ILASS – Europe 2013, 25th European Conference on Liquid Atomization and Spray Systems, Chania, Greece, 1-4 September

2013

Biodiesel fuel droplets: transport and thermodynamic properties

Ruslana Kolodnytska1, Mansour Al Qubeissi2 and Sergei S Sazhin2

1: Department of Mechanical Engineering, Zhytomyr State Technological University, Chernyahovskogo,

103, Zhytomyr 10005, Ukraine, e-mail: ruslanakol@yahoo.com
2: Sir Harry Ricardo Laboratories, School of Computing, Engineering and Mathematics,
University of Brighton, Brighton BN2 4GJ, UK

Abstract

A detailed comparative analysis of transport and thermodynamic properties of biodiesel fuels and
components of these fuels is presented. Five types of biodiesel fuels are considered: Palm Methyl
Ester, produced from palm oil; Hemp Methyl Esters, produced from hemp oil in the Ukraine and
European Union; Rapeseed oil Methyl Ester, produced from rapeseed oil in the Ukraine; and Soybean
oil Methyl Ester, produced from soybean oil. Up to 16 components (methyl esters in most cases) of
these fuels are considered. The results are applied to the analysis of biodiesel fuel droplet heating and
evaporation in conditions relevant to internal combustion engines, using the model described
elsewhere.

Introduction
As an alternative to Diesel fuel biodiesel fuels have been developed (1). The dominant oils for production of
these fuels are rapeseed oil in Europe, soybean oil in the USA, and palm oil in Asia (2). The ‘second-generation
biodiesels’ have been produced from inedible oil or algae (3); hemp biodiesel has been produced from waste (4).
Most studies of biodiesel fuels have focused on rapeseed, soybean and palm oil biodiesels (5). This paper
concentrates upon the investigation of biodiesel transport and thermodynamic properties in view of the
application of the results to the modelling of fuel droplet heating and evaporation.

Biodiesel fuels
Five types of biodiesel fuel are considered: Palm Methyl Ester (PME), produced from palm oil (6); Hemp
Methyl Esters, produced from hemp oil in the Ukraine (HME1) (4) and European Union (HME2) (7); Rapeseed
oil Methyl Ester (RME), produced from rapeseed oil in the Ukraine (5); and Soybean oil Methyl Ester (SME),
produced from soybean oil (8).
The Sauter Mean Diameters (SMD) of biodiesel and Diesel fuel droplets at temperature 80C, as reported in (9,
10), are shown in Table 1.

Table 1. The Sauter Mean Diameters (SMD) of biodiesel and Diesel fuel droplets at temperature 80C.

Reference PME HME1 HME2 RME SME Diesel

(9) 25.1 m - - 28.8 m 25.7 m 17.7 m
(10) - 23.55 m 23.55 m 26.69 m 23.87 m 18.3 m

The average values of SMD of biodiesel fuel droplets (25.32 μm) are larger than those of Diesel fuel droplets
which can be attributed to the higher viscosity of biodiesel fuels (10).

Chemical formulae and molar fractions of components of biodiesel fuels (methyl esters) are shown in Table 2.

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 25th ILASS – Europe 2013 Biodiesel fuel droplets, transport and thermodynamic properties

Table 2. Molar fraction and chemical formulae of components (pure methyl esters) for 5 biodiesel fuels.

Components Chem. form. PME HME1 HME2 RME SME

С12:0 М C13H26O2 0.0026 0.0000 0.0000 0.0000 0.0000
С14:0 М C15H30O2 0.0129 0.0000 0.0000 0.0000 0.0000
С16:0 М C17H34O2 0.4513 0.0662 0.0651 0.0495 0.109
С17:0 М C18H36O2 0.0000 0.0021 0.0000 0.0000 0.0000
С18:0 М C19H38O2 0.0447 0.0206 0.0246 0.0167 0.044
C20:0 М C21H42O2 0.0035 0.0045 0.0090 0.0056 0.004
C22:0 М C23H46O2 0.0000 0.0025 0.0000 0.0000 0.0000
С24:0 М C25H50O2 0.0000 0.0023 0.0000 0.0000 0.0000
С16:1 М C17H32O2 0.0021 0.0033 0.0000 0.0000 0.0000
С18:1 М C19H3602 0.3839 0.1188 0.1188 0.2671 0.240
C20:1 М C21H40O2 0.0017 0.0027 0.0090 0.0000 0.0000
C22:1 М C23H44O2 0.0000 0.0017 0.0000 0.2204 0.003
С24:1 М C25H48O2 0.0000 0.0015 0.0000 0.0077 0.0000
С18:2 М C19H34O2 0.0916 0.5671 0.5482 0.2484 0.528
С18:3 М C19H32O2 0.0019 0.2067 0.2007 0.0973 0.072
Other 0.0038 - 0.0246 0.0873 -

