In the present study the equilibrium condition reaches was identified as the condition when pressure and temperature in the optical cell and the concentration of the extracts remain constant within their experimental uncertainties. After reaching the equilibrium condition in the optical cell the sample stirring was

stopped. Then optical cell installed in vertical position and waited for 40 minute. The sampler-9 with volume of 4.1 cm3 was used for sample extraction. Before the sampling the sampler-9 was weighed using electronic balance Vibra with uncertainty of 0.001 g. During the sampling the sampler-9 was connected with valve. The extracted sample in the sampler-9 is the mixture of the SC (propane+n-butane) as a solvent and the component under study (naphthalene as a solute). The measurement procedure was carried out as follows. After a quick sampling from any phase (liquid or gas) at given T and P experimental condition, the phase equilibrium is shifting (concentration of the phases is changing) and the pressure in the system also changes. For this

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reason, the next sampling from other phase, at the same thermodynamic condition (at the same temperature and pressure) is impossible. Therefore, next sampling we are repeating again after thorough stirring of the sample and reaching equilibrium condition at other T and P conditions

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(not at the same T and P as it was for first sampling). For convenience and expedite of the

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process, we first analyze one phase, and then another one, separately at different T and P conditions. Thus, in this method it is impossible simultaneously (at the same T and P conditions)

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to measure of the concentration of both liquid and gas phase (at equilibrium conditions). This is technically simplifying the method of VLE measurements.

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Separating of the extracted sample into gas (propane+n-butane mixture) and solid or liquid (component under study, naphthalene) phases was implemented by cooling the sampler-9

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to 293 K. At this temperature, the dissolved in propane+n-butane mixture naphthalene is precipitating. We experimentally found that the procedure of separation at temperature of 293 K

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is most optimal. At temperatures below 353.41 K naphthalene is crystallizing and propane+nbutane mixture transforms into gas phase. As a result naphthalene is completely separating from the solvent (propane+n-butane mixture). We experimentally found that separation at temperature below 273 K causes some condensation on the sampler’s walls, which is introducing an additional uncertainty in the concentration measurements. For this reason, cooling the sampler-9 to very low temperatures (below 273 K) is not applicable. In order to avoid of possible removal

of the naphthalene with the propane+n-butane mixture during gas phase release from the sampler-9, the particle trap was mounted to the outlet valve of the sampler -9 (see Fig. 1). The mass of the propane+n-butane mixture in the sampler-9 was determined as difference between the mass of the full sampler and remained mass after gas phase released. The mass of the naphthalene was calculated as a difference between the mass of remained after gas phase (propane+n-butane) release and empty sampler-9. The solubility of the naphthalene in binary propane+n-butane mixture solvent in this

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method was calculated as m naph M

y 

m C 3 C 4 M

(1)

naph

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M

,

is the mass of the dissolved naphthalene in the supercritical propane+n-butane

mixture;

M

naph

is the molar mass of naphthalene;

mixture;

M

C 3 C 4

m C 3 C 4

is the mass of the propane+n-butane

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m naph



C 3 C 4

m naph

is the molar mass of the propane+n-butane mixture. The combined expanded

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where

naph

uncertainty of the concentration measurements was 3 %.

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2.3. Test measurements

In order to validate of the performance and the reliability of the new apparatus for phase

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equilibrium (VLE) property measurements, check the accuracy of the method, correct operation of the experimental apparatus, and confirm the reliability of VLE data measured by the present

