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Cost , Energy and Material

Analysis of Biodiesel
Production Using
Homogeneous and
Heterogeneous Catalyst

Prepared by:
Nik Nor Azrizam Bin Nik Norizam 11609 (ID Number)
Muhamad Hazim Bin Azemi 11605 (ID Number)
Introduction


Biodiesel definition
üProduct of the reaction of an alcohol (methanol or
ethanol) with a animal fat or vegetable oil to
form glycerol, mono-alkyl esters of fatty acids
and excess methanol.
üCatalyst is used during the formation of biodiesel.
Purpose of biodiesel production
üPromising alternative to conventional petroleum
based diesel fuel.
üAnswer to overcome global warming by reducing
carbon dioxide and nitrogen dioxide gas emission.



Advantages of biodiesel
üDerived from a renewable domestic resource
(vegetable oil).
üReduces carbon dioxide emissions by 78% compared
to diesel fuel.
üNon-toxic and biodegradable.
üEnvironmental fuel.
Methods to Produce Biodiesel
a) Using supercritical methanol.
b) Using fast and slow pyrolysis.
c) Using catalyst.



 Reason using catalyst method in biodiesel production
ü Convenient to use catalyst in small scale
operation.
ü Easy to conduct experiment in laboratories.
ü More cheaper compare to other methods.
ü No need additional equipment.

v

Overview

To compare biodiesel production using homogeneous and
heterogeneous catalysts.
To study on how homogeneous and heterogeneous catalysts
will affect on material, energy and cost for the
process.
To compare effectiveness of homogeneous and
heterogeneous catalysts towards biodiesel production.
All simulation and modeling are done using MATLAB
software and it based on small scale batch mode
process.
3 factors are being studied which are materials, energy
and cost.
üThey contribute the most in determining which
catalyst is the best.
üTo see effect of all three factors towards
environment and business.
üAll the factor can be related to each other.
 Process Diagram for Both
Homogeneous and
Heterogeneous Catalysts
 ( Base Line )
Figure 1 : Homogeneous Catalyst Process Diagram
Figure 2 : Heterogeneous Catalyst Process Diagram
 Equipment Modeling

Heat to raise temperature (Q raise)
 This heat is required to increase temperature of the system
to operating temperature and is define as


Q raise =m i C p i (T f −T i)
 Heat Released by conduction or by convection (Q out
conduction / Q out convection)
 This heat occurs when there is temperature different
between equipment and surrounding.


Q out convection = [ h air Aequipment (T equipment −T air )] ×total time


(T equipment −T air )
 Q out conduction = [k equipment A equipment ] × total time
( x1 − x 2 )


 Heat of reaction (Q reaction)


 This heat occurs due to chemical reaction from two or more
substances. There are two type heat of reaction which is exothermic and
endothermic heat of reaction. Exothermic heat of reaction will release heat
from the system to environment and for endothermic reaction will require
heat for reaction to take place
 Qrxn = ∆H of @ 25°C + ∆H @T out


∆ H of @ 25° C = ∑ (ni ∆ H of i ) product− ∑ (ni ∆ H of i ) reactan t

∆ H @T out= ∑ (ni C pi) prod(T − T @ 25° C) − ∑ (ni C pi) reactant (T − T @ 25° C)


 Heat to maintain temperature (Q maintains)
 This heat is required for the system to maintain its operating
temperature for period of time until the process is done.

 For exothermic reaction


 Q ma int ain =Q out convection / conduction −Q rxn


 For endothermic reaction


Q ma int ain =Q out convection / conduction +Q rxn

 Heat Release by temperature drop (Q drop)


 This heat is due to cooling down substance before going to next
process.

