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Estimation Methods for Thermophysical Properties of Camelina Sativa Crude Oil

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Estimation Methods for Thermophysical Properties of Camelina Sativa Crude Oil U.P.B. Sci. Bull., Series B, Vol. 78, Iss. 1, 2016 ISSN 1454-2331 ESTIMATION METHODS FOR THERMOPHYSICAL PROPERTIES OF CAMELINA SATIVA CRUDE OIL Andreea Cristina PETCU1, Valentin PLEŞU2, Corneliu BERBENTE3 Camelina is one of the most promising sources of renewable fuels. The crude oil obtained from this plant can be chemically treated and converted into bio-diesel or bio-kerosene. To study straight camelina oil combustion process is very important to know as many of its properties as possible. In this article, estimation methods of several thermophysical properties, such as: critical properties, density, thermal conductivity, and specific heat are presented. Where it was possible, the estimated values have been compared with experimental measurements, thus validating the used method. Keywords: camelina oil, estimation methods, thermophysical properties 1. Introduction Camelina oil is a new, promising feedstock for second generation bio- fuels. The bio-kerosene obtained from camelina oil meets all the performance and safety requirements so that it can be used in aviation. Blends of classic aviation fuel / bio-kerosene obtained from camelina oil have been successfully tested on fighting planes and passenger planes [1]. According to European directives 2003/30/CE and 2009/28/CE, crude vegetable oils are also considered biofuels. In the specialized literature, there is scarce information regarding the combustion process of crude vegetable oils, in particular camelina oil. The possibility of using straight camelina oil as fuel for terrestrial applications has been taken in consideration because the process of obtaining the vegetable oil is cheaper and less time consuming then obtaining biofuels from vegetable oils. To understand better the combustion process of the crude camelina oil, is very important to know as many of its properties as possible. In this paper, estimation methods for several thermophysical properties are presented and applied for the particular case of crude vegetable camelina oil. To validate the used methods, the estimated values have been compared with experimental 1 PhD. student, Romanian Research & Development Institute for Gas Turbines COMOTI Bucharest, Romania, e-mail: [email protected] 2 Prof., Faculty of Applied Chemistry and Materials Science, University POLITEHNICA of Bucharest, Romania, e-mail: [email protected] 3 Prof., Faculty of Aerospace Engineering, University POLITEHNICA of Bucharest, Romania, e- mail: [email protected] 60 Andreea Cristina Petcu, Valentin Pleşu, Corneliu Berbente measurements, where such data were available. A detailed presentation of the experimental procedure used for obtaining the experimental data which will be presented in this paper, can be found in reference [2]. 