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technique for ternary mixture naphthalene+propane+n-butane, the VLE measurements were made on one of the pure component (propane, well-studied pure component) and propane+nbutane binary mixture for which reliable VLE data are available in the NIST/TRC Data Base [26]. The critical parameters of pure propane are well-established and were reported by many authors (see also our publications [64-66]). Accurate reference thermodynamic properties data for propane were reported by Lemmon and McLinden [67]. Propane has been recommended [67] as a reference fluid for calibration of the experimental apparatus. NIST recommended values of

the

critical

parameters

 C  220 . 48 kg  m

-3

for

propane

are

T C  369 . 89 K

, PC

 4 . 2512 MPa

,

and

[27]. The present measured critical parameters of pure propane sample

were compared with the NIST reference data (see below). The binary naphthalene+propane mixture was also used for test measurement of the VLE properties with the present high-temperature and high-pressure optical cell. The results of the present test VLE measurements for naphthalene +propane mixture are given in Table 2 together with reported data [56] for two selected isotherms of (373 and 415) K.

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3. Results and discussions Described above high-temperature and high-pressure VLE apparatus was used to measure phase-equilibrium properties of naphthalene in supercritical binary mixture of (0.527

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propane+0.473 n-butane mole fraction). As was mentioned above (see sec. 2.3) the same apparatus was used to measure critical property data for pure propane, (0.609 propane+0.391 n-

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butane mole fraction) mixture, and VLE properties of binary mixture of naphthalene+propane. A critical point of pure propane was determined by visual observation of the critical opalescence

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and the simultaneous disappearance and reappearance of the meniscus, i.e., of the liquid−vapor interface from the middle of the view cell. Heating the two- phase (L-G) propane at constant

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volume can lead to various different sequences of phase transitions, depending on the fill coefficient (ratio of the volume of the sample to the volume of the measuring cell at ambient

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temperature) or the average fill density (ratio of the mass of sample to the volume of the cell at

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ambient temperature):

1. At highest average densities (  S

 C

), the liquid part of the initial two- phase (L-V) system

expands on heating at constant volume and fills the entire vessel (measuring cell), while the vapor phase disappears, i.e., disappearance of the meniscus (L−V interface) on the top of the cell is observing. A transition from two phase (L-V) to one phase (L), (L-V L) occurs. The temperature ( T S ) at which the vapor−liquid interface disappearing at the initial filled density

(  S ) is the phase transition temperature ( T S ) at the liquid-gas coexistence curve (saturated liquid density,  S =  S' , see Fig. 3, right photos); 2. At the lowest average densities (  S

 C

), heating increases the vapor density resulting in

disappearance of the liquid phase (vapor part of the two-phase L-V system expands and fills the entire vessel), i.e., disappearance of the meniscus (vapor−liquid interface) on the bottom of the cell is observing. A transition takes place from two-phase (L-V) to one-phase (V), (L-VV) occurs. The temperature ( T S ) at which the vapor−liquid interface disappearing at the initial filled

vapor density,  S =  S" , see Fig. 3, left photos);

  C ),  S   S   C . '

"

In this case the vapor−liquid

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3. At some intermediate average density (  S

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density (  S ) is the phase transition temperature at the liquid-gas coexistence curve (saturated

interface became cloudy, thick, and then occupied the entire cell when the temperature of the

identical,

S  S  C . '

"

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system approaches to the critical value where both saturated liquid and vapor densities became The cell became orange (see Fig. 3, middle), which is characterizing the

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critical opalescence. After reaching supercritical phase, the temperature of the cell was gradually decreased (cooling run). At a little above the critical temperature and pressure, the fluid color

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changed from colorless to yellow, then from yellow to yellow−red, and finally became dark orange. Then the vapor−liquid interface reappeared in the middle of the view cell. The critical

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temperature and pressure were recorded at the point where complete darkness was observed in

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the cell. For each measurement, the heating and cooling processes were repeated a few times, and the average of the recorded temperatures and pressures were taken as the critical values of the propane. The same phenomena were observed for different near-critical isochores. Therefore, this technique is not accurate for the critical density determination. Although this technique is widely using to determine the parameters of the coexistence curve ( T S

,  S ,  S ), '

"

the visual

observation of the meniscus disappearance lacks objectivity. For example, approaching the critical point, where the difference between the liquid (  S' ) and vapor (  S" ) phase density

vanishes (  S'

