Phase Equilibria of Clathrate Hydrates of Ethyne + Propane - Journal

Article pubs.acs.org/jced

Phase Equilibria of Clathrate Hydrates of Ethyne + Propane Kaniki Tumba,†,‡ Saeedeh Babaee,†,⊥ Paramespri Naidoo,† Amir H. Mohammadi,†,§,* and Deresh Ramjugernath*,† †

Thermodynamics Research Unit, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V, Avenue, Durban, 4041, South Africa ‡ Department of Chemical Engineering, Mangosuthu University of Technology, Umlazi, Durban 4031, South Africa § Institut de Recherche en Génie Chimique et Pétrolier (IRGCP), Paris Cedex, France ⊥ Department of Chemical Engineering, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran ABSTRACT: In this communication, experimental dissociation data for mixed ethyne (acetylene) and propane hydrates are reported in the temperature and pressure ranges of (274.6 to 280.8) K and (0.250 to 1.280) MPa, respectively. Moreover, three-phase equilibrium conditions inside the hydrate stability region with compositional analysis are reported in the temperature and pressure ranges of (275.6 to 278.9) K and (0.392 to 0.894) MPa. Experimental ethyne mole fractions at equilibrium on a water free basis ranged between 0.053 and 0.523. The van der Waals and Platteeuw solid solution theory, together with the Valderama-Patel-Teja equation of state and nondensity dependent mixing rule were combined to model phase equilibria of clathrate hydrates of ethyne + propane. The proposed modeling approach was found to be reliable as good agreement was observed between the experimental and predicted data for this system.

1. INTRODUCTION

The design and optimization of these processes require inter alia the knowledge of the phase behavior under hydrate forming conditions. Bearing this in mind, experimental phase equilibrium data for mixed hydrates of propane and ethyne (acetylene) are reported in the present study. Propane, ethyne, and their mixtures are interesting gases from an industrial point of view. Propane is essentially used as a fuel,20 as well as a refrigerant,21 whereas ethyne is involved in chemicals’ manufacturing and metalworking.22 Propane− ethyne mixtures are encountered in some natural gas processes and petroleum refining streams.23,24 This pair of chemicals is part of the products in some novel and emerging ethyne manufacturing processes such as catalytic oxidation of propane,25 propane pyrolysis,26 partial oxidation of natural gas,27 direct catalytic conversion of natural gas by microwave plasma,28 etc. Equilibrium data for simple propane hydrates have been extensively studied in the literature.29−40 It was observed that most of the reported data were in good agreement with each other. Conversely, for the ethyne + water system, only two data sets41,42 have been published in the open literature. The deviation between data from the two sources was discussed in a previous work.42 A survey of the literature revealed the total absence of phase equilibrium data for mixed hydrates of these

Clathrate hydrates, or gas hydrates, are nonstoichiometric compounds that form when appropriately sized small molecules (guests, typically gases and small volatile liquids) are entrapped in cage-like structures made of hydrogen-bonded water molecules (hosts).1,2 The hydrate structure is stabilized by van der Waals forces between the guest and the host molecules.1 Favorable conditions for clathrate hydrate formation are generally those of high pressures and low temperatures. Exceptionally, some gases form hydrates at pressure−temperature combinations that are close to atmospheric conditions. Examples include refrigerants3,4 such as 1,1,1,2-tetrafluoroethane (C2H2F4 or HFC-134a or R-134a), 1,1-difluoroethane (C2H4F2 or HFC-152a or R-152a), difluoromethane (CH2F2 or HFC-32 or R-32), and 1,1-dichloro-1fluoroethane (C2H3Cl2F or HCFC-141b or R-141b). During oil or natural gas exploitation and transportation, gas hydrates are undesirable as they cause plugging of pipelines as well as blocking of other process facilities.5 Nonetheless, some potential positive applications of gas hydrates have been identified, increasing the interest for these compounds by many researchers. Numerous scientific investigations are currently underway to better understand and evaluate gas hydrate-based processes in the areas of gas storage and transportation,6−9 water treatment and desalination,10 carbon dioxide capture and sequestration,11,12 separation,13 refrigeration,14,15 natural gas recovery from natural hydrate formations,16−18 fire extinction,19 etc. © 2014 American Chemical Society