Q drop =m i C p i (T f −T i)
 HEATING TANK (PREHEATING PROCESS)

In p u t O u tp u t

F e e d in
Q
Temp
in itia l
Temp Feed
fin al out

M o d e l d ia g ra m

Pro ce ss d ia g ra m
 Calculation of Heat Required in Preheating
Process

Q required total =Q raise

Q required total =m veg oil Cp veg oil (T f −T i)

Symbol Definition
Q Heat required (J)
m veg oil Mass vegetable oil enter (kg)
Cp veg oil Specific Heat Capacity
Tf (1670 J/kg K)
Final temperature system
Ti (333K)
Initial temperature system
(298 K)
 OVEN ( CALCIUM CARBONATE DECOMPOSE
PROCESS)

Heat Release Heat Release


by Conduction by temperature
drop

CaCO3

Qrxn

Heat to Heat to
maintain raise
temperature temperature

Pro ce ss d ia g ra m
M o d e ld ia g ra m
Chemical Equation in Decompose
Process
Calculation of Total Heat Required
Q required total =Q raise +Q out conduction +Q reaction
(T oven−T air )
Q required total = [n CaCO 3 C PCaCO3 ](T f −T i) + [(k oven A oven ) × total time × 6]
( x1 − x 2 )
+ (∆H of @ 25°C + ∆H @T out )
where
( ) (
∆H @T out = [ n CaO Cp CaO +n CO 2 Cp CO 2 − n CaCO 3 Cp CaCO 3 ] ×(T out −T @ 25 °C) )
Symbol Definition
k oven Thermal conductivity of cotton (0.03 W/m K)
A oven Surface area of oven (m2)
T oven Temperature inside oven (1073 K)
T air Ambient temperature (308 K)
Total time Time required for process (10800 s)
(x1 – x2) Oven thickness (0.22m)
ΔH ̊f @ 25 Enthalpy formation at 25 C̊
Tf Final temperature (1073 K)
Ti Initial temperature (308 K)
Calculation of Total Heat Wasted
Q wasted total = (Q out conduction × total time ) +Q drop

(T oven−T air)
Q wasted total = [k ovenA oven × total time× 6] + n CaOC p CaO (T f −T i)
( x1 − x 2 )

Symbol Definition
k oven Thermal conductivity of cotton (0.03 W/m K)
A oven Surface area of oven (m2)
T oven Temperature inside oven (1073K)
T air Ambient temperature (308K)
Total time Time required for process (10800 s)
(x1 – x2) Oven thickness (0.22 m)
Tf Final temperature (1073 K)
Ti Initial temperature (308 K)
 MIXER TANK (MIXING PROCESS)

Pro ce ss d ia g ra m

M o d e ld ia g ra m
Chemical Equation in Mixing Process

For Homogeneous Catalyst

Potassium Methanol Potassium Water


hydroxide methoxide

For Heterogeneous Catalyst

Calcium Methanol Calcium Calcium


Oxide methoxide hydroxide
 Calculation of heat in mixer:

1 For homogeneous catalyst (endothermic)


ØHeat released total
ØHeat required total

1 For heterogeneous catalyst (exothermic)


ØHeat released total
ØHeat required total

 Calculation for Heat Wasted from Mixer for
Homogeneous and Heterogeneous Catalyst

 - Heat release from mixer using homogeneous and


heterogeneous is the same using convection
mode.

Q wasted total = [[h air Amixer (T mixer −T air )] × total time ]

Symbol Definition
Q wasted total Heat released by system (J)
h air Heat transfer coefficient
(50 W/m2 K)
A mixer Area of mixer (m2)
T mixer Temperature mixer (333 K)
T air Temperature air (308 K)
Total Time Total Time for mixing
process (1800 s)
 Calculation of Total Heat Required for
Homogeneous Catalyst

 - Since the reaction of methanol and potassium


hydroxide is endothermic, we must add heat of
reaction in heat required total calculation.

