Calculation of the molar heat of formation of fatty acid

triglycerides from the heat of combustion of vegetable oils

Łukasz Jęczmionek*

University of Applied Sciences in Tarnow, Polytechnic Faculty, ul. Mickiewicza 8, 33-100 Tarnów, Poland

Article history Abstract

Received: 15 October 2020 The results of the research on estimation the molar heat of formation (enthalpy) of model
Received in revised form: triglycerides found in natural oils and fats are presented. In this work a calculation method
2 January 2021 and calorimetric one were used. It was found that combustion heat values determined
Accepted: 10 January 2021 by separate methods are comparable; their difference was a maximum of 155 kJ/kg, and
Available online: 10 January 2021 thus was significantly lower than the tolerance for the calorimetric method according to
PN 86/C-04062.

Keywords: vegetable oils, enthalpy, triacylglycerols

Introduction The relatively high thermal effect of the reaction is asso-

ciated with strongly exothermic reactions of hydrooxidation,
Hydroconversion of vegetable oils and/or animal fats to bio-hy- decarboxylation and decarbonylation of fatty acids, as well as
drocarbons is a process known to all engineers involved in the hydrogenation of multiple bonds in fatty acid chains [3, 4]. The
problem of producing liquid biofuels. The success of the Neste authors also pay attention to the occurrence of the strongly exo-
Oil company, which developed and implemented the MExBTL thermic secondary methanation reaction during hydroconversion
process on an industrial scale, as well as actions taken following [3–5]. In the paper [6] the thermal effect of hydroconversion
its example by other leading companies in the industry, caused of 20% (V/V) mixtures of various vegetable oils with a liquid
that many engine fuel producers are considering launching paraffin fraction was investigated. The thermal gradient accom-
a similar process in their refinery. Taking into account the pos- panying the hydroconversion of these oils ranged from 5.5 to
sibility of beginning the co-processing of vegetable oils / fats 9.2 ºC and was higher the more unsaturated fatty acids contained
in Polish refineries in the near future, the subject of the thermal in the oil. The research was carried out on a laboratory scale
effect of the hydroconversion process is discussed [1]. using a 100 ml reactor. In work [7] an attempt was made to esti-
The issue seems to be trivial only seemingly. Nevertheless, it mate the temperature gradient during co-processing of rapeseed
is of key importance when it comes to the use of existing units oil with diesel oil fraction. It was found that this effect varies
for the implementation of co-processing. Hydroconversion of significantly depending on the assumptions made; whether the
fatty oils is associated with a relatively high exothermic effect, process in the liquid or steam phase is being considered. It was
which in practice leads to the formation of high temperature estimated at 26.6 ºC for a 20 (V/V) mixture of rapeseed oil in the
gradients and even to overheating the catalytic bed, for which ex- liquid phase and 35.2oC for a 30% (V/V). However, at 33.9 ºC
isting units are not built [2]. The thermal effect can really cause for 20% (V/V) rapeseed oil in the steam phase and 46.3 ºC for
a significant problem. It is evidenced by the fact that in 2007 in 30% (V/V). In real conditions the process takes place in the liq-
Parvoo (Finland) the first unit in the world according to NExBLT uid – steam phase [8]. According to Chen [8], the fraction with
technology was launched. The thermal effect associated with the a boiling range of light vacuum oil (and thus slightly heavier
hydroconversion proved to be higher than anticipated, which than the diesel fraction) at 350 ºC, at a pressure of 5 MPa, is
caused the necessity to modify the reactor by introducing addi- steamed in about 60%. On the other hand, the introduction of
tional quench giving hydrogen as a cooling agent [2]. vegetable oil or animal fat into the crude oil derived naphtha
fraction results in a reduction of the vaporization rate. According
to [8], the pressure increase in the reactor leads to a decrease in
*
Corresponding author: [email protected] the thermal effect, because the degree of vaporization is reduced.

