[1] J.M. Smith, H.C. Van Ness and M.M. Abbott, Introduction to Chemical Engineering Thermodynamics, 7th edn.
[2] Eugene S. Domalski and Jr Vlastimil Ruzicka, ‘Estimation of the Heat Capacities of Organic Liquids as a Function of
Temperature Using Group Additivity. II. Compounds of Carbon, Hydrogen, Halogens, Nitrogen, Oxygen, and Sulfur’,
JPCRD, 22.3 (1993), 619–57.
[3] Bruce E. Poling and others, ‘Physical and Chemical Data’, in Perry’s Chemical Engineer’s Handbook (McGraw-Hill
eBooks, 2008).
[4] Elizabeth D. Hearing and Eugene S. Domalski, ‘Estimation of the Thermodynamic Properties of C-H-N-O-S-
Halogen Compounds’, Journal of Physical Chemistry Reference Data, 22.4 (1993), 805.
DESCRIPTION
Using the energy balance, the heat supplied by the heat exchanger is calculated. This will allow the reactor to operate
at the desired temperature optimum for the reaction. Estimation of heat capacities and heat of formation at standard
states involves the use of Ruzicka-Domalski and Domalski-Hearing method of correlation of thermodynamic properties,
respectively.
ASSUMPTION(S)/BASIS
1. Liquid heat capacity can be estimated by the summation of the individual group [1]
contribution for organic compounds.
2. The triglyceride of the rice bran oil is composed of triolein.
3. Potential energy, kinetic energy and work is negligible in the system.
4. The standard enthalpy (heat) of formation is the enthalpy change upon formation of 1 mol [3] [2]
of the compound in its standard state from its constituent elements in their standard states.
Therefore, estimation of thermal properties from group contributions in organic compound
is applicable.
NOMENCLATURE(S)
𝐵 = 𝑛𝑔,𝑖 𝑏𝑖 °
∆𝐻𝑓,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝑛𝑟,𝑖 , 𝑛𝑝,𝑖 °
∆𝐻𝑓,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
𝐷 = 𝑛𝑔,𝑖 𝑑𝑖
∆𝐻°𝑟𝑥𝑛 ሺ25°𝐶ሻ
𝐴, 𝐵, 𝐷 𝑅
= 𝑛𝑟,𝑖 ∆𝐻°𝑓,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
〈𝐶𝑝 〉𝐻 𝐵 𝐷 − 𝑛𝑝,𝑖 ∆𝐻°𝑓,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
=𝐴+ 𝑇𝑜 ሺ𝜏 + 1ሻ + 𝑇 2 ሺ𝜏 2 + 𝜏 + 1ሻ
𝑅 100 3ሺ100ሻ2 𝑜
〈𝐶𝑝 〉𝐻 𝑇, 𝑇0
∆𝐻
𝑛̇
̇
∆𝐻𝑟𝑥𝑛 ሺ60°𝐶ሻ
= 𝑛̇ ∆𝐻
̇
∆𝐻
SYSTEM SKETCH
Inlet Stream
Triglyceride TG
4, 068.41
(kg/h)
Free Fatty Acid
30.93 Outlet Stream
FFA (kg/h)
Water (kg/h) 47.83 Triglyceride TG
81.46
(kg/h)
Methanol (kg/h) 7136.62
Free Fatty Acid
Glycerol (kg/h) 656.84 30.93
FFA (kg/h)
FAME (kg/h) 7, 059.17
Water (kg/h) 47.83
Temperature (K) 333.15
Methanol (kg/h) 7, 788.60
Pressure (MPa) 0.128
Glycerol (kg/h) 1, 071.25
Methanol Stream FAME (kg/h) 11, 064.54
Methanol (kg/h) 1084.52 Temperature (K) 333.15
Temperature (K) 333.15 Pressure (MPa) 0.128
Pressure (MPa) 0.128
CALCULATIONS
To find the heat needed to maintain the temperature in the reactor an energy balance is made.
𝑑𝐸 1 ∆𝑃
= −𝑚̇ (∆𝑈 ̂ + 𝑔∆ℎ + ∆𝑣 2 + ) + 𝑄̇ + 𝑊̇
𝑑𝑡 2 𝜌
Potential energy and kinetic energy contribution to energy in the system is considered to be negligible. The work is also
negligible compared to the heat term. Therefore, the energy balance is reduced to:
∆𝑃
−𝑚̇ (∆𝑈 ̂ + ) + 𝑄̇ = 0
𝜌
For the heat transfer in a constant-pressure, closed system process, the enthalpy of the system is equal to U+PV.