Received: June 28, 2014 Accepted: August 4, 2014 Published: August 18, 2014 2914

dx.doi.org/10.1021/je500598j | J. Chem. Eng. Data 2014, 59, 2914−2919

Journal of Chemical & Engineering Data

Article

60 cm3, which can withstand pressures up to 20 MPa. The cell was immersed in a temperature-controlled ethylene glycol/ water bath. A detailed description of the experimental setup shown in Figure 1, along with the calibration procedure for the temperature probes and the pressure transducer, has been provided in previous publications.47,48 The combined expanded uncertainties were estimated as ± 0.007 MPa and ± 0.1 K for pressure and temperature measurements, respectively. The equilibrium cell was connected to a Shimadzu 2010 gas chromatograph (GC) equipped with a thermal conductivity detector (TCD) with sampling via a ROLSI43 autosampler. A POROPAK Q packed column was used to separate the two hydrocarbons contained in the sampled vapor phase. Table 2

two gases. This, in addition to the importance of the two gases and their mixtures, motivated the present study. Dissociation data for mixed propane and ethyne hydrates were measured by the isochoric pressure search method using three different feed compositions, 0.093, 0.172, and 0.882 mole fraction of ethyne in the gaseous feed. The temperature and pressure ranges were (274.6 to 280.8) K and (0.250 to 1.280) MPa, respectively. On the other hand, HLV (hydrate−liquid− vapor) equilibrium conditions inside the hydrate forming region were experimentally determined in terms of equilibrium temperature, pressure, and vapor phase composition. The latter set of measurements was undertaken in the temperature and pressure ranges of (275.6 to 278.9) K and (0.392 to 0.894) MPa, respectively. Experimental ethyne mole fractions at equilibrium on a water-free basis ranged between 0.053 and 0.523. These compositions were determined by gas chromatography from samples withdrawn from the equilibrium cell using a ROLSI43 autosampler. It is worth noting that prior to the newly reported measurements, some pure propane hydrate dissociation data were generated to check the reliability of the experimental setup as well as that of the experimental procedure as used in the present study. Finally, a modeling approach has been suggested for the system under investigation. It involves the solid solution theory developed by van der Waals and Platteeuw,44 the ValderramaPatel-Teja equation of state45 (VPT EoS), and nondensitydependent (NDD) mixing rules.46 The performance of the proposed model was examined on the basis of the deviation between its predictions and the reported experimental data.

Table 2. GC Specification and Set-up, Including the Detector Temperature (Td), the Carrier Gas Flow Rate (Ucg), the Injection Port Temperature (Tinj), the Column Temperature (Tcol), the Column Inner (i.d.) and Outer (o.d.) Diameters, and the Column Lengh (L) data acquisition software detector type Td/K carrier gas Ucg/m3·s−1 Tinj/K column type i.d./m o.d./m L/m Tcol/K

2. EXPERIMENTAL SECTION 2.1. Materials. The purities and suppliers of propane and ethyne which were used in this study are provided in Table 1. Table 1. Purities and Suppliers of the Materialsa

a

gas

origin

mole fraction purity

ethyne propane

Afrox Afrox

0.999 0.995

GC solution TCD 523.15 helium 1.0·10−6 523.15 packed column POROPAK Q 2.2·10−3 3.2·10−3 2.5 323.15

lists the conditions under which samples of the vapor phase were analyzed by means of the GC. The TCD was calibrated for propane and ethyne using helium as carrier gas. In both cases, a straight line was used to fit the obtained calibration data. The combined expanded uncertainty in determining concentrations was estimated to be ± 0.005 mole fractions. 2.3. Experimental Procedure. Details of the experimental procedure used to generate all the reported data are detailed in previous publications.47,48 They are summarized below.

Ultrapure Millipore Q water was used in all experiments.