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© 2020 University of Applied Sciences in Tarnow. Published under the
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Ł. Jęczmionek Calculation of the molar heat of formation of fatty acid triglycerides… 9

So far, research related to the development of the thermody- combustion, at least n different mixtures of these compounds.
namic model of hydroconversion has been conducted in a limited Of course, in practice, the described method may have sig-
way [9, 10]. It should be noted here that such a model requires nificant limitations resulting e.g. from the specific properties of
the adoption of many variable assumptions depending on the given substances. However, if we are dealing with a homoge-
conditions of the process as well as knowledge of thermodynamic neous mixture of substances of similar structure, not significant-
data for the reagents present in the system, such as e.g. the heat ly differing in physico-chemical properties, e.g. triglycerides of
of formation (enthalpy) of fatty acid triglycerides. An attempt to fatty acids, this method may be considered [6, 7].
determine the molar heat of formation of model triglycerides of Let’s assume that a given vegetable oil is composed solely
fatty acids occurring in vegetable oils obtained from plant seeds of triglycerides of two fatty acids having saturated hydrocarbon
was made in the work [7]. In paper [9] an analysis of the thermo- chains of different length (different number of carbon atoms) -R1
dynamic aspect of the hydroconversion process was performed, and -R2, where the R1 chain is shorter than the R2 one. According
taking into account all occurring reactions, primary and secondary, to the heat of additivity principle, it can be said that the molar heat
in connection with process conditions. In the paper [10] a thermo- of combustion [Q(s)] of a triglyceride consisting of three identical
dynamic model of stearic acid hydroconversion for standard con- R1 residues will be lower than for an analogous triglyceride but
ditions is presented, based on the results obtained in the paper [7]. containing three identical R2 residues (dependence 1):
This article presents the results of research on the development
of a thermodynamic model of hydroconversion, starting from the Q(s) C6H5O6(R1)3 < Q(s) C6H5O6(R2)3 (1)
experimental determination of the heat of formation of model fatty
acid triglycerides by a different method than in the work [7]. The It is easy to see that the dependence (2) will also be met:
practical significance and application of these data for conducting
the hydroconversion process in real conditions was also indicated. Q(s) C6H5O6(R1)3 < Q(s) C6H5O6(R1)2R2 < Q(s) C6H5O6(R2)2R1 <
< Q(s) C6H5O6(R2)3 (2)
Experimental
The average molar heat of combustion of such a mixture will de-
Assumptions of the hydroconversion model − pend on the share of individual fatty acids in triglycerides. Therefore,
molar heat of triglyceride formation for the sake of simplicity, it can be assumed that the above-men-
tioned oil consists exclusively of two types of triglycerides: contain-
A hydroconversion model involving the heat of combustion ing only R1 residues or only R2 residues, the proportion between
of model triglycerides has been discussed in papers [6, 7]. them being identical to the practically indicated ratio between R1
According to this article [7], the heat of combustion is a mea- and R2 fatty acids. In other words, in the proposed model, the shares
sure of the chemical energy contained in the fuel. According of individual acids in triglycerides correspond to the shares of model
to the definition in PN-86/C-04062, the heat of combustion is triglycerides with three identical acid residues.
the amount of heat released during the complete combustion These conditions also apply to oils consisting of triglycerides
of a mass of fuel containing only carbon, hydrogen, oxygen, of n fatty acids, of different length and with different amounts
nitrogen and sulfur, in an atmosphere of oxygen, the products of double bonds in the chain.
of combustion being: dioxide carbon, sulfur dioxide, gaseous Taking into account selected highly refined natural oils ob-
nitrogen and liquid water, and starting materials and combustion tained from plant seeds, according to the proposed model, it
products are in standard conditions. can be assumed that they are mixtures of model triglycerides
One of the basic features of heat of combustion is its additiv- with identical C14 ÷ C24 acid residues (thirteen different com-
ity [9–11]. The consequence of the additive heat of combustion pounds) in different proportions (Table 1). It is assumed that
is the fact, that in the case of two organic compounds with dif- acids present in trace amounts can be omitted. Similarly, com-
ferent enthalpy of formation, the total heat of combustion will pounds present in oils in relatively small amounts (dyes, sterols,
be the sum of the shares of heat of combustion brought by each alcohols, triglycerides, free acids, etc.). You can additionally
of these compounds. take action to remove at least some of the compounds – the con-
Similar reasoning can be made for a system containing n com- stituent natural oils, which are not triglycerides or triglycerides
ponents. In the case where we have a mixture of n known com- with an unusual structure, which will be discussed later.
pounds, but with unknown enthalpies of formation, theoretically, The heat of combustion of the mixture of model triglycerides
it is possible to determine these parameters based on the heat of will be virtually identical to the heat of combustion of real

