CHEMICAL REACTION ENGINEERING 1

BKF 2453

SEM II 2015/2016

MINI PROJECT

PRODUCTION OF ETHYLENE FROM METHANE

Name of Lecturer : Dr Siti Zubaidah Binti Sulaiman

Section : 03 G

Date of Submission : 12 May 2016

Group member :

MUHAMMAD SYARIF WIRA’I BIN ABD RAZAK KA 14127

NUR IZZIANA BINTI ISHAK KC 13036

JESSY LYNN JASPIN KC 13045

INTAN ZUFINA BINTI MOHD KHAIRI KE 13049

1
TABLE OF CONTENTS

1.0 Level 1 : Introduction

2.0 Level 2 : Input-Output Structure of the Process Flow Sheet
2.1 Mole Balances in Term of Extent of Reaction
2.1.1 Reaction Selectivity, Yield and Stoichiometry
2.2 Economic Potential
3.0 Level 3 Structure of flow sheet
3.1 Mole Balances
3.2 Thermal Effect
3.3 Reactor Design
3.4 Economic Potential
References
Appendix

2
1.0 LEVEL 1 : INTRODUCTION

The mode of operation for this project has been set as continuous rather than batch.
The decision made is because of the capacity and the nature of the reaction. It was
decided to run the operation in a continuous mode as the plant capacity is greater than
typical maximum batch operation of 5,000 metric ton per annum and the process will
be fed with constantly-unchanged feedstock of methanol and hydrogen.

2.0 LEVEL 2 : INPUT-OUTPUT STRUCTURE OF THE PROCESS FLOW

SHEET

This input-output structure of the process flow sheet is important because it is related
to the cost of raw materials and also cover almost 80% of the overall cost of the
process. These costs should be estimated before proceeding with any detail that
related to the design. At this 2nd level, no recycle stream is considered. Methane will
be supplied as in natural gas (containing 95% methane and 5% hydrogen) at ambient

temperature and 1.5 atm and costing RM0.34/m3 with 0.8 kg/m3 density at standard

temperature and pressure (STP). The density of methane and hydrogen is 0.7 kg/m3 and 0.09

kg/m3, respectively as STP. The destination of products and the impurity in the process

can be illustrated based on the boiling point at atmospheric pressure as shown in

Table 1:

Component (Symbols) Boiling Point (oC) Destination Code

Methane (A) - 161.49 Purge
Ethane (B) -88.5 Purge
Ethylene (C) -103.7 Main Product
Acetylene (D) -80.8 Purge
Hydrogen (E) -252.9 Side valuable Product
Carbon (F) 3642 Side valuable Product
Table 1 : Destination Code and Boiling Point for each Reactor Outlet Component of
Process
3
The rule of thumb is applied in the process design, so it is desirable to recover more
than 99% of all valuable chemicals. The output of the process will be ethylene,
unconverted methane, ethane, acetylene, hydrogen and carbon. Methane, Ethane and
acetylene can be combined into a purge stream, ethylene will be flowed as an
individual stream, hydrogen flows in a separate side product stream as well as carbon.
The block flow diagram of the process at level 2 decisions will be as depicted in
Figure 1.

CH4, C2H6 , C2H2

C2H4
PROCESS
H2
CH4, H2
C

Figure 1 : Input-output Structure of process

2.1 Mole Balances in Term of Extent of Reaction

The formation of ethylene follows the reaction 2.1 with another side reaction of as
follow :

1 1
CH4  C2H6 + H2 (2.1)
2 2

1 1
(A) (2 B ) (2 E)

C2H6  C2H4 + H2 (2.2)

(B) (C) (E)

C2H4  C2H2 + H2 (2.3)

(C) (D) (E)

4
 C2H2  2C + H2 (2.4)
(D) (2 F) (E)

Analysis of mole balance follows the extent of reaction method. The symbols Ɛ1, Ɛ2, Ɛ3
and Ɛ4 are used to denote the extents of reaction for the first, second, third and fourth
reactions which is equation 2.1, 2.2, 2.3 and 2.4 respectively. The mole balance of all
chemicals species are generally computed using the correlation as follows