  S ), "

and the visual determination of the moment at which the phase transition

occurs becomes ever less reliable. In addition, the observations are impeded by the development of critical opalescence (see Fig. 3). Therefore, the region of temperatures near the critical point (within 1 K of critical

TC )

becomes virtually unattainable for investigation. The present values of the

temperature,

PC  4 . 25  0 . 02 MPa

pressure, , and

and

density

 C  227 . 27  5 kg  m

for -3

propane

are

T C  371 . 15  1 . 0 K

,

, respectively. These values of the critical

temperature, pressure, and density are agreed with the reference data [27] within 1.26 K, 0.03 %,

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and 3 %, respectively. The relative large discrepancy in the critical temperature value is the result of purity effect.

All these cases (see above) have been found in the present experiments (see Fig. 3). The

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case 3 have been encountered in our experiment for the critical state observation. In Fig. 3 the P-

 diagram of pure propane calculated from reference equation of state (NIST/REFPROP [27]) is

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depicted for various sub-, near-, and supercritical isotherms including one- (liquid and vapor)

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and two-phase (liquid + vapor) regions. This figure demonstrate a comparison of the liquid+vapor interface (meniscus) disappearing and the intensity of the critical opalescence using

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photos of the observed meniscus at the temperature where meniscus is disappearing for various densities. For three different densities of 250.00, 227.27, and 200.00 kg∙m-3 the location of the meniscus at different temperatures shown in Fig. 3. At density of 250.00 kg∙m-3, which is higher

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than the reference critical density of 220.48 kg∙m-3 [27] by 13.6 %, the meniscus disappearance T S  369 . 81 K

(reference value is

Jo

was observed in the top of the cell at temperature of T S  369 . 70 K

S '

[27]). Therefore, we considered this value of density as a saturated liquid density

(right side of the L+V coexistence curve). At density of 200.00 kg∙m-3 , which is lower than

the reference critical density [27] by about 10.2 %, the meniscus disappearance was observed in the bottom of the cell at temperature of

T S  369 . 89 K

( reference value is

therefore, we considered this value of density as a saturated vapor density

T S  369 . 81 K

S

"

[27]),

(left side of the

L+V coexistence curve). In the case of 227.27 kg∙m-3, we observed disappearance of the meniscus at the center of the cell. In this case we found the critical opalescence with high intensity. Thus, we considered the density of 227.27 kg∙m-3 as one of the near-critical density of propane. The difference between the present and reference critical density [27] is within 3.08 % (typical uncertainty in the critical density measurements is within 5 %, including singular diameter behavior). This is acceptable agreement because the critical density of the fluids is difficult to accurate measure due to high compressibility ( K T

 

1

 

/  P  T   at T  T C

)

ro of

of the system near the critical point. The small changes in the temperature (even within it experimental uncertainty) and pressure near the critical point is causing large changes in the density. In order to accurate determination of the critical parameters in this method, the set of

-p

various near-critical isochores should be studied. However, it is very hard to visually identify the difference between the phase behaviors of the system for various near-critical isochores within

re

the temperature range of 1-2 K around the critical point. Thus, the critical value of the density should be determined based on the measurements for series near-critical isochores. The same

lP

procedure was used to measure of the critical parameters and phase equilibrium (VLE) properties of propane+n-butane mixture. The measured values of the critical parameters for the selected

na

mixture of (0.609 propane+0.391 n-butane mole fraction) are

T C  394 . 25 K

and

PC  4 . 3 MPa

(see Fig. 4). Figure 4 illustrates the critical opalescence with high intensity for the binary (0.609

ur

propane+0.391 n-butane mole fraction) mixture. The present measured critical property data for

Jo

(0.609 propane+0.391 n-butane mole fraction) were compared with reported data [20,22,25]. All these reported data together with the present values of  C  227 . 27 kg  m

-3

T C  394 . 25 K

,

PC  4 . 3 MPa

, and

for binary mixture (0.609 propane+0.391 n-butane mole fraction) are

depicted in Figs. 5 to 8 in the various projections of

TC  x

,

PC  x

, C

 x

, and

T C  PC

.