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10 Science, Technology and Innovation Original Research

vegetable oil having an analogous sequence of fatty acids, can determine the heat of combustion of each of these com-
provided that all (or almost complete) removal of other chem- pounds by solving a system of thirteen (at least) equations
ical compounds except triglycerides that could significantly with thirteen unknowns. In practice, there is a fourteenth
influence the measurement of the heat of combustion. With unknown related to the so-called triglycerides “unmarked”,
thirteen different mixtures of these model triglycerides (or hence fourteen mixtures and fourteen equations appear in the
real oils with an analogous sequence of fatty acids), one calculations [7].

Table 1. Fatty acids found in the tested vegetable oils and model triglycerides, their derivatives

Fatty acid / triglyceride Number of carbon atoms in the acid molecule: Formula of a model fatty acid triglyceride
number of double bonds in the hydrocarbon chain

Mirystic 14 : 0 C45H86O6
Palmitic 16 : 0 C51H98O6
Palmitoleic 16 : 1 C51H92O6
Stearic 18 : 0 C57H110O6
Oleic 18 : 1 C57H104O6
Linoleic 18 : 2 C57H98O6
Linolenic 18 : 3 C57H92O6
Arachidic 20 : 0 C63H122O6
Eikozeic 20 : 1 C63H116O6
Behenic 22 : 0 C69H134O6
Erucic 22 : 1 C69H128O6
Lignoceric 24 : 0 C75H146O6
Nervonic 24 : 1 C75H140O6

Experimental procedure acids, i.e. substances that could potentially increase the mistake
in determining the heat of combustion of oils. Because all of
Four natural vegetable oils with a clearly differentiated fatty these compounds are characterized by relatively high polarity,
acid sequence were selected to make triglyceride “mixtures”: bleaching earth was used to remove them. The effectiveness of
hazelnut oil (N), linseed oil (L), grapeseed oil (G), rapeseed this operation has been confirmed in IR studies.
oil (R). The selection criterion was the possibly diverse com- The compositions of individual oils (N, L, G, R) were deter-
position of fatty acids in these oils. Mixtures of these have also mined with an estimated tolerance of approximately (± 0.3%).
been prepared: For acids with a low content (less than 1%) this caused a signif-
Two-component: icant mistake. In order to limit the influence of this factor, each
N + L; N + G; N + R; L + G; L + R; G + R determination was performed twelve times and after removing
Ternary: the extreme determinations, the average content was adopted.
N + L + G; L + G + R; N + G + R Oil mixtures were prepared by weight, determining the mass
Quaternary: of oils and the entire mixture on an analytical scale. Efforts were
N+L+G+R made to mix the oils in an equal weight ratio. Knowing the com-
Before determining the heat of combustion of oils and their position of fatty acids in individual oils and the exact masses of
mixtures by calorimetric method according to PN 86/C-04062, individual oils in mixtures, the content of individual fatty acids
as well as before determining the composition of fatty acids in these mixtures was calculated. These contents, for individual
present in triglycerides by the method according to PN-EN ISO oils as well as their mixtures, are given in Table 2.
5508 and PN-EN ISO 5509, oil samples natural ones were re- Ultimately, 14 samples consisting of fatty acid triglycerides
fined according to the procedure described in work [7]. (four individual vegetable oils, six two-component mixtures of
The purpose of refining was to remove solid oil components these oils, three ternary and one four-component) were available.
(solid residues after pressing), sterols, dyes (e.g. carotene), al- According to the presented assumptions, refined natural oils
cohols and possible mono- and triglycerides of fatty acids, free and their mixtures were considered to be mixtures of model fatty

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Ł. Jęczmionek Calculation of the molar heat of formation of fatty acid triglycerides… 11

Table 2. The content of fatty acids in triglycerides of selected natural oils and their mixtures after refining. Average values for 12
determinations are given (after rejecting extreme values), % (m/m)
Model triglycerides

