Model Of Tubular Reactor

Overall transesterification reaction can be represent by the following reaction shown in Figure 1

Figure 1

The reaction is reversible biased to product and the reaction is exothermic with heat of reaction
range from 34 to 100 kJ/mol of Palm oil converted [ ]. Various kinetic models being purposed
show transesterification as 3 steps reaction. However the overall reaction is being considered for
modeling purpose. The process will involve excess methanol by 6:1 mol ratio of methanol to
palm oil and 1mol of catalyst per 1 kg of oil catalyst loading. The reaction kinetic can be written
as follows:

𝑟𝑎 = −𝑘𝑓 [𝑇𝐺][3𝑀𝑒𝑂𝐻] + 𝑘𝑟 [𝐺][3𝑀𝐸]

The stochiometric table for plug flow system is as follows;

Species Feed Rate Mol Ratio Change Final Rate at Simplified Final
to Reactor with respect Progression Reactor Outlet Change
(mol/s) to TG (mol/s) (mol/s) (mol/s)
TG FTG0 FTGӨTG -FTGX FTGӨTG--FTGX FTG (ӨTG-X)
MeOH FMeOH0 FTGӨMeOH -3FTGX FTGӨMeOH-3FTGX FTG (ӨMeoH-3X)
G FG0 FTGӨG FTGX FTGӨG +FTGX FTG (ӨG+X)
ME FME0 FTGӨME 3FTGX FTGӨME+ 3FTGX FTG (ӨMe+3X)

Plug flow reactor employs such equation;

𝑑𝑋 −𝑟𝑎
=
𝑑𝑉 𝐹𝑇𝐺0

Rearrange equations gives:

𝑋0
𝑑𝑋
𝑉 = 𝐹𝑇𝐺0 ∫
𝑋=𝑋𝑓 −𝑟𝑎

Concentration of every species can be interchange by using equation as below

𝐹𝑇𝐺 = 𝐶𝑇𝐺 𝜐

Substitute the following equation gives;

 𝑋0
𝑑𝑋
𝑉 = 𝐶𝑇𝐺0 𝜈𝑜 ∫
𝑋=𝑋𝑓 −𝑟𝑎

Heat evolved during reaction gives rise to temperature

Adiabatically the temperature can be obtained along the reactor by the following equation:

Δ𝐻𝑅𝑛𝑥 𝑋
𝑇𝑃𝐹𝑅 = 𝑇𝐹𝑒𝑒𝑑 +
𝐹𝑇𝐺0 ∑𝑛𝑖 Θi Cpi

Equilibrium Constant can be expressed in as follows;

𝑘𝑓
𝐾𝐶 =
𝑘𝑟

Adiabatic reactor temperature with initial feed temperature of T=60oC is as follows, initial flow
rate of 1.63309 mol/s with initial 3m3 volume of reactor.

The summary of adiabatic reactor is as follows.

POLYMATH Report No Title
Ordinary Differential Equations 16-Mar-2018

Calculated values of DEQ variables

Variable Initial value Minimal value Maximal value Final value
1 V 0 0 3. 3.
2 X 0 0 0.999999964048 0.999999964048
3 CpT 1.88 1.88 1.88 1.88
4 Ca 808.63 808.63 808.63 808.63
5 CpET 0.32 0.32 0.32 0.32
6 CpG 0.22 0.22 0.22 0.22
7 CpA 0.0863 0.0863 0.0863 0.0863
8 Tinlet 60. 60. 60. 60.
9 Tref 25. 25. 25. 25.
10 Hrnx0 -100.5 -100.5 -100.5 -100.5
11 delCp -0.9589 -0.9589 -0.9589 -0.9589
12 thetaCp 2.3978 2.3978 2.3978 2.3978
13 T 60. 60. 153.1694294032 153.1694294032
14 k2 0.000000162446 0.000000162446 0.0000008884669 0.0000008884669
15 k1 0.0000016166696 0.0000016166696 0.0000377935739 0.0000377935739
16 ra -6.342671697803 -9.4609881928 -3.893920573E-16 -3.893920573E-16

Differential equations
1 d(X)/d(V) = -ra / 1.63309
Conversion Profile

Explicit equations
1 CpT = 1.88
2 Ca = 0.80863 * 1000
3 CpET = 0.32
4 CpG = 0.22
5 CpA = 0.0863
6 Tinlet = 60
7 Tref = 25
8 Hrnx0 = -100.5
9 delCp = CpG + 3 * CpET - CpT - 3 * CpA
10 thetaCp = CpT + 6 * CpA
11 T = Tinlet - X * (Hrnx0 + delCp * (Tinlet - Tref)) / (thetaCp + X * delCp)
12 k2 = (1.251 * (10 ^ (-4))) * exp(-2214.2892 / (T + 273.15)) * ((T + 273.15) / 333.15)
13 k1 = (959.0547/1000) * exp(-4428.6746 / (T + 273.15)) * ((273.15 + T) / 333.15)
meter cubic /mol
14 ra = -k1 * (Ca ^ 2) * (1 - X) * (6 - 3 * X) + k2 * (Ca ^ 0) * (X) * (3 * X)