2. Camelina oil molar weight estimation The calculations presented in this article are based on the fatty acids camelina oil chemical composition, given in Table 1. The camelina oil fatty acids composition has been analyzed at the Dangerous substances, waste and residual water testing laboratory from the National Research and Development Institute for Chemistry and Petrochemistry. Table 1 Camelina oil fatty acids composition Fatty acid Molar fraction Molar weight MWi (g/mol) 1 Palmitic acid(C16) 0.0747 256 2 Stearic acid (C18) 0.0127 284 3 Oleic acid (C18:1) 0.1687 340 4 Linoleic acid (C18:2) 0.2449 282 5 Linolenic acid (C18:3) 0.3407 280 6 Eicosanoic acid (C20:1) 0.1479 278 7 Behenic acid (C22) 0.0042 310 8 Erucic acid (C22:1) 0.0058 338 The fatty acids composition of the camelina oil cultivated in Romania, and presented in Table 1, is similar, but not the same as those reported for oils obtained from camelina seeds cultivated in Spain [3] and in Slovenia [4]. The differences in the composition may be due to different cultivation regions and different growing conditions. These fatty acids are found in the camelina oil in the form of triglycerides. The mathematical methods presented in this article estimate the termophysical properties of these triglycerides. The camelina oil thermophysical properties are calculated starting from these values and considering that the molar fraction of these triglycerides is equal with the molar fraction of the fatty acid in their composition. The camelina oil molar weight has been calculated using the following relation [5]: MW= 3 x MW + 38.0488 oil∑ i i (1) where xi represents the molar fraction of the fatty acid i in the oil's composition, and MWi is the molar weight of the respective fatty acid. According to equation (1), in order to estimate the molar weight of camelina oil is necessary to calculate first the weight average molecular weight of all the fatty acids components of the compound, based on their individual molecular weights and mole fractions. This Estimation methods for thermophysical properties of camelina sativa crude oil 61 is multiplied by 3 to take into account the 3 identical fatty acid chains found in the fatty acid corresponding triglyceride. In addition, one also needs to take into account the glycerol part of the triglyceride, which is composed of 3 carbon atoms and 5 hydrogen atoms (-CH2-CH-CH2-), as well as the difference of 3 hydrogen atoms between the fatty acids and the fatty acid chains in the composition of the triglyceride. The sum of these contributions, calculated using equation (2) [5], leads to the obtaining of the second term on the right-hand side of equation (1): 3⋅+⋅−⋅=MWCarbon 5 MW Hidrogen 3 MW Hidrogen 38.0488 (2) By applying equation (1) the molar weight of the camelina oil has been estimated to 886.88 g/mol. 3. Critical properties estimation methods To determine the thermophysical properties of a substance, estimation methods use as input data the characteristic constants of the respective compound, defined in the following: normal boiling point, critical temperature, critical pressure, critical volume and acentric factor. To determine experimentally these constants is very difficult, because the majority of substances chemically decompose before reaching the critical point. The critical temperature represents the temperature value above which the substance can no longer be liquefied, no matter how much pressure is applied. The critical pressure is the pressure of the substance's vapor pressure at the critical temperature. The critical volume is the volume occupied by 1 mole of substance at its critical temperature and pressure. The normal boiling point represents the temperature value at which the compound's vapor pressure is equal to the atmospheric pressure [6]. The acentric factor is a measure of the sphericity of the molecule [7]. The used estimation methods are presented in Table 2. Table 2 Critical properties estimation methods Method Equation Joback [7] TKbbi[]198=+∑ xi ⋅Δ T (3) −1 ⎡ 2 ⎤ TK[ ]=+⋅Δ−⋅Δ T 0.584 0.965∑∑ x T() x T (4) c b ⎣⎢ iciici⎦⎥ −2 Pbarc[ ]=+⋅−Δ() 0.113 0.0032 nA ∑ xici P (5) 3 Vcmmolc[/]17.5=+Δ∑ xVici (6) Constantinou & Gani [8] TKbbibi[ ]=⋅⋅Δ+⋅Δ 204.359 ln(∑∑ xii T12 y T ) (7) TKc[ ]=⋅⋅Δ+⋅Δ 181.128 ln(∑∑ xTiici12 xT c i ) (8) 62 Andreea Cristina Petcu, Valentin Pleşu, Corneliu Berbente −2 Pc[ bar ]=⋅Δ+⋅Δ+ (∑∑ xii Pci12 y P c i 0.10022) + 1.3705 (9) 3 Vcmmolc[ / ]=− 0.00435 + (∑∑ xii ⋅Δ Vci12 + y ⋅Δ V c i ) (10) Fedor [6,9] TKc[ ]=⋅ 535 log10 (∑ xici ⋅Δ T ) (11) 3 Vcmmolc[ / ]=+⋅Δ 26.6 ∑ xici V (12) Marrero & Gani [10] TKbbibi[ ]=⋅⋅Δ+⋅Δ 222.543 ln(∑∑ xii T12 y T ) (13) TKc[ ]=⋅⋅Δ+⋅Δ 231.239 ln(∑∑ xTiici12 xT c i ) (14) −2 Pbarc[ ]=⋅Δ+⋅Δ+ (∑∑ xii Pci12 y P c i 0.108998) + 5.9827 (15) 3 Vcmmolc[/]7.95(=+∑∑ xii ⋅Δ+⋅Δ Vci12 y V c i ) (16) Nannoolal [11] ∑ xTi ⋅Δ TK[ ]=+bi 84.3395 (17) b 0.6583 n +1.6868 Banks [12] log10 TKb [ ]=− 2.98 4 / M (18) Burnop [12] log10 TKbbi [ ]=⋅Δ−∑ xi T M 8 / M (19) The results obtained using the above estimation methods are summarized in Tables 3 - 6. Table 3 Estimation of normal boiling point Tb Constantinou Gani & T [K] Joback Nannoolal Banks Burnop b & Gani Marrero Tripalmitin 1,540.5 806.66 825.51 909.78 690.41 893.49 Tristearin 1,677.78 827.41 847.72 946.93 701.33 918.25 Triolein 1,690.26 827.39 849.66 1,030.36 700.59 921.81 Trilinolein 1,702.74 827.37 851.58 1,113.79 699.85 925.43 Trilinolenin 1,715.22 827.36 853.48 1,197.24 699.11 929.13 Trieicosanoin 1,815.06 846.25 867.91 981.59 710.28 750.07 Tribehenin 1,952.34 863.49 886.42 1,014.16 719.49 960.51 Trierucin 1,964.82 863.48 888.05 1,089.35 718.91 963.74 Camelina oil 1,710,95 828,65 852,33 1,090.23 700.49 897.66 Table 4 Estimation of critical temperature Gani & T [K] Joback Constantinou & Gani Fedor c Marrero Tripalmitin 3,008.84 958.80 1,009.48 1,020.29 Tristearin 4,487.05 976.93 1,031.86 1,042.35 Triolein 4,019.29 977.88 1,035.11 1,043.28 Trilinolein 3,665.24 978.82 1,038.31 1,044.22 Trilinolenin 3,389.76 979.76 1,041.47 1,045.16 Trieicosanoin 8,638.16 993.41 1,052.26 1,062.49 Estimation methods for thermophysical properties of camelina sativa crude oil 63 Tribehenin 94,741.78 1,008.51 1,071.01 1,081.03 Trierucin 23,514.85 1,009.31 1,073.75 1,081.82 Camelina oil 4,824.19 979.53 1,038.60 1,045.23 Table 5 Estimation of critical pressure Pc[bar] Joback Constantinou & Gani Gani & Marrero Tripalmitin 2.72 3.66 7.51 Tristearin 2.27 3.28 7.24 Triolein 2.43 3.33 7.28 Trilinolein 2.61 3.39 7.32 Trilinolenin 2.82 3.44 7.36 Trieicosanoin 2.02 2.98 7.04 Tribehenin 1.65 2.75 6.88 Trierucin 1.84 2.78 6.91 Camelina oil 2.56 3.35 7.29 Table 6 Estimation of critical volume Constantinou & Gani & V [cm3/mol] Joback Fedor c Gani Marrero Tripalmitin 2,963.5 2,967.73 2,970.33 2,818.01 Tristearin 3,299.5 3,302.29 3,308.01 3,134.62 Triolein 3,239.5 3,253.96 3,265.62 3,094.68 Trilinolein 3,179.5 3,205.63 3,223.23 3,054.74 Trilinolenin 3,119.5 3,157.29 3,180.84 3,014.79 Trieicosanoin 3,635.5 3,636.84 3,645.69 3,381.14 Tribehenin 3,971.5 3,971.41 3,983.37 3,767.87 Trierucin 3,911.5 3,923.08 3,940.98 3,727.93 Camelina oil 3,228.31 3,250.64 3,266.67 3,085.15 There are no experimental data or information in the specialized literature regarding these properties for the camelina oil.
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