Grapeseed oil (G)

Rapeseed oil (R)

Hazelnut oil (N)

Lineseed oil (L)

N+ L + G + R
N+G+R
N+L+G

L+G+R
G+R
N+G

N+R
N+L

L+G

L+R
Mirystic 0.03 0.05 0.05 – 0.04 0.04 0.02 0.5 0.03 0.03 0.04 0.03 0.03 0.03
Palmitic 5.1 5.8 6.8 4.5 5.45 5.95 4.8 6.3 5.15 5.65 5.9 5.7 5.47 5.55
Palmitoleic 0.23 – 0.2 0.2 0.12 0.22 0.22 0.1 0.1 0.2 0.22 0.14 0.21 0.16
Stearic 1.9 0.1 3.9 1.8 1.0 2.9 1.85 2.0 0.95 2.85 1.97 1.94 2.54 1.92
Oleic 76.18 3.3 18.1 63.0 39.75 47.14 69.59 10.7 33.15 40.55 32.53 28.14 52.43 40.15
Linoleic 15.7 15.6 69.2 18.7 15.65 42.45 17.2 42.4 17.15 43.95 33.5 34.5 34.5 29.8
Linolenic 0.15 71.3 0.2 7.4 35.75 0.08 3.78 35.75 39.35 3.8 23.89 26.3 2.58 19.76
Arachidic 0.1 1.8 0.15 0.6 0.95 0.12 0.35 0.98 1.2 0.38 0.69 0.85 0.28 0.67
Eikozeic 0.16 0.3 0.27 1.7 0.09 0.22 0.93 0.29 1.0 0.98 0.25 0.76 0.71 0.61
Behenic – – 0.02 0.4 – 0.01 0.2 0.01 0.2 0.21 – 0.14 0.14 0.1
Erucic – – – 1.3 – – 0.65 – 0.65 0.65 – 0.44 0.44 0.33
Lignoceric – 0.2 0.6 0.2 0.1 0.3 0.1 0.4 0.2 0.4 0.27 0.34 0.27 0.25
Nervonic – 0.6 – 0.1 0.3 – 0.05 0.3 0.35 0.05 0.2 0.24 0.04 0.18
Unidentified 0.45 0.95 0.51 0.1 0.8 0.47 0.26 0.27 0.52 0.39 0.54 0.48 0.36 0.49

acid triglycerides (Table 2). Thus, the mass fractions of individ- to the principle of additivity, by individual model triglycerides.
ual fatty acids in triglycerides of natural oils corresponded to the Three natural vegetable oils were selected for this purpose: soy-
mass fractions of these model triglycerides in model natural oils. bean oil, olive oil and sesame oil. Refined and unrefined samples
A system of equations was created (their number was equal of these oils were used in this study.
to the number of oils and mixtures used in the study – in this
case = 14) with fourteen unknowns in which the coefficients for Results and discussion
individual variables were weight percentages of individual fatty
acids (Table 2). On this basis, in turn, a fourteenth-degree matrix For the input data, variable values within the respective con-
was created from which the values of individual variables were fidence intervals were obtained. Proposed on the basis of cal-
determined. The calculation method has been comprehensively culations of molar heat of combustion of individual model tri-
presented in the work [7], hence it is not discussed in detail here. glycerides and molar enthalpies of formation are given in Table
Attention has been paid to several selected aspects. Appropriate 3. It should be said that in the literature generally no data on the
confidence intervals [7] as well as limit values [7] were deter- molar heat of triglyceride formation of fatty acids. This limits
mined for variables, and then it was checked to what extent the the possibility of a wide discussion, as there is very little work
calculated calorific values of individual oils were within the on this subject.
tolerance. The task required taking variable free words (within For comparison, the values of molar heat of triglyceride for-
the appropriate confidence intervals), and then checking whether mation obtained in the work were cited [7].
the obtained solution of the matrix is correct (whether all ob- What are the calorimetric values of the heat of combustion of in-
tained values of the variables are within the accepted confidence dividual vegetable oils calculated and calculated from the system of
intervals). Because the task was quite difficult, MathCad was equations? These data are presented in Table 4 and also illustrated in
used to solve it. Figure 1. They were compared with the data obtained in the paper [7].
The last part of the experiment was checking the usefulness of Considering calorimetrically determined heat of combustion
the developed model for calculation of combustion heat of natural of vegetable refined oils and comparing them with calculated val-
oils without an initial refining. This check consisted in a propor- ues, very good agreement of these results was observed (Table 5).
tional addition of the heat of combustion brought in, according The obtained results testified to the good precision of calorimetric