As Figs. 5 to 8 demonstrate, the present critical properties data for (0.609 propane+0.391 n-butane mole fraction) mixture is in good agreement with reported data, deviations are within 1.7 K and 0.68 %, for the critical temperature and pressure, respectively. The measured value of

the critical density of the (0.609 propane+0.391 n-butane mole fraction) mixture deviates from the reported data [20,22] (see Fig. 7) within 2.2 %. However, the present value for the critical density of the mixture is in good agreement (deviation within 0.7 %) with the value reported by reported by Nysewander et al. [25]. The maximum deviation within 2.2 % is still acceptable because, how it was mentioned above, the typical uncertainty in the critical density measurement 1 is within 5 % due to gravitational effect ( K T ∞) coexistence    /singular   and  P T   at T  T C curve diameter.

The measured VLE data for binary naphthalene +propane mixture are given in Table 2 and

ro of

depicted in the Fig. 9 (in P-x projection) for two selected temperatures of (373 and 415) K together with reported data [56]. The quantitative comparison of the present PTxy measurements with the data reported by other authors is difficult due to the temperature, pressure, and

-p

concentration differences between the various data sets. Therefore, a data interpolation procedure was employed for the data reported in [56] for the composition dependence of pressure for each

re

isotherms. Table 2 includes the comparison between the present VLE data and the values derived from [56] by using the data interpolation procedure. The uncertainty of the interpolation

lP

procedure is negligible small because the interpolation range is very small and linear, except for gas phase where rapid changes of pressure with small changes of propane concentration is

na

observing near the end point (around x=1 mole fraction of propane). As can be note from Table 2 (last column) the deviations is for liquid phase is good (within 0.23 to 1.3 % for the liquid

ur

phase pressure), while for gas phase the deviation is large (up to 12 %) due to the large uncertainty in interpolation procedure.

Jo

Figure 10 demonstrate the comparison of the present measured P-T data for naphthalene+

propane with the reported by Tobaly and Marteau [56] and the values predicted from GREG model [68]. As Fig. 10 shows the agreement between the measured and predicted data is acceptable. However, the good agreement between the present and reported data [56] for phaseequilibrium properties of naphthalene + propane mixture confirms the reliability and high accuracy of the present VLE measurements for ternary mixture of naphthalene + SC (propane+n-

butane, see below) and gives us an assurance that our instrument is operation correctly. As was mentioned above, there are no reported VLE and critical properties data for naphthalene + nbutane mixture. In Fig. 11 the predicted from GERG model [68] VLE and the critical curve data in the P-T projection for various isopleths are depicted together with the vapor-pressure data for pure components calculated from REFPROP [27]. The measured VLE properties of the mixture of naphthalene+SC (0.527 propane+0.473 nbutane mole fraction) are given in Table 3 and depicted in Fig. 12 in x-P projection for three experimental temperatures of 403, 423, and 443 K. The measurements were made for three

ro of

selected isotherms of 403, 423, and 443 K at pressures up to 6.21 MPa. GERG model [68] is widely using (see above Introduction) for calculation of the VLE properties of binary and ternary mixtures of the natural gas main constituents and other natural gas component containing

-p

mixtures. We have used GERG model [68] to predict the VLE properties of the present binary

re

propane+naphthalene and ternary naphthalene+propane+n-butane mixtures. Figure 13 shows comparison between the present measured VLE (P-T projection for various isopleths) data and

lP

the values predicted from GERG model [68]. As one can see, the prediction is acceptable enough (the mixing parameters of the model have been estimated, not fitted to the direct measured

na

experimental data). Especially the good agreement was observed for low naphthalene containing mixtures. This is understandable because naphthalene is not in the list of 21 natural gas

ur

components, which were used GERG model to fit experimental data. Figure 14 shows the critical curves behavior for binary constitutes of ternary naphthalene

