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Solubility of Ethylene in Methyl Propionate

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Solubility of Ethylene in Methyl Propionate Solubility of ethylene in methyl propionate Citation for published version (APA): Shariati - Sarabi, A., Florusse, L. J., & Peters, C. J. (2015). Solubility of ethylene in methyl propionate. Fluid Phase Equilibria, 387, 143-145. https://doi.org/10.1016/j.fluid.2014.12.019 DOI: 10.1016/j.fluid.2014.12.019 Document status and date: Published: 01/01/2015 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 24. Sep. 2021 Fluid Phase Equilibria 387 (2015) 143–145 Contents lists available at ScienceDirect Fluid Phase Equilibria journal homepage: www.elsevier.com/locate/fluid Solubility of ethylene in methyl propionate a b c,d, Alireza Shariati , Louw J. Florusse , Cor J. Peters * a School of Chemical and Petroleum Engineering, Shiraz University, Molla Sadra Street, Shiraz 71345, Iran b DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands c Chemical Engineering Department, The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates d Separation Technology Group, School of Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands A R T I C L E I N F O A B S T R A C T Article history: In this work, the solubility of ethylene in methyl propionate was measured within a temperature range of Received 22 August 2014 283.5–464.8 K and pressures up to 10.7 MPa. Experiments were carried out using the Cailletet apparatus, Received in revised form 5 December 2014 which uses a synthetic method for the experiments. The critical points of several isopleths have also been Accepted 8 December 2014 determined experimentally for this system. The Peng–Robinson equation of state was used to predict the Available online 10 December 2014 solubility of ethylene in methyl propionate. The absolute average deviation for all of the calculated points was 5.8%. Keywords: ã 2014 Elsevier B.V. All rights reserved. Phase behavior Vapor–liquid equilibria High pressure Equation of state Ethene 1. Introduction As can be seen from this reaction, there is no waste nor by-product; therefore, the produced methyl propionate only needs Fatty acids are very important material in the chemical industry to be separated from the unreacted reactants, commonly by because they can be used as raw material for producing various distillation. Therefore, methyl propionate can be considered as a compounds. Methyl esters are alternatives to fatty acids that can be chemical whose production is green for the environment. used for the production of several derivatives. However, using Ethylene, carbon monoxide, and methanol are very common methyl esters can have some advantages in comparison to fatty reactants for producing hundreds of chemicals, using different acids. Generally, esters are easier to fractionate than the fatty acids combinations of these reactants. due to their lower boiling points. They are also usually more stable In order to have a better understanding of the phase behavior of and less corrosive than the corresponding fatty acids [1]. the different constituents of the methyl propionate reaction, in this Methyl propionate is one of the methyl esters, with a number of work, we have studied the solubility of ethylene in methyl applications in the industries, for example, as a reactant for propionate. The temperature range of our experiments was within producing methyl methacrylate; as raw material for producing 283.5–464.8 K and pressures were measured up to 10.7 MPa. The paints; as one of the ingredients of perfumes; and as a flavor Peng–Robinson equation of state (PR EOS) [3] was then used to additive in the food industry. predict the solubility of ethylene in methyl propionate. Methyl propionate can be produced by the esterification of propionic acid, but industrially, it is prepared by the reaction 2. Experimental of ethylene with carbon monoxide and methanol in the presence of nickel carbonyl in the temperature range of 160–200 C and Table 1 indicates the suppliers and the purities of ethylene and pressures up to 50 bar [2]: methyl propionate used in this study. These chemicals were used without further purification. The experiments were carried out in a 2C2H4 + CO + CH3OH ! CH3CH2COOCH3 Cailletet apparatus. The main part of this apparatus is a capillary glass tube, called the Cailletet tube, with one closed end. This tube works as the equilibrium cell. For the VLE experiments of the binary system of ethylene + methyl propionate, a fixed amount of methyl propionate was injected into the equilibrium cell and then * Corresponding author at: Chemical Engineering Department, The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates. Tel.: +971 2 607 5492 a known volume of ethylene at known temperature and pressure E-mail address: [email protected] (C.J. Peters). was added to the Cailletet tube. In this way, a binary sample with http://dx.doi.org/10.1016/j.fluid.2014.12.019 0378-3812/ã 2014 Elsevier B.V. All rights reserved. 144 A. Shariati et al. / Fluid Phase Equilibria 387 (2015) 143–145 Table 1 evaluate the predictive capability of the PR EOS for determining the The suppliers and the purities of the chemicals. phase behavior of the binary system of ethylene + methyl propio- Chemicals Supplier Purity nate, the calculations were performed without the use of any binary interaction parameters. For determining the solubility of Ethylene Linde 99.9 mol% Methyl propionate Fluka 99.8 mass% ethylene in methyl propionate at different conditions, an algorithm for bubble point calculations was used [5]. known composition was synthesized. The open end of the Cailletet 4. Results and discussion tube was submerged in mercury, and was placed in the autoclave of the Cailletet apparatus. In this equipment, pressure (or tempera- Table 2 presents the experimental bubble point pressures of the ture) can be fixed, and temperature (or pressure) can be changed binary system of ethylene + methyl propionate for eight different until a phase change is visually observed for the synthetic sample isopleths. In the case of those isopleths for which the critical point in the Cailletet tube with known composition. Temperatures can be of the mixture was also determined, the critical temperatures and set between 250 and 450 K in this apparatus depending on the pressures have been marked with a star symbol in Table 2. These thermostat fluid which is used inside the apparatus. The phase critical points were measured visually by considering the physical transition can be measured at pressures up to 15 MPa. The Cailletet criteria of the critical point, such as critical opalescence and tube is placed in a glass jacket, in which thermostated silicone oil, equality of the volumes of the two phases becoming critical. Fig. 1 from a thermostat bath, is circulated. The fluctuations of the bath shows these data in a P–T diagram for all of the mixture isopleths. temperature are not more than 0.04 K. A platinum-resistance As can be seen in Fig. 1, for the two isopleths having mole fractions thermometer is placed very close to the equilibrated sample to measure temperature. The accuracy of the temperature readings Table 2 are Æ0.01 K. The pressure is kept constant and measured using a Bubble point pressures of the binary system of ethylene + methyl propionate for several isopleths. dead weight gauge with an accuracy of Æ0.003 MPa for the whole range of the pressure measurements. Shariati and Peters [4] have Mole fraction of C2H4 = 0.0408 previously explained the Cailletet apparatus extensively. T P T P (K) (MPa) (K) (MPa) 346.42 0.544 392.64 0.943 3. Modeling 361.37 0.640 408.06 1.144 361.68 0.647 423.65 1.392 The PR EOS [3] was used to calculate the solubility of ethylene in 377.25 0.780 439.04 1.685 377.36 0.778 methyl propionate: RT a Mole fraction of C2H4 = 0.0803 P ¼ À (1) v À ð þ Þ þ ð À Þ b v v b b v b T P T P (K) (MPa) (K) (MPa) In the above equation, P is pressure, T is temperature, and v is the 331.19 0.855 392.72 1.552 molar volume.
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