The reaction seemly does have significant effect on the adiabatic environment as heat of reaction
is moderate and the molar capacity of species is small However from simulation even
considering the reaction is reversible increasing temperature will not affect the reverse reaction
significantly temperature significantly.

From adiabatic reaction curve it can be determined that the volume needed to achieve 99.4%
conversion is 0.26 m3 at inlet temperature T=60 oC whereas the temperature of the reaction peak
up to T=153.17 oC drastically pass over boiling point of methanol T=65oC.

Indeed increase the temperature will increase the reaction kinetic however for safety of the
process the temperature will be raised at maximum of T=68oC and pressure P=1.4atm just above
bubble point of methanol and above methanol vapor pressure at 65oC at P=1 atm. Therefore by
mean of trial and error method at the inlet temperature the maximum temperature of T=68oC is
obtained.

From the simulation in figure 2 the volume needed to meet 99.4% conversion at constant
temperature T=68 is 3.5m3 with inlet temperature of T=10.39oC. In practice, cooling the palm oil
down to T=20oC cause the viscosity of the palm oil to increase which is unfavorable condition
for fluid transferring. Taking the fact that the reaction is exothermic as advantage, removing heat
during reaction can increase the overall reaction, according to Le Chatelier’s principal. This
consideration must include the mechanism of heat transfer that can be done by mean of heat
exchange from reaction vessel with cooling environment such as cooling water.
Overall heat evolved during reaction assuming 100% conversion is 219kJ adiabatically at inlet
temperature T=60oC. The summary of Polymath result is as follows.

POLYMATH Report No Title

Ordinary Differential Equations 17-Mar-2018

Calculated values of DEQ variables

Variable Initial value Minimal value Maximal value Final value
1 V 0 0 3.5 3.5
2 X 0 0 0.999999964048 0.999999964048
3 CpT 1.88 1.88 1.88 1.88
4 Ca 808.63 808.63 808.63 808.63
5 CpET 0.32 0.32 0.32 0.32
6 CpG 0.22 0.22 0.22 0.22
7 CpA 0.0863 0.0863 0.0863 0.0863
8 Tinlet 60. 60. 60. 60.
9 Tref 25. 25. 25. 25.
10 Hrnx0 -100.5 -100.5 -100.5 -100.5
11 delCp -0.9589 -0.9589 -0.9589 -0.9589
12 thetaCp 2.3978 2.3978 2.3978 2.3978
13 T 60. 60. 153.1694294032 153.1694294032
14 k2 0.000000162446 0.000000162446 0.0000008884669 0.0000008884669
15 k1 0.0000016166696 0.0000016166696 0.0000377935739 0.0000377935739
16 ra -6.342671697803 -9.511911482955 -8.620327573E-15 -8.620327573E-15
17 heat 0 0 218.9344871639 218.9344871639

Differential equations
1 d(X)/d(V) = -ra / 1.63309
Conversion Profile

Explicit equations
1 CpT = 1.88
2 Ca = 0.80863 * 1000
3 CpET = 0.32
4 CpG = 0.22
5 CpA = 0.0863
6 Tinlet = 60
7 Tref = 25
8 Hrnx0 = -100.5
9 delCp = CpG + 3 * CpET - CpT - 3 * CpA
10 thetaCp = CpT + 6 * CpA
11 T = Tinlet - X * (Hrnx0 + delCp * (Tinlet - Tref)) / (thetaCp + X * delCp)
12 k2 = (1.251 * (10 ^ (-4))) * exp(-2214.2892 / (T + 273.15)) * ((T + 273.15) / 333.15)
13 k1 = (959.0547/1000) * exp(-4428.6746 / (T + 273.15)) * ((273.15 + T) / 333.15)
meter cubic /mol

14 ra = -k1 * (Ca ^ 2) * (1 - X) * (6 - 3 * X) + k2 * (Ca ^ 0) * (X) * (3 * X)

15 heat = (thetaCp + X * delCp) * 1.63309 * (T - Tinlet)