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12 Science, Technology and Innovation Original Research

Table 3. Calculated heat of combustion and molar enthalpies of model triglycerides of fatty acids in natural refined oil

Model triglyceryde Chemical formula Molar combustion heat Molar heat of formation Molar heat of formation
[kJ/mol] ΔH0 [kJ/mol] according ΔH0 [kJ/mol]
to [7]

Mirystic C45H86O6 27710.6 −2252.5 −2296.6

Palmitic C51H98O6 31638.1 −2385.1 −2411.7
Palmitoleic C51H92O6 31187.1 −2048.8 −2039.2
Stearic C57H110O6 35726.6 −2520.2 −2434.8
Oleic C57H104O6 35183.0 −2216.9 −2180.6
Linoleic C57H98O6 34507.1 −1979.6 −1930.3
Linolenic C57H92O6 34030.6 −1601.5 −1556.2
Arachidic C63H122O6 39511.5 −2801.5 −2726.5
Eikozeic C63H116O6 38722.3 −2551.0 −2658.5
Behenic C69H134O6 43311.5 −2924.3 −3004.7
Erucic C69H128O6 42896.5 −2620.4 −2561.5
Lignoceric C75H146O6 47264.3 −3010.3 −3129.1
Nervonic C75H140O6 46661.4 −2786.5 −2873.9

determinations, much higher than the uncertainty (± 318 kJ/kg) oils (hazelnut, sesame, linseed, grape, pumpkin seed, poppy seed,
allowed by the PN 86/C-04062 standard. Calculated on the ba- avocado, apricot kernel, macadamia, olive oil, corn, soybean, sun-
sis of the system of heat equations for the formation of model tri- flower, rice, rapeseed) were used as a standard. It was found that the
glycerides of fatty acids, they were referred primarily to the results results obtained in both works are similar. A comparison of these
obtained in the work [7], in which a dozen or so natural vegetable results is given in Tables 4 and 5.

Table 4. The heat of combustion of natural refined oils determined experimentally and obtained as a result of substitution of cal-
culated values of heat into a system of equations

Vegetable natural oil Combustion heat determined Combustion heat calculated Combustion heat calculated
calorimetrically [kJ/kg] according to [7] [kJ/kg]
[kJ/kg] ± 318 kJ/kg

Hazelnut oil (N) 39796 39700 39611

Lineseed oil (L) 39298 39344 39113
Grapeseed oil (G) 39474 39420 39338
Rapeseed oil (R) 39545 39660 39580
N+L 39402 39291 –
N+G 39643 39560 –
N+R 39599 39680 –
L+G 39335 39271 –
L+R 39566 39411 –
G+R 39487 39540 –
N+L+G 39520 39427 –
L+G+R 39477 39414 –
N+G+R 39642 39594 –
N+L+G+R 39515 39486 –

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Ł. Jęczmionek Calculation of the molar heat of formation of fatty acid triglycerides… 13

Figure 1. Comparison of the heat of combustion for selected natural refined oils and their mixtures; values determined calorimetrically and ob-
tained as a result of substitution of calculated values of heat to the system of equations