2.2. Apparatus. The main part of the experimental setup is a stainless steel cylindrical cell with an approximate volume of

Figure 1. Schematic diagram of the apparatus used in this study: (1) equilibrium cell; (2) ROLSI sampler; (3) motor and magnet; (4) ethanol bath; (5) pressure transducer; (6) immersion temperature controller; (7) refrigeration unit; (8) acrylic tank; (9) vacuum pump; (10) gas cylinder; (11) ROLSI inlet line, from the GC; (12) ROLSI outlet line, to the GC injector; (13) drain line; (14) temperature probe in the upper flange; (15) temperature probe in the lower flange; (16) liquid and gas feeding line; (V1 to V4) valves. 2915



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2.3.1. Simple Hydrate Dissociation Conditions. Hydrate dissociation conditions were experimentally determined by means of the isochoric pressure search method.49−53 Care was taken to first wash the equilibrium cell with deionized water. Before the materials of interest were loaded, the cell was dried, immersed in the temperature-controlled ethylene glycol bath, and finally evacuated down to 0.8 kPa for approximately 2 h. A volume of water corresponding to approximately 40% of the total volume of the cell was added. Subsequently, propane was loaded into the vessel at the desired starting pressure. The cell contents were agitated to allow proper mixing of the components. After the stability of pressure and temperature was observed (far enough from the hydrate formation region), the temperature was slowly decreased to form the hydrate. This was followed by stepwise heating, during which the hydrate was progressively dissociated. After each temperature increment, it took 4 to 5 h for the system to reach thermodynamic equilibrium. It must be noted that in order to ensure accuracy, a stepwise increase of 0.1 K was adopted in the vicinity of the dissociation point. The point corresponding to the sharp change of the slope on the pressure−temperature data plot was considered as the dissociation point.49−53 2.3.2. Mixed Hydrates Equilibrium Data. The composition of the mixture was prepared in situ, that is, inside the equilibrium cell by successively loading the gases from their respective cylinders. The gas feed composition was determined by means of GC analysis. To ensure reproducibility, five samples were withdrawn for GC analysis. Sampling of the gas feed in the absence of water was done for GC analysis via a ROLSI43 sampler. To estimate the number of moles of the gaseous components of the feed, the volume of the cell was measured by the so-called “liquid filling” method. A well-known amount of water was added to the cell using a calibrated injector. The isochoric pressure search method, as described in section 2.3.1 was then followed. After hydrate formation the system was gradually heated and at each step the temperature was maintained. At equilibrium, sampling was repeated every 30 min until successive vapor phase compositions agreed with each other within 0.001 mole fraction. At each temperature step, the average concentration was recorded as the composition of the vapor phase at the corresponding equilibrium pressure. Measurements at a higher pressure could be undertaken after adding water to the cell until reaching the desired starting pressure. The dissociation point was identified in the same manner as was the simple hydrates.

Figure 2. Experimental propane hydrate dissociation data and comparison with selected literature data: ■, this work; ◇, from ref 38; ⧫, from ref 37; −, from ref 36; ●, from ref 35; □, from ref 32; ▲, from ref 31; ○, from ref 30; +, from ref 29.

Table 3. Experimental (Texp) and Predicted (Tcal) Dissociation Temperatures for Simple and Mixed Ethyne and Propane Hydrates at Different Pressures (P); z′o,eth Represents Ethyne Mole Fraction in the Feed, on a WaterFree Basisa zo,eth ′ 0

0.093

0.172

0.882

1d

3. RESULTS AND DISCUSSION Because of the wide availability of literature data for phase equilibria for the water + propane system, only three dissociation data points for pure propane hydrate were measured. This was done to check the reliability of both the experimental setup and the experimental procedure used in this study. As shown in Figure 2, there is good agreement between the newly measured and the previously reported data. Dissociation data for simple ethyne hydrate were reported in our previous work.42 New experimental dissociation data for mixed propane and ethyne are reported in Table 3 as well as Figure 3 and compared with model predictions. It was observed that propane hydrate formation was inhibited by the addition of ethyne, whereas in the presence of propane, the hydrate stability region for ethyne was shifted to lower pressures and higher temperatures. This was expected as propane hydrates are stable at lower pressures than those of ethyne.