Q required total =Q raise +Q ma int ain

Q required total =Q raise +Q out convection +Q reaction


where ( ) ( )
∆ H @T out= [ n K (CH 3)O CpK (CH 3)O + n H 2O CpH 2O − n CH 3OH CpCH 3OH + n KOH CpKOH ] × (T out−T @ 25° C)

Symbols Definition
Cp CH3OH Specific heat capacity of methanol (86.2 J/mol K)
Cp KOH Specific heat capacity of potassium hydroxide
( 49.4626 J/mol K)
Tf Temperature final of system (333 K)
Ti Temperature initial of system (308 K)
ΔH ̊f @25 ̊C Standard enthalpy formation of product at 25 ̊ C
(J/mol)
h air Heat transfer coefficient of air (50W/m2 K)
A mixer Area of mixer (m2)
T mixer Temperature mixer (333 K)
T air Temperature air (308 K)
Time Total Time for mixing process (1800 s)
 Calculation of Total Heat Required for
Heterogeneous Catalyst

 - Since the reaction of methanol and calcium oxide


is exothermic, we can use the heat release by the
reaction process as heat to maintain system
temperature.

 Q required total =Q raise +Q ma int ain

Q required total =Q raise +Q out convection −Q reaction


Q required total = [n CH 3OH C P CH 3OH + n KOH C P KOH ](T f −T i) + [h air Amixer (T mixer−T air)] × time
− (∆H of @ 25°C + ∆H @T out )
where
( ) ( )
∆ H @T out= [ n Ca(OCH3) 2 CpCa(OCH3) 2 + n Ca(OH ) 2 CpCa(OH ) 2 − n CH 3OH CpCH 3OH + n CaO CpCaO ] × (T out−T @ 25° C)
Symbols Definition
Cp CH3OH Specific heat capacity of methanol (86.2 J/mol K)
Cp CaO Specific heat capacity of Calcium Carbonate
(44.1036 J/mol K)
Tf Temperature final of system (333K)
Ti Temperature initial of system (308K)
ΔH ̊ f @25 ̊ C Standard enthalpy formation of product at 25 ̊ C
(J)
h air Heat transfer coefficient of air (50W/m2 K)
A mixer Area of mixer (m2)
T mixer Temperature mixer (333K)
T air Temperature air (308K)
Time Total Time for mixing process (1800 s)
 BATCH REACTOR (TRANSESTERIFICATION
PROCESS)
 Process diagram

Model diagram
 Chemical Equation for Transesterification Process

C h e m ica l e q u a tio n u sin g h o m o g e n e o u s ca ta lyst


( exothermic )

Feedstoc Methanol Biodies Excess


k el Methanol

C h e m ica l e q u a tio n u sin g h e te ro g e n e o u s ca ta lyst


( exothermic )

Feedstoc Methanol Biodies Excess


k el Methanol
 Calculation of Heat Wasted for Homogeneous
and Heterogeneous Catalyst

 - Heat release from reactor using homogeneous


and heterogeneous is the same using convection
mode.


Q wasted total = [[h air Areactor (T reactor−T air)] × total time]

Symbol Definition
 Q wasted total Heat released by system (J)
 h air Heat transfer coefficient

A reactor (50
AreaW/m2 K) (m2)
of mixer
T reactor Temperature reactor (333
T air K)
Temperature air (308 K)
Total Time Total Time for mixing
process (3600 s)
 Calculation of Total Heat Required for
Homogeneous and Heterogeneous Catalyst

 - Since the reaction for potassium hydroxide and


calcium oxide with vegetable oil is exothermic, thus
calculation of heat required total is :


Q required total =Q ma int ain


Q required total =Q out convection −Q reaction
Q required total = [ h A
air reactor(T −
reactor T air) × total time] − [ ∆ H f @ 25° C + ∆ H @T out ]
o

Where,

[
∆H @ T = ( n glycerol C P glycerol ) + (n FAME CP FAME ) + (n excess MeoH CP excess MeOH ) ] prod (T −T @ 25°C ) −
[( n veg oil CP veg oil ) + (n initial MeOH CP initial MeOH ]
) reac tan t (T −T @ 25°C ) ( 6)