The numbers of carbons in fatty acids ( nacid ) and numbers of double bonds (DB) are shown by the numbers on
the left and on the right of ‘:’ respectively in the expressions for the components. For example, C18:2 M has
nacid = 18 and DB = 2. The total number of carbon atoms in methyl esters is equal to nacid +1.

Transport and thermodynamic properties of liquid components

The methyl ester density shown in Table 2 is estimated based on the following formula which is valid in the
temperature range 288.15 T Tcr (11):
l  l 0 T (T  288.15) , (1)
where
250.718DB  280.899 7.536
l 0  851.471  , T   0.446 .
1.214  nacid ln( nacid )  3.584
The methyl esters’ kinematic viscosity in the temperature range T  0.7 Tcr in the case of saturated molecules
(DB=0) is estimated as (12):
 
ln  l  106  2.177  0.202nacid 
403.66 109.77nacid
T

T
; (2)
in the case of unsaturated molecules (DB>0), it is estimated using the Orrick and Erbar method (13):
  106 B
ln l l  Ak  k , (3)
l (20) M T
where l ( 20) is liquid density at T = 293.15 K.
The molar latent heat of evaporation of components is estimated as (14):
L  (aL  bL M ) L , (4)
where
Tcr  acr  bcr M , Tb  ab  bb M , (5)
0.38
 T T 
 L   cr  . (6)
 Tcr  Tb 

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 25th ILASS – Europe 2013 Biodiesel fuel droplets, transport and thermodynamic properties

Eq. (4) gives good agreement with experimental data (15) for saturated molecules as shown in Fig. 1.
160

140

120
L (kJ/mol)

100

80
L (modelling)
60 L (experiment)

40
12 14 16 18 20 22 24
Number of carbons

Figure 1. Latent heat of evaporation at 298.15 K for saturated methyl esters against experimental data (15).

The liquid heat capacity and liquid thermal conductivity of components are estimated as (14,13):
cl  (a pl  b plT  c plT 2 )103 , (7)
A * Tb1.2 (1  Tr ) 0.38
kl  , (8)
MTcr0.167 Tr 1/ 6
T
where Tr  .
Tcr
Eqs. (4), (7), (8) are used in our analysis for temperatures from 300 K up to the critical temperature. The
coefficient A* in Eq. (8) was set at A*= 0.0713 which is different from A*= 0.0415 suggested by Latini (13).
The values of coefficients in Eqs. (3), (4), (5), (6), (7) are given in Table 3 (16, 17). The values for C18:3M in
Eqs. (4), (7) have been obtained via the linear extrapolation of the values of coefficients for C18:1M and C18:2
M.

Table 3. The values of coefficients used in Eqs. (3) - (7).

Coefficients C12:0 M – C24:0 M C16:1 M – C24:1 M C18:2 M C18:3 M

Ak - -10.83 -9.93 -9.03
Bk - 2099 1721 1343
ab 348.7 350.4 352.1 353.82
bb 0.8478 0.8463 0.8463 0.8472
acr 534.3 538.5 542.6 546.8
bcr 0.784 0.777 0.772 0.7711
aL 1.506  10 7
1.389  10 7
1.270  10 7
1.154  107
bL 1.814  105
1.822  10
5
1.834  10 5
1.843 105
(Tcr  Tb )0.38 7.027 7.047 7.067 7.087
a pl 1.816 1.915 2.018 2.115
b pl - 1.4 62 10-3 - 2.16310-3 - 2.87810-3 - 3.580 10-3
c pl 7.5110-6 8.2910-6 9.09 10-6 9.92 10-6

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 25th ILASS – Europe 2013 Biodiesel fuel droplets, transport and thermodynamic properties

The liquid diffusivity of biodiesel Dl is estimated using the Wilke-Chang approximation (13) assuming that
liquid diffusivity is the same for all components:
7.4  10 15 M v T
Dl  , (9)
lVv0.6
where M v is the average molar mass of components,  l is the liquid dynamic viscosity, kg m-1 s-1.
Molar volume Vv at the normal boiling point and Lennard-Jones length  v for individual components is
estimated as (18,19):
Vv  v / 1.183 , (10)
v  1.486M 0.297
. (11)
The plots of liquid diffusivity for PME, SME and HME2 calculated based on Eq. (9) are shown in Fig. 2.