P/MPa

Texp/K

Tcal/K

0.250 0.336 0.540 0.489 0.554 0.587 0.646 0.940 0.956 0.971 1.020 0.858 0.979 1.065 1.280 0.614 0.780 0.986 1.224 1.554 1.968 2.223 2.467

274.6 276.4 278.1 277.7 278.3 278.6 279.2 280.2 280.4 280.5 280.8 277.4 278.6 279.3 280.5 273.2 275.5 277.6 279.5 281.7 283.6 284.5 285.5

274.6 276.1 278.3 277.6 278.2 278.5 278.9 280.5 280.5 280.6 280.8 277.3 278.5 279.2 280.7 272.9 275.2 277.4 279.4 281.6 283.7 284.8 285.7

b

ARD% 0.0 0.1 0.1 0.0 0.0 0.0 0.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.1 0.1 0.1 0.0 0.0 0.0 0.1 0.0

c

AD/K 0.0 0.3 0.2 0.1 0.1 0.1 0.3 0.3 0.1 0.1 0 0.1 0.1 0.1 0.2 0.3 0.3 0.2 0.1 0.1 0.1 0.3 0.2

Combined expanded uncertainties Uc are Uc(Texp) = ± 0.1 K, Uc(P) ′ ) = 0.005. The reported uncertainties are = ± 0.007 MPa, Uc( zo,eth based on combined standard uncertainties multiplied by a coverage factor k = 2, providing a level of confidence of approximately 95 %. b ARD % = (|Texp− Tcal|/Texp)·100, absolute relative deviation. cAD = | Texp − Tcal|, absolute deviation. dData reported in ref 42 (2013). a

The modeling approach used in this study has been detailed previously.52 It relies on the equality of fugacity for each component in all three coexisting phases. The Valderrama modification of the Patel and Teja equation of state45 and the nondensity-dependent mixing rules46 allowed calculation of the 2916



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Table 6. Values for Acentric Factors (ω) as Well as Critical Temperatures (TC), Pressures (PC), and Compressibility Factors (ZC) Used in This Study component

TC/K

PC/MPa

ω

ZC

data source

acetylene propane water

308.30 369.83 647.29

6.138 4.248 22.089

0.1920 0.2760 0.3438

0.2680 0.1532 0.2290

56 56 56

Table 7. Binary Interaction Parameters (kij, lij0 and lij1) Associated with the VPT EoS45 and NDD Mixing Rules46 for Water−Propane and Water−Ethyne

fugacity of water and that of hydrate formers (ethyne and propane) in the fluid phases. The solid solution theory of van der Waals and Platteeuw44 was used to model the gas hydrate phase. Phase transition parameters53,54 between the empty hydrate lattice and liquid water or ice are given in Table 4.

Δh0w −1

cm ·mol 4.6 5.0

−1

J·mol

−4620.5 −5201

Δμ0w J·mol−1

structure

data source

1297 883

I II

53 54

a

Molar enthalpy difference between the empty hydrate lattice and liquid water. bReference chemical potential difference for water between the empty hydrate lattice. cVolume difference between the empty hydrate lattice and liquid water.

a

σ/Åb

(ε/k)/Kc

data source

ethyne propane

0.445 0.680

3.230 3.303

171.94 200.94

42 55

data source

water (i)−ethyne (j) water (i)−propane (j)