Jo

+propane+n-butane mixture together with vapor-pressure curves for pure components calculated from reference equation of state (REFPROP [27]). The present experimental VLE results for ternary mixture of naphthalene+SC (0.527 propane+0.473n-butane) confirmed Type-I behavior according Williams’s classification [69]. The present results clearly demonstrate that the Type of the phase behavior of the complex system of solute (extracting component) +SC solvent can be

changed by selecting of the SC mixture solvent. This is very important for supercritical fluid technology applications. 4. Conclusions The solubility of naphthalene in supercritical solvent (0.527 propane+0.473 n-butane mole fractions) was studied at three constant temperatures (403, 423, and 443) K over the pressure range from (1.1 to 6.21) MPa. In order to check and confirm of the accuracy and the reliability of the method and correct operation of the new high-pressure VLE apparatus the critical point parameters of pure component of (propane) and binary mixture (0.609 propane+0.391 n-butane

mixture (0.609 propane+0.391 n-butane mole fraction) are

ro of

mole fraction) have been measured. The measured values of the critical parameters for the binary T C  394 . 25 K

and

PC  4 . 3 MPa

. We

experimentally found that using binary mixture of (0.527 propane+0.473 n-butane mole fraction)

-p

as a supercritical solvent, instead of SC carbon dioxide, changes the type of phase equilibria. We

re

also experimentally observed that the ternary mixture of naphthalene+ SC (0.527 propane+0.473 n-butane mole fraction) confirmed Type-I behavior according Williams’s classification [69]. The

lP

physical-chemical nature and properties of the supercritical agent (solvent) are strongly affecting on the type of phase behavior of system “extracting component (solute) +SC agent (solvent)”.

na

This is very important for extraction process efficiency enhancements because for the systems with continues critical curve the extraction with SC solvents is more efficiency than extraction

ur

with liquid solvents. Acknowledgment

Jo

This work was supported by the Russian Fund of Basic Research, Project number 18-19-00478. References

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ro of

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-p

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re

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re

the extraction of hydrocarbons from oil sludge with supercritical propane-butane mixture,

ur

Table 1

na

lP

J. Physics: Conference Ser. (2019) accepted.

Description of the samples of propane, naphthalene, n-butane and the propane +n-butane mixture

Jo

studied in this work Chemical name

CASRN 74-98-6

Water content (mass %) Not found

Purity (mass %) ≥99.80 (NMR)

Propane

n-butane

106-97-8

<0.05

>99.75 (NMR)

Naphthalene 0.527 mole fraction (propane)a +0.483mole fraction (n-butane)a

91-20-3 -

≤ 0.005

≥ 99.00 (GC) -

Not found

Source OOO MONITORING (Moscow) OOO MONITORING (Moscow) ООО “REACHIM” ООО «UralOrgSynthesis»

a

Uncertainty in concentration of the propane+n-butane mixture determination is 0.99 %

(propane) and 0.77 % (n-butane) Table 2 Measured values of composition of naphthalene (1) and propane (2) in the gas (y) and liquid (x) phases at various fixed temperatures together with the reported data [56] (interpolated data) Mole fraction of propane (this work)

Pressure P, MPa (this work)

Pressure P, MPa (Ref. [56])

Deviations (%)

6.02

6.75

12

5.28 6.73

1.3 0.9

0.25

ro of

0.980

-p

T=415 K Gas-phase Liquid-phase 0.479 0.727

5.35 6.67 T=373 K Liquid-phase

0.740

3.88

Standard uncertainties u are:

u T

 =7.5 mK;

(level of confidence=95 %).