Where
ṅ = molar flow rate of the species i and
vi = stoichiometric coefficient.
Ɛ = extent of reaction

Hence, the final flow rate can is summarised as in Table 2 as shown below :

Species Inlet Change Outlet

Methane FAO -Ɛ1 0
Ethane 0 1 0
Ɛ1 – Ɛ2
2

Ethylene 0 Ɛ2 – Ɛ3 FC
Acetylene 0 Ɛ3 – Ɛ4 0
Carbon 0 2Ɛ4 FF
Hydrogen FEO 1 FE
Ɛ1 +Ɛ2 +Ɛ3 +2Ɛ4
2

Table 2: Mole Balance for Second Level of decision

There are total of 7 unknown variables in this process. The diagram below is the detail
of degree of freedom.

Number of unknown =4
4 independent reaction =+4
6 equation of extent of reaction = -6
1 ratio =1
0 inert =0
Total =1
5
From the degree of freedom analysis in the diagram above, we need to specify molar
feed and conversion. In our polymaths calculation and excel calculation, specification
such as molar feed ratio of methane to hydrogen and conversion of methane are used
as in mini project reactor design calculation.

2.1.1 Reaction Selectivity, Yield and Stoichiometry

The extent of reaction will be calculated in stoichiometric manner employing the

conversion and flow of limiting reactant. Maximizing the selectivity toward ethylene
is important in reactor design. The limiting reactant can first be identified from the
scheme of reactor through selectivity analysis. Thus,

rC
SC/EF = (1)
rE  rF

rA = -r1 (2)

1
rB  r1  r2 (3)
2

rC  r2  r3 (4)

rD  r3  r4 (5)

1
rE  r1  r2  r3  r4 (6)
2

rF  2r4 (7)

r1  kCA r2  kCc r3  kCB r4  kCD

6
Substitute the rate equation (2), (3), (4), and (5) into the selectivity equation (1). Then
combine the mole balance and the selectivity equation. Subsequently, calculate the
selectivity and conversion of methane at various feed ratio of methane to hydrogen by
using the Ordinary Differential Equation (ODE) in Polymath. Obtain the graph by
using Selectivity versus Conversion of methane in Figure2 using Excel by substituting
the value calculated in Polymath.

The selectivity equation (1) cannot simply quantify the difference between both
reactant feed flows required as taught in the subject BKF 2453. Hence, some detail
analyses by using the batch reactor algorithm is necessary to delineate the effect of
feed ratio of methane to hydrogen.

From the equation, the selectivity of ethylene increase as conversion of hydrogen

increases. The graph of Selectivity against Conversion of methane is shown in Figure
2.

Selectivity against conversion

0.50000000

0.40000000
Selectivity

0.30000000

0.20000000

0.10000000

0.00000000
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000
Conversion

Figure 2 : Selectivity against Conversion of methane

7
The equation of yield is

rC r r
Yield   3 2 (7)
 rA r1

moles of desired product ( formation of ethylene)

overall yield  (8)
moles of limiting reactant (methane react)

By assuming all the purging product is near to zero;

FA=0 , FB=0 , FD=0

Thus;

FA = FAO  Ɛ1
0 = FAO  Ɛ1
Ɛ1= FAO
Fc
FAO = (1)
y

Y = Ɛ2  Ɛ3
FC
Y= Ɛ1

FC
Ɛ1 = (2)
Y

1
FB = 2Ɛ1  Ɛ2

1
0 = 2Ɛ1  Ɛ2

1
Ɛ2 = 2Ɛ1

1 FC
Ɛ2 = (3)
2 Y

FC = Ɛ2  Ɛ3
Ɛ3 = Ɛ2  FC
1 FC
Ɛ3 = 2( Y )  FC (4)

FD = Ɛ3  Ɛ4
0 = Ɛ3  Ɛ4
Ɛ3 = Ɛ4
8
Ɛ4 =Ɛ3
1 FC
Ɛ4 = 2( Y )  FC (5)

FF = 2Ɛ4
1 𝐹𝐶
FF = 2[ 2( 𝑌 )  FC ] (6)