0.2260 0.6512

0.9373 1.81373

0.0019 0.0038

42 57

zo,water

zo,eth

T/K

P/MPa

yeth

ypr

0.937 0.937 0.983 0.983 0.983 0.888 0.983 0.910 0.981 0.983 0.983

0.006 0.006 0.002 0.002 0.002 0.061 0.002 0.022 0.003 0.002 0.002

275.6 276.1 276.6 276.9 277.4 277.6 278.1 278.2 278.3 278.6 278.9

0.392 0.390 0.470 0.477 0.508 0.894 0.578 0.675 0.681 0.613 0.663

0.078 0.079 0.065 0.065 0.061 0.523 0.055 0.232 0.173 0.054 0.053

0.922 0.921 0.935 0.935 0.939 0.477 0.945 0.768 0.827 0.946 0.947

zo,eth and zo,water refer to ethyne and the water mole fraction in the feed, respectively. yeth and ypr represent the experimental vapor phase mole fraction on a water-free basis for ethyne and propane, respectively. Combined expanded uncertainties Uc are Uc(Texp) = ± 0.1 K, Uc(P) = ± 0.007 MPa, Uc(z0,eth) = Uc(z0,water) = Uc(yeth) = ± 0.005. The reported uncertainties are based on combined standard uncertainties multiplied by a coverage factor k = 2, providing a level of confidence of approximately 95 %.

Table 5. Kihara Potential Parameters Used in This Study α/Åa

lij1

a

Structure II was assumed for modeling the mixture of ethyne + propane hydrates. Kihara potential function parameters42,55 which are used in this study are reported in Table 5. These

component

lij0

Table 8. HLV Equilibrium Temperatures (T), Pressures (P), and Vapor Phase Compositions Obtained in the Hydrate Stability Region with Various Feed Compositionsa

Table 4. Phase Transition Parameters (Δh0w,a Δμ0w b and Δν0w c) between the Empty Hydrate Lattice and Liquid Water or Ice Δν0w

kij

clearly illustrated in Figure 3, there is good agreement between the model predictions and the reported measurements. Phase equilibrium data with compositional analysis under hydrate forming conditions as measured in the present study are presented in Table 8. These data are reported in terms of

Figure 3. Experimental data and prediction of hydrate dissociation conditions for the ethyne + propane + water system at various ethyne mole fractions in the gas/vapor feed, Symbols represent experimental data: ◇, 0.093 ethyne mole fraction; −, 0.172 ethyne mole fraction; ●, 0.882 ethyne; ▲, pure propane; ■, pure ethyne.

3

system

experimental pressures, temperatures, and vapor phase compositions inside the hydrate stability region for the ethyne + propane + water system.

Molecular core radius. bCollision diameter. cCharacteristic energy.

4. CONCLUSIONS New experimental dissociation data were measured for mixed ethyne and propane hydrates in the temperature and pressure ranges of (274.6 to 280.8) K and (0.250 to 1.280) MPa, respectively. Furthermore, HLV phase equilibria inside the hydrate stability region are reported in terms of pressure, temperature, and vapor phase composition in the temperature and pressure ranges of (275.6 to 278.9) K and (0.392 to 0.894) MPa. The reported ethyne mole fractions at equilibrium on a water-free basis ranged between 0.053 and 0.523. The modeling approach proposed in this study for the ethyne + propane + water system under hydrate forming conditions was found to be

parameters were required for water fugacity calculations in the hydrate phase. In relation to fluid phase fugacity calculations, the acentric factors (ω) and critical properties56 for water and the hydrate formers are provided in Table 6. The binary interaction parameters42,57 used in the NDD mixing rules46 and VPT EoS45 for ethyne−water and propane−water systems have been shown in Table 7. In this communication, dissociation conditions for the ethyne + propane + water system under HLV equilibria are predicted, whereas the compositional model is not yet developed. As 2917



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reliable. It consisted of the solid solution theory44 owed to van der Waals and Platteeuw, the VPT equation of state,45 and the NDD mixing rules.46 The findings of the present study give enough information to examine the phase behavior of the investigated system under various conditions. The reported results can be used to analyze hydrate-based processes such as gas storage, gas transport, or separation in which the ethyne− propane pair would be involved.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected], [email protected]. *E-mail: [email protected]. Funding

This work is based upon research supported by the South African Research Chairs Initiative of the Department of Science and Technology and National Research Foundation. The authors would also like to thank the National Research Foundation of South Africa (NRF) for financial assistance. Notes

The authors declare no competing financial interest.

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Phase Equilibria of Clathrate Hydrates of Ethyne + Propane - Journal

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