The calculated heat of palmitin triglyceride formation was at work [7], i.e. 254 kJ/kg. Greater differences were obtained
also compared with the result obtained for the reference com- between the values of heat of combustion of triglycerides – cal-
pound. Palmitic triglyceride (Sigma-Aldrich CAS reagent: culated and calorimetrically determined than for the method
555-44-2) was available. The heat of combustion of this described in this paper, in which only four oils were used. The
compound was calorimetrically determined at 39329 kJ/kg, key parameter determining the precision of the calculations was
i.e. 31699.4 kJ/mol. The molar heat of formation of this the accuracy of the determination of fatty acid composition in
compound was determined at −2425.3 kJ/mol (molar heat of individual oils. On the other hand, calorimetrically determined
formation calculated: −2411.7 kJ/mol). These values were heat of combustion was of secondary importance in this case,
therefore very similar. However, it should be remembered because the algorithm used to calculate the value of heat of
that this reagent had a degree of purity of about 95% (ac- combustion for individual triglycerides in the course of calcu-
cording to the Sigma-Aldrich specification) and contained lations estimated calorimetrically determined values according
admixtures of other triglycerides. to imposed assumptions (discussed in the testing methodology).
The obtained results were also compared with the works [6, 9, It should be noted that the determined heat values of the com-
10]. It was found that they are consistent with the previous data. bustion of vegetable oils, theoretically, could be at almost the
In work [6], the heat of triglyceride formation was considered same level for most samples, taking into account the uncertainty
in the context of partial reactions of lipid hydroconversion. In of the methodology according to PN 86/C-04062. In fact, the
works [9] and [10], the directions of glyceride transformations maximum difference between the obtained heat of combustion
during catalytic hydroconversion and the thermal effects accom- values of all vegetable oils and their mixtures was 498 kJ/kg. On
panying this process were investigated. the other hand, the difference was greater than 318 kJ/kg for only
The calculations were verified for vegetable oils and their three samples, while the number of all samples was fourteen.
mixtures, comparing their heat of combustion obtained by two Estimating the uncertainty of the determined heat values for
separate methods: based on the content of model triglycerides the formation of model triglycerides is very important because of
and calorimetrically. It was found that the heat of combustion the usefulness of these parameters to develop a thermodynamic
values determined by these methods are comparable; their differ- model of hydroconversion [9, 10]. Such estimation was carried
ence was a maximum of 155 kJ/kg, and therefore was definitely out in work [7] for the value of heat of creation determined for
lower (twice) than the allowable uncertainty value for the calo- the methodology using fourteen vegetable oils. Referring to the
rimetric method according to PN 86/C-04062 (± 318 kJ/kg), but methodology described in [7], as well as to the methodology of
also significantly lower than the maximum difference obtained this paper, it was found that the uncertainty of the determined

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14 Science, Technology and Innovation Original Research

values is primarily affected by the accuracy of the determination The last part of the discussion was the assessment of the
of fatty acid composition in triglycerides, and to a lesser extent usefulness of the presented method for estimating the heat of
the accuracy of the determination of the heat of combustion. combustion of vegetable oils other than those used to determine
Initial refining of samples and the use of average values for the heat of combustion of triglycerides, in connection with the
calculations, from several measurements, improves precision [7]. assessment of the effect of refining these oils with JELTAR 300
It should be noted that the poor precision of the trace fatty acids bleaching earth on their heat of combustion. For selected veg-
in vegetable oils, below 1% (e.g., lignoceric, behenic, nervonic etable oils: soybean oil, sesame oil and olive oil, good compli-
acid) carries a high risk of mistake. Taking into account the ance of the calculated heat of combustion with calorimetrically
obtained results, the measurement uncertainty in determining determined heat was found (Table 5). For the tested oils, the
the heat of formation of model triglycerides was estimated to differences found did not exceed 93 kJ/kg. The obtained results
be less than ± 5%, which for the molar heat of formation of could therefore indicate a small impact of the initial refining of
2000 ÷ 3000 kJ/mol is ± (100 ÷ 150) kJ/mol. This result was vegetable oils on the estimation of the heat of combustion using
similar to the one in [7]. the accounting method.

Table 5. Heat of combustion of selected natural oils, pre-refined and not refined, determined calorimetrically in comparison to
calculated value

Vegetable natural oil Combustion heat (oils unrefined) Combustion heat (oils refined) Combustion heat calculated [kJ/
[kJ/kg] ± 318 kJ/kg [kJ/kg] ± 318 kJ/kg kg]

Olive oil 39706 39799 39768

Sesame oil 39504 39525 39550
Soybean oil 39372 39391 39458

Summary and Conclusions related to the uncertainty of their determination was estimated
at about 100–150 kJ/mol.
The molar heat of formation of model fatty acid triglycerides
contained in natural vegetable oils was calculated with good References
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