Therefore, the balance becomes,
𝑚̇∆𝐻̂ = 𝑄̇
For heat transfer in molar basis,
𝑛̇ ∆𝐻 = 𝑄̇
The equation below calculates for the required heat to sustain the reaction at a temperature that is not at standard
conditions
∆𝐻 = ∆𝐻𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 ሺ60°𝐶 → 25°𝐶ሻ + ∆𝐻°𝑟𝑥𝑛 ሺ25°𝐶ሻ + ∆𝐻𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 ሺ25°𝐶 → 60°𝐶ሻ
To calculate for the total heat that must be added to the system for the reaction triglyceride and methanol to produce
fatty acid methyl ester and glycerol, a one mole of triglyceride is used as basis.
The governing chemical equation is described by Figure 1. From the stoichiometry in the reaction, 1 mole of triglyceride
reacts with 3 moles of alcohol, methanol in this reactor’s case, to form 3 fatty acid alkyl esters and glycerol/glycerin. The
triglyceride in the rice bran oil is assumed to be composed of triolein, therefore, the alkyl ester is methyl oleate.
Figure 1. Transesterification reaction for biodiesel production using a basic catalyst
𝐶𝑝 𝑇 𝑇 2
= 𝐴+𝐵( )+𝐷( )
𝑅 100 100
Where A, B and D are,
𝐴 = 𝑛𝑔,𝑖 𝑎𝑖 𝐵 = 𝑛𝑔,𝑖 𝑏𝑖 𝐷 = 𝑛𝑔,𝑖 𝑑𝑖
Table 1 shows all the individual values of a, b, and d for each group i in the compound.
For A.
𝐴 = 𝑛𝑔,𝑖 𝑎𝑖 = 1 ∙ 0.98790 + 3 ∙ 12.9520 + 2 ∙ 1.45960 = 42.76310
For B,
𝐵 = 𝑛𝑔,𝑖 𝑏𝑖 = 1 ∙ 0.39403 + 3 ∙ −10.14500 + 2 ∙ 1.46570 = −27.10957
For D,
𝐷 = 𝑛𝑔,𝑖 𝑑𝑖 = 1 ∙ −0.01612 + 3 ∙ 2.62610 + 2 ∙ −0.27140 = 7.31938
Table 2 summarizes all the values of A, B, and D for TG, Methanol, Methyl Oleate and Glycerol.
𝑇
Where 𝜏 = , and this expression could be reduced into the equations below to separate the ∆𝑇 (or 𝑇- 𝑇𝑜 )
𝑇𝑜
∆𝐻𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 = 〈𝐶𝑝 〉𝐻 ሺ𝑇 − 𝑇𝑜 ሻ
and
〈𝐶𝑝 〉𝐻 𝐵 𝐷
=𝐴+ 𝑇𝑜 ሺ𝜏 + 1ሻ + 𝑇 2 ሺ𝜏 2 + 𝜏 + 1ሻ
𝑅 100 3ሺ100ሻ2 𝑜
The standard enthalpy (heat) of formation is the enthalpy change upon formation of 1 mole of the compound in its
standard state from its constituent elements in their standard states [3]. Enthalpy of formation of the compounds is
calculated by Domalski-Hearing method which uses group contribution of the groups constituting the organic
compounds to account the heat of formation of the compound.