Specifying the inlet temperature to be T=30oC and outlet temperature of reactor to be T=68oC
and cooling water to be 68oC the overall heat transfer to cooling media can be obtained by using
heat balance equation the temperature different between inlet and outlet for 5kg/s cooling water
is T=9.56oC. As exothermic reaction heat generated can be used to heat the feed with inlet
temperature of T=30oC by energy balance temperature different be lowered as heat is recovered
to heat up the reaction at reactor inlet. Heat exchange can be done by two mode counter current
and co current, the simulation for both mode of heat exchange where the inlet is kept at T=30oC
final discharge temperature of the reactor is T=68oC, by varying the flow rate of cooling water
and cooling water inlet temperature one can obtain the satisfactory economic result for both
parameter without reducing the overall conversion. Based on energy balance equation at steady
state, the cooling water flow rate follows radical function of cooling water inlet temperature,
with asymptote of outlet temperature of cooling water equilibrium. A flow rate of 5kg/s of
cooling water is chosen for this design, and the temperature different is expected to be about
∆T=4.40oC. For selected operating condition, required volume to achieve 99.4% conversion is
V=1.81m3 as shown in simulation below.

The basis volume will be used as reactor volume for PFR is V=1.82m3 , to account any flow rate
overload and temperature fluctuation the volume is scaled up by +20% and the final volume for
the reactor is 2.2m3. However, as expected the hot spot will be occur in near after inlet region of
the reactor where the temperature peak up to almost 80oC, this is due to the nature of PFR with
counter current heat exchanger, from the fact that heat generated from near end of the reactor is
recovered back to near inlet of reactor as a result temperature peak up exponentially and cross
over the controlled temperature, to solve this problem higher flow rate and lower cooling water
outlet must be utilized or much higher inlet temperature of cooling water will be used, lowering
the temperature will lower the overall conversion significantly and higher temperature will pose
major hazard to operating hazard. As for the co current heat exchange mode, from energy
balance equation at steady state, cooling water flow rate is again a rational function of
temperature different. Figure shows cooling water mass flow rate as function of temperature
different. As shown, small change of flow rate will induce small temperature different as
compare to counter current mode. This fact can reduce the fluctuation of temperature due to
fluctuation in cooling water flow rate. Simulation of Co current mode heat exchanger in figure
below at cooling water inlet temperature of T=63oC and mass flow rate of 2.8kg/s. Co current
mode is designed based on temperature different rather than mass flow rate from counter current
mode. The temperature profile of reactor shows that the controllability of the temperature is
difficult for co current exchange mode despite of inefficient temperature control, the temperature
does not spike like counter current exchanger and this one of good advantage in term of safety
operating condition. Moreover as compare to volume of reactor, co current give smaller volume
and also smaller mass flow rate of cooling water which can justify the co current exchange mode
as design basis.

Volume required to achieve 99.4% conversion for co current mode is V=1.7m3. Taking account
the reactor flow rate and temperature overload the volume is scaled up to +20% and the final
volume required is, V=2.04m3.
As final design consideration the following feature summarized the PFR design basis.

Operating Condition
Feed Flow Rate (mol/s) 11.63
Volume (m3) 2.04
Reactor Inlet Temperature (oC) 30
Cooling Water Flow Rate (Kg/s) 2.8
Cooling Water Inlet Temperature (oC) 63
Pressure Reactor (atm) 1.5
Cooling Water Pressure (atm) 1.2
Material Construction CS/SS

Based on study, PFR provide better conversion compare to CSTR, due to this PFR was first to
be consider for reaction vessel. Other advantages of PFR are simple structure with no moving
part as per CSTR that require mechanical stirring known as agitator, the effective cooling area
provided by PFR is also better compare to CSTR, by equivalent volume CSTR respectively will
need larger volume to achieve same conversion. Small volume of PFR also provide better safety
advantage such that the volume is relatively thus will have smaller magnitude of hazard
especially when dealing with flammable chemical. Requirement for level control can be avoided
in PFR. PFR can be further modified to have additional feature like staged baffle ring or can be
form of numerous bundle of tubes like tubular reactor, baffle and bundle tube are effectively
increase performance of reactor and also additional feature such as integrated heat exchanger is
possible due to its simplicity in design dimension.

In previous year transesterification of palm oil by methanolysis catalysed by NaOH in

continuous staged CSTR was studied by[ ]. The result shows interestingly good potential
candidate of reactor design, the reactor consist of baffle ring with stirrer along the PFR geometric
reactor.

The reactor vessel is assembly of tubes and shell pipe, the tube was design according to API 660
with stainless steel 316 and carbon steel casing is utilized.
 Energy Balance of Cooling Water Flow Rate Vs
Temperature Different For Reactor Exchanger
20

18

16

14
Cooling Water Flowrate

12

10

0
0 1 2 3 4 5 6 7 8 9
Temperature Different

Co Current Counter Current