u r  P  =0.025

%;

u r  x  =1.5

%; and

lP

Table 3

3.89

u r  y  =1.5

%

re

a

Measured values of composition of naphthalene in the gas (y) and liquid (x) phases for

Mole fraction of naphthalene

ur

Pressure P, MPa

na

naphthalene (1) + SC propane/n-butane (2) mixture at various fixed temperaturesa

0.017 0.016 0.008

1.08 2.06 2.65 3.31 3.68 3.73

0.844 0.642 0.528 0.397 0.326 0.312

Jo

1.81 2.84 4.30

Mole fraction of propane

T=403 K Gas-phase 0.580 0.581 0.585 Liquid-phase 0.092 0.211 0.278 0.356 0.398 0.406

Mole fraction of n-butane

0.403 0.403 0.407 0.064 0.147 0.194 0.247 0.276 0.282

0.656 0.567 0.419 0.364 0.314 0.249 0.196 0.102 0.059

1.20 3.18 4.31 6.11 6.21

0.035 0.009 0.019 0.056 0.088 0.909 0.793 0.613 0.492 0.378 0.326 0.362 0.251

Jo

ur

1.10 2.16 3.35 4.27 5.07 5.33 5.21 5.68

a

0.141 0.178 0.238 0.261 0.281 0.308 0.330 0.368 0.386

ro of

2.30 2.82 3.66 3.98 4.41 4.70 4.88 5.24 5.34

0.394 0.399 0.401 0.405 0.404 0.398

-p

0.039 0.028 0.023 0.012 0.014 0.030

0.292 0.329 0.386

re

1.12 1.68 1.93 3.08 4.05 5.32

0.419 0.474 0.555 T=423 K Gas-phase 0.567 0.573 0.576 0.583 0.582 0.572 Liquid-phase 0.203 0.255 0.343 0.375 0.405 0.443 0.474 0.530 0.555 T=443 K Gas-phase 0.569 0.585 0.579 0.557 0.538 Liquid-phase 0.054 0.122 0.228 0.300 0.367 0.398 0.376 0.442

0.396 0.406 0.402 0.387 0.374

lP

0.289 0.197 0.059

na

3.87 4.14 4.30

Standard uncertainties u are:

(level of confidence=95 %).

u T

 =7.5 mK;

u r  P  =0.025

0.037 0.085 0.159 0.208 0.255 0.276 0.262 0.307 %;

u r  x  =1.5

%; and

u r  y  =1.5

%

ro of

Fig. 1. Schematic diagram of the VLE property measurement apparatus with high-pressure

-p

optical cell. 1–cylinder; 2–filter-dryer; 3–high-pressure pump; 4– high-pressure optical cell; 5 –

re

copper jacket; 6 – thermal insulation; 7 – valve for extracting sample from upper (gas) phase; 8 – valve for extracting sample from lower (liquid) phase; 9– sampler; 10 – thermostated bath; 11–

Jo

ur

na

lP

valve.

Fig. 2. High-pressure optical cell with copper jacket. 1-body; 2-coper jacket; 3-sapphir window; 4-sealing ring (rubber with polyimide cover); 5- cell cap. All numbers in mm.

ro of -p

re

Fig. 3. P- phase diagram of pure propane calculated from REFPROP [27]. Observation of the liquid-vapor interface (meniscus) location and the critical opalescence at various temperatures

na

lP

for different filling densities of propane.

4.5

3.5

ur

CP (C3H8)

P / MPa

Jo

x=

2 0.

x=

CP (C4H10)

9 60 0.

x=

8 0.

2.5

1.5

0.5 340

355

370

385

400

415

430

T/ K C3+C4 -P-T Phase Exp N

Fig. 4. P-T phase diagram of binary propane + n-butane mixture for various concentrations. Dashed-dotted curve is the critical line calculated from the correlations by Soo et al. [23]. Solid curves are predicted from GERG model [68]. Dashed lines are vapor-pressure curves of pure components calculated from REFPROP [27]; ▲, the present work for (0.609 propane+0.391 nbutane mole fraction).