FEO
= 0.05
FAO+FEO

FEO = 0.05FAO + 0.05FEO

0.95FEO = 0.05FAO
0.05
FEO = FAO
0.95

0.05 𝐹𝐶
FEO = (𝑌) (7)
0.95

0.05 FC 1 FC 1 FC 1 FC 1 FC
FE = ( Y ) + 2( Y ) + 2( Y ) + ( ) + ( )  FC  FC
0.95 2 Y 2 Y

0.05 FC FC
FE = ( Y ) + 2( Y )  2FC
0.95

39 FC
FE = ( Y )  2FC (8)
19

Species 1 2

Methane FC 0
Y

Ethane 0 0

Ethylene 0 FC

Acetylene 0 0

Carbon 0 𝐹𝐶
2[ ( 𝑌 )  FC ]

Hydrogen 0.05 𝐹𝐶 0.05 FC FC

0.95
(𝑌) ( )
0.95 Y
+ 2( Y )  2FC

Table 3 : Mole Balance in Term of Yield

9
From the equation, the selectivity of ethylene increase as conversion of methane
increases.The graph of Selectivity against Conversion of methane is shown in figure 3

Figure 3 : Yield Against Conversion

From the non-linear regression, the following equation was obtained for yield against
the conversion of for the methane. The equation of power with 0.999 R-square fits the
correlations are shown in Appendix A.

2.2 Economic Potential (EP2)

The practical values of the design variables depends on the process economics. Thus,
the stream costs are calculated where all the costs of raw materials and product stream
equated in term of design variables. The raw material of this process, methane will be
supplied as in natural gas (containing 95% methane and 5% hydrogen) at ambient
temperature and 1.5 atm and costing RM0.34/m3 with 0.8 kg/m3 density at standard
temperature and pressure (STP). The density of methane and hydrogen is 0.7 kg/m 3

10
and 0.09 kg/m3, respectively as STP. The potential of economics (EP) at seconds level
is calculated as below :

EP 2 = Revenue – Raw Material Cost

= Ethylene value – Methane gas

Fc
= Fc Pc  PA
Y

Where
FC = Product of ethylene (metric ton/annum)
PC = Price of ethylene (
PA = Price of methane gas (methane + hydrogen)
Y = Yield of ethylene

Yield of Ethylene is calculated using as shown below :

Y = 0.2599603+B*Xa^C
Where
B = 0.5556662
C = 1.841617
The price of material for cost is illustrated as Table 2.2 below

Component (Symbols) Prices (RM/ton)

Methane (A) RM 450.00
Ethylene (C) RM 4 500.00
Table 4 : Price of material

From the result of the economic potential analysis above, it clearly implies that the
production of 30,000 metric ton of ethylene with 35% purity is feasible (EP2 > 0) at
the continuous mode of operation.

11
 EP against Xa
140000000

120000000

100000000

80000000
EP

60000000

40000000

20000000

0
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000
Xa

Figure 4 : Graph of Economic Potential against conversion of methane

Economic potential is the annual profit that does not have to pay anything for capital
cost and utilities costs, all the analysis are just catering the sales of products
(including by-products) and the purchasing of raw materials. The next level of
decisions will use the positive range obtained from this level.

12
 Level 3

𝐹𝐴

𝐹𝐵

𝐹𝐶

𝐹𝐷
𝐹𝐶
𝐹𝐴𝑂 𝐹𝐶 𝐹𝐸 𝐹𝐹
𝐹𝐸
MAIN
𝐹𝐸𝑂 PRODUCT
𝐹𝐸 SEPARATO PRODUC
SEPARATO
REACTOR T
R1 R2

𝐹𝐸 𝐹𝐹
𝐹𝐴 𝐹𝐵
𝐹𝐷 BY
PRODUCT
PURGE

Figure 5 : Block Flow Diagram

3.1 Mole balance for the reactor

Before solving the mole balance , the unknown variables must be ensured that they
can be solved by using specifications and equations available from the process .