Figure 2. The liquid diffusivity Dl for PME, SME, and HME2 calculated based on Eq. (9).

As one can see from Fig. 2 the highest liquid diffusivity is for PME, the diffusivities for SME and RME are close
to each other, the liquid diffusivity for HME2 is very close to the diffusivity for HME1 (plots are not presented).
An alternative approximation for liquid diffusivity of components was suggested by Hayduk and Minhas (13):
 P 0.5  T 1.29
0
DAB  15.5  1012  0B.42  0.23 0.92 , (12)
 PA  VB  B
where  B is the dynamic viscosity of solvent B, cP; PA and PB are Parahors (see (10,13) for the details) for the
solute and solvent.
The following approximation was derived for liquid diffusivity of saturated molecules (C12:0 M - C24:0 M) at
the temperature 293.15K using Eqs. (12), (10) and (11):
D 0AB  AD 108 e( 0.142nacid ) , (13)
where AD =2 for methyl esters C12:0 M – C24:0 M.

Transport and thermodynamic property of methyl esters vapour

The saturated vapour pressure (in Pa) of pure liquid methyl esters is estimated based on the following general
formula which is valid in the temperature range (260 K < T <610 K) (20):
 c 
pv  103 aCN ,0 auc ( DB  1)  bUC  uc  exp (a CN ,1 nacid ) , (14)
 DB  1
where

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 25th ILASS – Europe 2013 Biodiesel fuel droplets, transport and thermodynamic properties

aCN ,0  1.908 exp[0.01715T ].

aCN ,1  5.656  0.02649T  4.5417 105T 2  2.6571108T 3 ,
for DB  0 or T  323 K, auc  0 , buc  1 , cuc  0 , otherwise,
auc  4.62  105 T 2  3.06  102 T  5.05 , buc  3.39  102 T  9.93 , cuc  2.97  102 T  9.62 .
Using data provided in (21), the following approximation for the vapour heat capacities of the components of
biodiesel fuels in the range of temperatures 300 K< T <1500 K has been derived:
c pv  4184C pv,0C pv,1M 1 ( J kg1K 1 ) (15)
where C pv ,0  (6.37561  n acid  6.6472) ln(T) - 31.361  n acid - 26.118 ,
C pv,1 = exp(0.01105ln( T )  0.0425)DB .
Vapour diffusion coefficients were approximated as (17, 22):
2  10 10 T 1.75
Dv  ,
p
where p is ambient pressure in bars.

Transport and thermodynamic properties of biodiesel fuels

Data presented earlier allow us to calculate average values of liquid density, specific heat capacity, dynamic
viscosity and thermal conductivity for all 5 biodiesel fuels using the mixture rules (23, 24).
Table 3 shows the values of calculated/estimated (27) density and viscosity for RME and calculated/estimated
(28) values of thermal conductivity for RME.

Table 4. The values of calculated liquid density and viscosity versus experimental data (27); and calculated/
estimated thermal conductivity (28) for RME.

Dynamic viscosity Density Thermal conductivity

Temperature Temperature
Measured/Calculated Measured/Calculated Estimated/Calculated
293.15 K 0.0063413/0.0058339 879.6/878.823 300 K 0.17696/0.16423
303.15 K 0.0048825/0.0046859 872.9/871.729 350 K 0.16860/0.15349
313.15 K 0.0038665/0.0038166 865.7/864.634 400 K 0.15991/0.14320
323.15 K 0.0031336/0.0031482 858.3/857.540 450 K 0.15083/0.13306
333.15 K 0.0025883/0.0026269 851.0/850.445 500 K 0.14125/0.12280
343.15 K 0.0021724/0.0022151 843.7/843.350 550 K 0.13104/0.11415
353.15 K 0.0018320/0.0018860 836.4/836.256 600 K 0.11997/0.11317
363.15 K 0.0015837/0.0016198 829.1/829.161
373.15 K 0.0013923/0.0014026 821.7/822.066