∆𝐻°𝑓,𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 = 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯
𝑖
Table 5. Individual Group Contribution for the heat of formatiion at standard conditions
TG: Triolein
𝑘𝐽
Group 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ * 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ ( )
𝑖 𝑖 𝑚𝑜𝑙
C-(2C),(H),(O) 1 -21.00 -21.00
C-(2H),(C),(O) 2 -35.80 -71.60
O-(C),(CO) 3 -23.50 -70.50
CO-(C),(O) 3 -149.37 -448.11
C-(C),(CO),(2H) 3 -24.14 -72.42
C-(2C),(2H) 33 -25.73 -849.09
C-(C),(2H),(Cd) 6 -25.73 -154.38
Cd-(C),(H) 6 31.05 186.30
C-(C),(3H) 3 -47.61 -142.83
Methanol
𝑘𝐽
Group 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ * 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ ( )
𝑖 𝑖 𝑚𝑜𝑙
C-(3H,OH) 1 -47.61 -47.61
O-H,C 1 -191.50 -191.50
FAME: Methyl Oleate
𝑘𝐽
Group 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ * 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ (𝑚𝑜𝑙)
𝑖 𝑖
O-(C),(CO) 1 -23.50 -23.50
CO-(C),(O) 1 -149.37 -149.37
C-(C),(CO),(2H) 1 -24.14 -24.14
C-(2C),(2H) 11 -25.73 -283.03
C-(C),(2H),(Cd) 2 -25.73 -51.46
Cd-(C),(H) 2 31.05 62.10
C-(C),(3H) 1 -47.61 -47.61
C-(3H),(O) 1 -47.61 -47.61
Glycerol
𝑘𝐽
Group 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ * 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ ( )
𝑖 𝑖 𝑚𝑜𝑙
C-(2C),(H),(O) 1 -27.60 -27.60
O-(H),(C) 3 -191.50 -574.50
C-(2H)(C)(O) 2 -35.80 -71.60
Sample calculations
∆𝐻°𝑓,𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 𝑛𝑔,𝑖 ൫∆𝐻°𝑓 ൯ = ሺ1ሻሺ−47.61ሻ + ሺ1ሻሺ−191.50ሻ
𝑖
𝑘𝐽
∆𝐻°𝑓,𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = −239.11
𝑚𝑜𝑙
*data taken from [3]
Heat of reaction
∆𝐻 = ∆𝐻𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 ሺ60°𝐶 → 25°𝐶ሻ + ∆𝐻°𝑟𝑥𝑛 ሺ25°𝐶ሻ + ∆𝐻𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 ሺ25°𝐶 → 60°𝐶ሻ
∆𝐻 = −25 484.57455 J + −6 600 𝐽 + 25 484.88929 J
∆𝐻 = −6 599.685263 𝐽
𝐽
Since the calculation is done in 1 mole TG basis, the heat is −6 599.685263 𝑚𝑜𝑙 𝑇𝐺. To calculate for the total Q that
must be added to the system to maintain the reaction at 60°C, multiply the total moles of TG reacted in the system per
hour. Since the conversion changes along the length of the reactor, the total Q is evaluated at different moles of TG
reacted.
̇
𝑛̇ ∆𝐻 = 𝑄𝑡𝑜𝑡
Table 7.
X n (mol reacted TG) L (m) ̇ (KJ/h)
𝑄𝑡𝑜𝑡
0.000 - 0 -
-
0.173 795.85 0.228650227
5,252.34
-
0.316 1,453.91 0.457300454
9,595.37
-
0.435 1,998.04 0.685950681
13,186.44
-
0.533 2,447.95 0.914600909
16,155.69
-
0.614 2,819.94 1.143251136
18,610.74
-
0.681 3,127.51 1.371901363
20,640.59
-
0.736 3,381.81 1.60055159
22,318.86
-
0.782 3,592.05 1.829201817
23,706.40
-
0.820 3,765.87 2.057852044
24,853.57
-
0.851 3,909.58 2.286502271
25,801.98
-
0.877 4,028.38 2.515152498
26,586.05
-
0.898 4,126.60 2.743802726
27,234.25
-
0.916 4,207.79 2.972452953
27,770.11
-
0.930 4,274.91 3.20110318
28,213.09
-
0.942 4,330.40 3.429753407
28,579.29
-
0.952 4,376.27 3.658403634
28,882.00
-
0.961 4,414.18 3.887053861
29,132.22
-
0.968 4,445.52 4.115704088
29,339.06
-
0.973 4,471.43 4.344354315
29,510.04
-
0.978 4,492.84 4.573004543
29,651.36
-
0.980 4,502.94 4.698
29,717.96
35.00
30.00
25.00
-Qtot (kJ/h)
20.00
15.00
10.00
5.00
-
0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000
XTG
35.00
30.00
25.00
-Qtot (kJ/h)
20.00
15.00
10.00
5.00
-
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
L (m)
For X=0.980,
𝑚𝑜𝑙 𝑇𝐺 𝐽
𝑄̇ = 4502.936 (−6 599.685263 )
ℎ 𝑚𝑜𝑙 𝑇𝐺
𝒌𝑱
𝑸̇ = −𝟐𝟗 𝟕𝟏𝟕. 𝟗𝟔𝟐𝟕𝟓
𝒉
From the calculated heat above, the reaction is exothermic and heat should be supplied to maintain the
desired temperature of the system. The rate of heat transfer to the system is a function of conversion and the
𝒌𝑱
maximum heat that must be supplied is −𝟐𝟗 𝟕𝟏𝟕. 𝟗𝟔𝟐𝟕𝟓 𝒉 .
.
A 05/31/2017