Symbols Definition
ΔH ̊ f @ 25 ̊ C Standard enthalpy formation of product at 25 ̊ C
(J)
ΔH ̊ @ T out Enthalpy of formation of product at operating
temperature (J)
h air Heat transfer coefficient of air (50 W/m2 K)
A reactor Area of reactor (m2)
T reactor Temperature reactor (333 K)
T air Temperature air (308 K)
Total time Total Time for mixing process (3600 s)
 GRAVITY SETTLER (GLYCEROL SEPARATION
PROCESS)

Process diagram for Process diagram for


homogeneous catalyst heterogeneous catalyst
Model diagram for homogeneous
catalyst

Model diagram for heterogeneous


catalyst
 Calculation of Heat Wasted for Homogeneous and
Heterogeneous Catalyst
 For homogeneous Q wasted total =Q drop subs tan ce
Q wasted total =Q MeOH +Q FAME +Q Glycerol +Q KOH

[
Q w asted total= (n M eO HC p M eO H ) + (n F A M EC p ) + (n gly C p
FAM E gly ) + (n K O H C p ]
) × (T f − T i )
KOH

Symbol Definition
n MeOH Mol of methanol (mol)
Cp MeOH Specific heat capacity methanol (86.2 J/mol K)
n FAME Mol of FAME(mol)
Cp FAME Specific heat capacity FAME (1.274 J/mol K)
n gly Mol of glycerol(mol)
Cp gly Specific heat capacity glycerol
( 229. 3 J/mol K)
n KOH Mol of potassium hydroxide (mol)
Cp KOH Specific heat capacity potassium hydroxide
(49.4626 J/kg K)
Tf Final temperature system (308K)
Ti Initial temperature system ( 333 K)
- For heterogeneous
catalyst
Q wasted total =Q drop subs tan ce

Q wasted total =Q MeOH +Q FAME +Q Glycerol

Q wasted total [
= (n MeOHC p M eOH ) + (n FAM EC p FAM E ) + (n gly C p gly ]
) × (T f − T i)
Symbol Definition
m MeOH Mass of methanol (mol)
Cp MeOH Specific heat capacity methanol (86.2 J/mol K)
m FAME Mol of FAME (mol)
Cp FAME Specific heat capacity FAME (J/mol K)
m gly Mol of glycerol (mol)
Cp gly Specific heat capacity glycerol(229.3 J/mol K)
Tf Final temperature system (308K)
Ti Initial temperature system (333K)
 HEATING TANK (METHANOL REMOVAL PROCESS)

Process diagram for Process diagram for


homogeneous heterogeneous
catalyst catalyst
Model diagram for heterogeneous
catalyst

Model diagram for homogeneous catalyst


Calculation of Total Energy Required for
Homogeneous and Heterogeneous Catalyst

Q required total =Q raise 1 +Q vaporizati on methanol +Q raise 3


Calculation of Energy Required for Homogeneous and
Heterogeneous Catalyst

Q required total =n MeOH C p MeOH (T f 1−T i1) +n MeOH ∆H vaporizati on+n MeOH C p MeOH (T f 2−T i 2)

Symbol Definition
n MeOH Mol of methanol (mol)
Cp MeOH Specific heat capacity methanol
Tf 1 (86.2 temperature
Final J/mol K) process 1
Ti 1 (308
InitialK)temperature process 1
n MeOH (338)
Mol methanol (mol)
ΔH vaporization Enthalpy of vaporization
Tf 2 methanol (35.3 kJ/mol)
Final temperature process 2
Ti 2 (353
InitialK)temperature process 2
( 338 K)
 PURIFICATION TANK (POTASSIUM
HYDROXIDE PURIFICATION PROCESS)

Process Diagram
Model Diagram
Calculation for Amount of Water Needed
Calculation of Final Temperature of
Product
m H 2O C p H 2O (T f −T i H 2O ) =m mix C p mix (Ti mix −T f )

Symbol Definition
m H2O mass of water (g)
Cp H2O Specific heat capacity of water
Tf (Final J/g K)
4.1813temperature FAME with
Ti H2O water (K)
Initial temperature H2O (308 K)
m mix Mass of FAME with KOH (g)
Cp mix Specific heat capacity of FAME
Ti mix with KOH
Initial (J/g K) of FAME
temperature
with KOH (353 K)
 DRYER (MOISTURE REMOVAL PROCESS)