As one can see from Table 4, the calculated and experimental data for density and dynamic viscosity are very
close and the agreement between the predicted values of thermal conductivity for both approaches is reasonably
good. The thermal conductivity of biodiesel is higher than that of Diesel fuel (25). Biodiesel produced from
rapeseed oil has a thermal conductivity of 0.153 0.002 Wm-1K-1 (25) (or 0.17 W·m-1·K-1(26)) at 298 K
compared to Diesel fuels, for which the respective value is 0.115 0.002 Wm-1K-1 (25).

Biodiesel droplet evaporation modelling

The above results were applied to the analysis of biodiesel fuel droplet heating and evaporation in conditions
relevant to Diesel engines, using the Effective Thermal Conductivity/Effective Diffusivity (ETC/ED) model (23,
24). Our analysis is focused on the following values of parameters (assuming that the ideal gas law is valid):  a =
11.9 kg/m3, Ta= 880K, pa = 30 bar and assuming that droplets have a velocity of 10 m/s. Fig. 3 shows the results
of calculations using the multi-component evaporation model taking into account the contribution of some or all
of the 16 components shown in Table A2 for SME and HME1. Our results show that HME1 droplets take
slightly longer to evaporate than SME droplets and the surface temperatures of HME1 droplets at the final stage
of droplet evaporation are slightly higher than the ones predicted for the SME droplets or HME2 droplets (plots
for HME2 are very close to SME and are not presented in Fig. 3). The difference in evaporation between HME1
and HME2 can be attributed to the presence or absence of the heaviest components (C22:1 and C24:1 M) in
HME2 and HME1 (see Table 2). A more detailed analysis of biodiesel fuel droplet heating and evaporation is
presented in our parallel paper (29).
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 25th ILASS – Europe 2013 Biodiesel fuel droplets, transport and thermodynamic properties

Conclusion
A detailed comparative analysis of transport and thermodynamic properties of biodiesel fuels and components of
these fuels (methyl esters) is presented. The analysis has been focused on five types of biodiesel fuels: Palm
Methyl Ester (PME); Hemp Methyl Esters, produced from hempseed oil in the Ukraine (HME1) and European
Union (HME2); Rapeseed oil Methyl Ester (RME), produced from rapeseed oil in the Ukraine; and Soybean oil
Methyl Ester (SME), produced from soybean oil. Up to 16 components of these fuels are considered. The results
are applied to the analysis of biodiesel fuel droplet heating and evaporation in Diesel engine-like conditions
using the previously suggested model that takes into account temperature gradient and recirculation inside
droplets and species diffusion within them. Our results show that the evaporation time for Hemp Methyl Esters is
very close to that of Soybean oil Methyl Esters.

Figure 3. The plots of SME and HME1 droplet surface temperatures (Ts) and radii (Rd) versus time predicted by
the multi-component model. Gas temperature and pressure are assumed to be equal to 880 K and 30 bar
respectively. The initial droplet radius is assumed to be equal to 12.66 μm. The droplet is assumed to be moving
with a constant velocity equal to 10 m/s.

Acknowledgements
The authors are grateful to the Ministry of Education of the Ukraine, Zhytomyr State Technological University
(Ukraine) and INTERREG IVa (Project E3C3, Reference 4274) for their financial support.

Nomenclature
Symbol Description Unit Subscripts Description
c specific heat capacity J·kg-1·K-1
D diffusion coefficient m2·s-1 A Solute
-
DB number of double bonds a air
k thermal conductivity W·m-1·K-1 B solvent
L latent heat of evaporation J·kmol-1 cr critical
M molar mass kg kmol-1 b boiling
nacid number of carbon atoms in acid - l liquid
p pressure Pa/bar p constant pressure
T temperature K r reduced
V molar volume at boiling temperature sm3mol-1 v vapour
 kinematic viscosity m2·s-1 0 initial
 density kg·m-3
 dynamic viscosity kg m-1 s-1/ cP
Lennard-Jones length 
v A

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 25th ILASS – Europe 2013 Biodiesel fuel droplets, transport and thermodynamic properties

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