427 CP (C 4 H10 )

ro of

417

397

-p

TC / K

407

re

387

TC  x

0.4

CP (C 3 H8 )

0.6

x / mole fraction of propane

0.8

1.0 C3+C4 -Tc-x

projection of the critical lines for binary propane+n-butane mixture reported by

ur

Fig. 5.

0.2

na

367 0.0

lP

377

various authors from the literature together with values calculated from correlation equation by

Jo

Soo et al. [23]. ▲- Juntarachat et al. [24]; -Barber [20]; -Nysewander et al. [25]; ○-Soo et al. [23]; ●-Kay [22]; □-this work for (0.609 propane+0.391 n-butane mole fraction).

4.5

4.4 CP (C 3H 8)

4.3

P C / MPa

4.2

4.1

ro of

4.0

3.9

3.8

3.7 0.0

0.2

0.4

-p

CP (C 4H 10)

0.6

PC  x

1.0 C3+C4 -Pc-x

projection of the critical lines for binary propane+n-butane mixture reported by

lP

Fig. 6.

re

x / mole fraction of propane

0.8

various authors from the literature together with values calculated from correlation equation by

na

Soo et al. [23]. ▲- Juntarachat et al. [24]; -Barber [20]; -Nysewander et al. [25]; ○-Soo et al.

□-this work for (0.609 propane+0.391 n-butane mole fraction).

Jo

ur

[23]; ●-Kay [22];

CP (C4 H10 )

228

224

ro of

 C / kg·m-3

226

222

CP (C3 H8 )

0.2

0.4

0.6

-p

220 0.0

x / mole fraction of propane

 x

1.0

C3+C4 -Rc-x

projection of the critical lines for binary propane+n-butane mixture reported by

re

Fig. 7.  C

0.8

lP

various authors from the literature. ●- Nysewander et al. [25]; -Barber [20]; ○-Kay [22];

□-this

work for (0.609 propane+0.391 n-butane mole fraction) (near-critical density). Dashed curve is

Jo

ur

na

smoothed values.

6

5

4.4 4.2 CP (C 3H 8)

P / MPa

4

4.0 CP (C 4H 10)

3.8

3 3.6 360

380

400

420

ro of

2

1

290

330

370

-p

0 250

410

450

PC  T C

C3+C4 -Pc-Tc Critical Line

projection of the binary critical curve of the propane+n-butane mixture reported

lP

Fig. 8.

re

T/K

by various authors from the literature together with vapor-pressure curve for the pure

na

components. Solid curves are vapor-pressure of the pure components calculated from reference equation of states (REFPROP [27]). Dashed curves are calculated from the correlations by Soo et

ur

al. [23]. ▲- Juntarachat et al. [24]; -Barber [20]; -Nysewander et al. [25]; ○-Soo et al. [23];

Jo

□-this work for (0.609 propane+0.391 n-butane mole fraction).

8

7

T=415.0 K 6

P / MPa

5

T=373.0 K 4

2

1

0.2

0.4

0.6

-p

0 0.0

ro of

3

0.8

1.0

x,y / mole fraction of propane

re

C3+C4 -P-x 413

Fig. 9. PTxy phase diagram of binary naphthalene+propane mixture reported by Tobaly and

lP

Marteau [56] together with the present data for two selected temperatures. ●,▲-this work; ,■,

na

(gas phase) and ,□ (liquid phase) Tobaly and Marteau [56]. Dashed curves are guide for the

Jo

ur

eye.