Process diagram
Model diagram
Calculation of Heat Required for
Homogeneous Catalyst

Q required total =Q raise 1+Q vaporizati on water +Q raise 3


Q required total = n H 2O C p H 2O (T f 1−T i1) + n H 2O ∆H vaporization+ n H 2O C p H 2O (T f 2−T i 2)

Symbol Definition
n water mol of water (mol)
Cp water Specificheat capacity of water
Tf 1 (75.327temperature
Final J/mol K) process 1
Ti 1 (373
InitialK)temperature process 1
ΔH vaporization (from
EnthalpyTf purification process)
of vaporization of
Tf 2 water temperature
Final (40.65 kJ/mol)
process 2
Ti 2 (393
InitialK)temperature process 2
(373 K)

Parameter
selection
Catalyst Homogeneous Heterogeneous
Mass of vegetable oil enter system 90 kg 90 kg
Mass of methanol recover 0 kg 0 kg
Surface area of mixer 0.0628319 m2 0.1099557 m2
Surface area of reactor 0.6126106 m2 0.6283185 m2
Temperature enter preheating process 35 °C 35 °C
Temperature leave preheating process 60 °C 60 °C
Temperature enter mixing process 35 °C 35 °C
Temperature leave mixing process 60 °C 60 °C
Temperature enter transesterification process 60 °C 60 °C
Temperature leave transesterification process 60 °C 60 °C
Temperature enter separation process 60 °C 60 °C
Temperature leave separation process 35 °C 35 °C
Temperature enter removal process 35 °C 35 °C
Temperature leave removal process 80 °C 80 °C
Temperature of mixture ( FAME + KOH ) enter purification 35 °C -
process
Temperature leave drying process 120 °C -
Weight percentage of methanol in FAME 60 % 60 %
Fraction of water in FAME 0.01 -
Solubility of KOH in water 1.21 kg/L -
Area of pipe for heat recovered from methanol removal 0.7539822 m2 1.5707963 m2
Temperature of heat recovered leave 35 °C 35 °C
Temperature of heat recovered enter 80 °C 80 °C
Temperature of water 35 °C 35 °C
Mass of CaO recover from filtration process - 0

Thermal conductivity of oven - 0.03

Thickness wall of oven - 0.22

Area of oven - 0.1275 m2


Temperature enter decompose process - 35 °C

Temperature outside oven - 35 °C

Temperature inside oven - 800 °C

Decomposition time - 10800 s / 3 hours

Table 1 : Parameter Selection

Table 2 : List of Chemical Price


Simulation Result &
Discussion for One Batch
 ( Base Line )
Heterogeneous
Homogeneous Heterogeneous
Homogeneous Heat He ter oge neo us Hea t
Wasted Wa ste d
Homogeneous Heterogeneous
Simulation Result &
Discussion for Multiple
Batches
( Base Line )
 Process Diagram for Both
Homogeneous and
Heterogeneous Catalysts
 ( Case 1 - Heat Recovered

from Methanol Recycle


Stream )
Figure 3 : Homogeneous Catalyst Process Diagram with Heat Recovered
Figure 4 : Heterogeneous Catalyst Process Diagram with Heat Recovered
 Equipment Modeling
 For Case 1
 HEAT RECOVERED PROCESS

Process Diagram
Heat out from
methanol vapor

Hot
Cold water
methanol

Heat in to cold
water

MeOH recovered
Area pipe hot
MeOH
Final Temp Time
MeOH
Vapor MeOH
temperature Heat Recovered
Water
temperature

Model Diagram
Physical Diagram for Heat Recovered Process

Assumptions use :
-Heat release by methanol occur by convection mode only.
-We don’t take into account heat release by conduction mode.
-Total Heat loss from methanol will be absorb by water.
-No heat loss from water to environment.
-We assume temperature of final methanol after heat recovered is 35 ̊ C
(liquid form).
Calculation of Heat Wasted from Methanol
Stream

