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 *

School of Chemical and Petroleum Engineering, Shiraz University, Molla Sadra Street, Shiraz 71345, Iran

DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

Chemical Engineering Department, The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates

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:

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

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 0.01 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 0.003 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 (1)

v ð þ Þ þ ð 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. The parameters a and b for a pure component are

346.27 0.998 408.06 1.795

determined using its critical temperature, TC, critical pressure, PC,

361.64 1.158 423.89 2.081

and acentric factor, v, as follows:

377.07 1.336 439.31 2.411 !

R2T2

ci Mole fraction of C2H4 = 0.1625 a ¼ 0:457235 (2) ci P ci T P T P

(K) (MPa) (K) (MPa)

315.63 1.468 392.22 2.873

RTci 330.70 1.718 407.71 3.209

bi ¼ 0:077796 (3)

346.01 1.983 423.23 3.574

Pci

361.43 2.263 438.81 3.969

376.75 2.558

a a a (4)

i ci i Mole fraction of C2H4 = 0.3218 T P T P

sffiffiffiffiffiffi ! (K) (MPa) (K) (MPa)

2 315.27 2.887 392.01 5.468

aiðTÞ ¼ ½1 þ mi 1 (5)

Tci 330.44 3.387 407.72 5.989

345.94 3.908 423.65 6.504

361.1 4.428 439.18 6.979

376.56 4.948

¼ : þ : v ¼ : v

mi 0 37646 1 54226 i 0 26992 i (6)

Mole fraction of C2H4 = 0.4839

The classical mixing rules were used for calculating the parameters

T P T P

a and b of the mixture:

XX (K) (MPa) (K) (MPa) À Á

0:5

¼ ð Þ

a xixj aiaj 1 kij (7) 315.68 4.336 392.02 8.111

i j 330.43 5.091 407.53 8.731

330.56 5.101 407.72 8.746

345.67 5.881 423.10 9.241

345.89 5.896 423.28 9.246

b ¼ x b (8)

i i 361.19 6.671 438.87 9.556

361.29 6.681 438.88 9.551

376.61 7.421 454.41 9.476

In Eqs. (7) and (8),x is in mole fraction and kij is the binary

376.91 7.431 455.37 9.451

interaction parameter between components i and j. In order to

A. Shariati et al. / Fluid Phase Equilibria 387 (2015) 143–145 145

Table 2 (Continued)

Mole fraction of C2H4 = 0.4839 T P T P (K) (MPa) (K) (MPa)

a a

391.98 8.116 464.80 9.038

Mole fraction of C2H4 = 0.6404 T P T P

(K) (MPa) (K) (MPa)

315.29 5.611 407.75 10.666

330.50 6.681 412.78 10.716

345.71 7.736 417.98 10.701

361.17 8.736 423.13 10.641

376.55 9.611 423.32 10.646

a a

392.33 10.301 428.43 10.476

Mole fraction of C2H4 = 0.8021 T P T P

(K) (MPa) (K) (MPa)

297.83 5.172 355.92 9.762

310.19 6.237 361.01 9.997

320.25 7.122 366.18 10.192 Fig. 2. The P–x diagram of the binary system of ethylene (1) + methyl propionate (2)

330.39 7.992 369.21 10.292 at 360 K (points represent experimental data and the dashed line shows the

340.61 8.802 370.27 10.322 calculated results).

* *

350.84 9.482 370.81 10.337

Mole fraction of C2H4 = 0.9009

T P T P

phase behavior of this binary system for comparison with our

(K) (MPa) (K) (MPa)

results. Fig. 1 also presents the results of modeling using the PR

283.51 4.416 322.86 7.891

EOS, in its predictive mode, for the bubble points of the system of

291.33 5.101 326.89 8.176

ethylene + methyl propionate. As can be seen from Fig. 1,

299.27 5.831 327.80 8.236

a a

307.08 6.561 328.79 8.301 the predictions of the PR EOS are acceptable. It is capable to

314.94 7.266

predict the general trend of the phase behavior of this system

u(T) = 0.04K; u(P) = 0.003 MPa; u(x) = 0.0050 correctly. The AAD% of the PR EOS for all of the calculated bubble

Critical temperature and pressure of the isopleth. points was 5.8%. Fig. 2 shows the P–x diagram of the system of

ethylene + methyl propionate at 360 K. Since the temperature

of 360 K is higher than the critical temperature of ethylene

(282.5 K), the P–x diagram of this system could not cover the whole

range of the concentrations at this temperature. The experimental

data obtained in this study on ethylene solubilities in methyl

propionate in a range of temperatures and pressures can assist in

the proper operation and optimization of current processes, as well

as in feasibility studies for future processes and separation

techniques involving these substances.

Acknowledgements

Alireza Shariati would like to thank both Shiraz University and

Eindhoven University of Technology, especially Prof. M.C. Kroon,

for giving him the opportunity to collaborate in this research.

References

[1] R.D. Farris, Methyl esters in the fatty acid industry, J. Am. Oil Chem. Soc. 56

(1979) 770–773.

[2] U.R. Samel, W. Kohler, A.O. Gamer, U. Keuser, Propionic acid and derivatives,

Ullmann’s Encyclopedia of Industrial Chemistry, 20, Wiley-VCH Verlag GmbH

Fig. 1. The solubility data of ethylene (1) in methyl propionate (2) at various

and Co., Weinheim, 2012, pp. 295.

temperatures and pressures.

[3] D.Y. Peng, D.B. Robinson, A new two-constant equation of state, Ind. Eng. Chem.

Fundam. 15 (1976) 59–64.

[4] A. Shariati, C.J. Peters, High-pressure phase behavior of systems with ionic

ﬂ

of ethylene equal to 0.4839 and 0.6404, there is a maximum in the liquids: measurements and modeling of the binary system uoroform + 1-ethyl-

3-methylimidazolium hexaﬂuorophosphate, J. Supercrit. Fluids 25 (2003)

bubble point pressure curve of the mixture. This means that

109–117.

–

the critical points of such mixtures are on the right side of their P T [5] J.M. Smith, H.C. Van Ness, M.M. Abbott, Introduction to Chemical Engineering

phase envelope. There are no data available in literature on the Thermodynamics, 7th ed., McGraw Hill, New York, 2005.