10 9 8 7

P / MPa

1 6 3 5 CP (C 3H 8)

4

2

CP (C 10H 8)

2 1

290

340

390

440

490

590

640

690

740

C3+Naph -P-T Phase

re

T/ K

540

-p

0 240

ro of

3

Fig. 10. PTxy phase diagram of binary naphthalene +propane mixture predicted from GERG

lP

model [68] together with the data reported by Tobaly and Marteau [56] and the present results for two selected temperatures. ●-(x=0.4787 mole fraction of propane) this work; ■- (x=0.7404

na

mole fraction of propane) this work; -(x=0.4787 mole fraction of propane) Tobaly and Marteau

ur

[56];○- (x=0.7404 mole fraction of propane) Tobaly and Marteau [56]; -critical point data from VLE measurements by Tobaly and Marteau [56]; 1- x=0.7404 mole fraction of propane; 2-

Jo

x=0.4787 mole fraction of propane; 3- is the critical curve predicted from GERG model [68]. Solid curves are calculated from GERG model (REFPROP [27]). Dashed lines are vaporpressure values for pure components (propane and naphthalene) calculated from reference equations REFPROP [27].

7

6

2

5

P / MPa

3

4

4

CP(C 4H 10) 5

3

ro of

1

2

6

310

380

450

520

re

0 240

-p

1

CP(C 10H 8)

590

660

730

lP

T/ K

C3+C10-P -T P has e C3+C10-P -T P has e

Fig. 11. P-T-x phase diagram of binary naphthalene +n-butane mixture predicted from GERG

na

model [68]. Solid curves are calculated from GERG model (REFPROP [27]). Dashed lines are vapor-pressure values for pure components (n-butane and naphthalene) calculated from reference

ur

equations REFPROP [27]. Dashed-dotted curve is the critical curve predicted from GERG model

Jo

[68]; 1-0.95 mole fraction of n-butane; 2-0.9 mole fraction of n-butane; 3-0.8 mole fraction of nbutane; 4-0.5 mole fraction of n-butane; 5-0.2 mole fraction of n-butane; and 6- 0.1 mole fraction of n-butane.

T=403.0 K

0.8

T=423.0 K

T=443.0 K

0.6

0.4

ro of

x / mole fraction of naphthalene

1.0

0.0 1

2

3

-p

0.2

4

5

6

7

P / MPa

P

) of naphthalene in the coexistence liquid and gas phases as a

for the mixture naphthalene + SC (propane+n-butane) at three constant

lP

function of pressure

y

re

Fig. 12. Concentrations ( x and

C3+C4 -P-T all

temperatures. ▲- 403.0 K (liquid); -403.0 K (gas); ■-423.0 K (liquid); □-423.0 K (gas); ●-

Jo

ur

na

443.0 K (liquid);○-443.0 K (gas). Solid curves are interpolated values (smoothed data).

9 8 7 3

P / MPa

6 5 2 4

1

2 1

340

390

440

490 T/ K

540

-p

290

590

640

690

C3+C4+Naph -P -T P has eComp

re

0 240

ro of

3

Fig. 13. P-T diagram of the naphthalene +SC (propane +n-butane) mixture predicted from

lP

GERG model [68] together with the present measurements. Solid lines are calculated from GERG model (REFPROP [27]). Symbols are the present measurements (some data points are

na

interpolated values). 1- isopleth (0.059 naphthalene+0.555 propane+0.386 n-butane); 2- isopleth (0.2 naphthalene+0.3 propane+0.5 n-butane); and 3- isopleth (0.364 naphthalene+0.375

Jo

ur

propane+0.261 n-butane).

10 9 8

P / MPa

7 6 5 CP (C 3 H 8 )

4

CP (C 4H 10)

2

ro of

3 CP (C 10H 8 )

1

330

410

490

570

-p

0 250

650

730

T/K

PC  T C

re

Fig. 14. Critical curve behavior of binary mixtures in

C3+C4 -Naph-Pc-Tc Critical Line

projection. Solid lines are vapor-

lP

pressure values calculated from REFPROP [27].  - from VLE data reported by Tobaly et al.

Jo

ur

na

[56]; Other symbols are the same as in Fig. 4.