Q methanol released = Q drop 1+ Q condensation + Q drop


methanol 3
Q methanol released = n MeOH C p MeOH (T f −T i) + n MeOH ∆H vaporization+ n MeOH C p MeOH (T f −T i)
Since, we specify final temperature of methanol after recovered
process, thus we simplify how long for hot methanol must be in
contact with water so that our final temperature that we want
can be achieve. Thus,
Qmethanol release =Q absorb water
Thus,

n M eOHC p M eOH (T f − T i) + n MeOH∆ H condensation+ n M eOHC p M eOH (T f − T i) = h H 2O AM eOH pipe (T water− T M eOH) × total time
Symbol Definition

ΔH condensation of methanol Enthalpy of condensation of methanol (35.3


kJ/mol)
T MeOH Temperature methanol from methanol removal
process (353K)
T water Initial water temperature (308 K)

h h2O Heat transfer coefficient of water 5000 W/m2 K

A MeOH pipe Area of pipe that carry hot methanol (m2)


 Simulation Result &
Discussion for Multiple
Batches
 ( Case 1 – Heat Recovered

from Methanol Recycle


Stream )
 Sensitivity Analysis
Graph Total Cost ( after 16 Batches with 90 kg of vegetable
oil )
VS Price of KOH / CaCO3 ( fixed CaCO3 price = 900 Baht / kg )
Graph Total Cost ( after 16 Batches with 90 kg of vegetable
oil ) VS Price of Water / MeOH ( fixed MeOH price = 184 Baht / L )
Conclusion & Recommendation

1.
2. Both homogeneous and heterogeneous catalysts have their
own advantage and disadvantage.
3. Even heterogeneous catalyst can be reused until 13
times, it still required more cost than homogeneous
catalyst.
4. From our project, we conclude that homogeneous catalyst
is better than heterogeneous catalyst at certain
conditions.
5. Using sodium methoxide catalyst for this biodiesel
production can lead towards better or clear phase
separation between FAME, glycerol and excess methanol.
6. For further improvement towards the biodiesel
production process, heat recovered from methanol can
be apply to purification process.
 References
1.
2.
3. Alex H. West, Dusko Posarac and Naoko Ellis. (2007).
Simulation, Case Studies and Optimization of a
Biodiesel Process with a Solid Acid Catalyst.
INTERNATIONAL JOURNAL OF CHEMICAL REACTOR
ENGINEERING, Vol. 5 (2007), Article A37, 1-8.
4. Alex H. West, Dusko Posarac and Naoko Ellis. (2008).
Assessment of four biodiesel production processes
using HYSYS. Plant. Bioresource Technology, 99 (2008),
6587-6601.
5. Y. Zhang, M.A. Dube, D.D. Mc Lean, M. Kates. (2003). Biodiesel
production from waste cooking oil: 1. Process design
and technological assessment. Bioresource Technology,
90 (2003), 1-16.
6. Y. Zhang, M.A. Dube, D.D. Mc Lean, M. Kates. (2003). Biodiesel
production from waste cooking oil: 2. Economic
assessment and sensitivity analysis. Bioresource
Technology, 90 (2003), 229-240.

5.
6. J.M. Marchetti, V.U. Miguel, A.F. Errazu. (2008). Techno-
economic study of different alternatives for
biodiesel production. FUEL PROCESSING TECHNOLOGY, 89
(2008), 740-748.
8. Tsutomu Sakai, Ayato Kawashima, Tetsuya Koshikawa. (2009).
Economic assessment of batch biodiesel production
processes using homogeneous and heterogeneous alkali
catalysts. Bioresource Technology, 100 (2009), 3268-
3276.
9. Albert J. Gotch, Aaron J. Reeder, and Aleesha McCormick.
(2008). STUDY OF HETEROGENEOUS BASE CATALAYSTS FOR
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Q & A
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