Degree Of Freedom analysis

UNKNOWN
𝐹𝐴𝑂 𝐹𝐸𝑂 𝐹𝐵 𝐹𝐶 𝐹𝐷 𝐹𝐸 𝐹𝐹

INDEPENDENT REACTIONS 4

BALANCE
-6

FEED CONDITION -1

INFORMATION FROM 2ND LEVEL -1

VARIABLE NEED TO BE SPECIFIED 3 ( 𝑋𝐴 , 𝐹𝐴𝑂 , 𝐹𝐸𝑂 )

13
3.2 Reactor Design

Since both rate laws are the power law models and the reaction occurs irreversibly in

gaseous phase (assuming the mass transfer limitation is deemed negligible), the right

and economical reactor is thus the plug flow reactor as can be clearly seen from the

plot of the Levenspiel.

Based on the selectivity analysis, methane feed must be limited at any cost. High

selectivity can be sustained if the concentration of ethylene is low. This probably can

be attained by having continuous exit flow of ethylene along the reactor length. In fact,

it is critical as the reactor has potential of distribution problem in the catalyst packing

due to the multiplicity of phases. The reactor scheme suggestion can be illustrated in

figure 3.3 where the liquid phase will flow downward of the catalyst packing.

Methane,
Hydrogen

Methane, Ethane, Ethylene,

Acetylene, Hydrogen, Carbon
3.3 Plug for reaction

14
3.2.1 Thermal Effect: Adiabatic or Non Adiabatic

The thermal effect of the reactor can be observed from the energy balance

calculation via the plot of reaction temperature versus propylene conversion.

From various references, heat capacities of the involving components are not

unique and changed with respect to absolute temperature as tabulated in Table

3.2.

Table 5 Heat capacities of components:

Component Cp (J/mol.K) Hrxn

Methane 560.1168 -74520

Ethane 52.6225 -83820

Ethylene 42.9165 52510

Acethylene 44.0076 227480

Hydrogen 28.64 0

Carbon 8.59597 0

0 0 0
∆𝐻𝑟𝑥𝑛 = ∑ 𝐻𝑃𝑟𝑜𝑑𝑢𝑐𝑡 − ∑ 𝐻𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡

Reaction ∆𝐻𝑟𝑥𝑛

1 32610 + 642.3793(T-TR)

2 136330 + 124.179(T-TR)

3 174970 + 115.5641(T-TR)

4 -227480 + 81.2436(T-TR)

15
In using ODE of polymath, only one dependent variable is allowed for one program.

Normally, Matlab software is used to solve it. Since this BKF2453 project encourages

students to use Polymath and the range of reaction temperature is just 1000°C, the

average heat capacities are used.

The result of the methane conversion against the reaction temperature can be seen in

Figure 6

Temperature vs Xa

0.8

0.7

0.6
Conversion, Xa

0.5

0.4

0.3

0.2

0.1

0
1020 1040 1060 1080 1100 1120 1140 1160 1180 1200
Temperature, T

Figure 6 The conversion versus reaction temperature for adiabatic reactor

16
The X-T plot in Figure 6 shows temperature increase due to the exothermic of the

reaction and the final temperature is not too high. There is no run away reaction

occurs at any temperature. Thus, adiabatic condition is preferable for the reactor of

choice, the plug flow reactor because of simpler design and cost incurred.

3.2.2 Reactor Design

The mole balance of a plug flow reactor is

𝑑𝐹𝑖
= ri whre i= A, B, C, D, E, F
𝑑𝑣

The net rate laws are calculated as following

r1 = K1CA for Reaction 1

r2 = K2CB for Reaction 2

r3 = K3Cc for Reaction 3

r4 = K4CD for Reaction 4

And

 381000
k1  4.5x1013 exp ( ) [s 1 ]
RT
 289000
k 2  9.0x10 13 exp ( ) [s 1 ]
RT

 167000
k 3  2.57x10 8 exp ( ) [s 1 ]
RT

 126000
k 4  1.7x10 3 exp ( ) [s 1 ]
RT

Energy Balance of adiabatic PFR changing the reaction temperature

17
𝑑𝑇
𝑑𝑉
( r1V(−∆Hrxn 1)) + (r2V(−∆Hrxn 2)) + (r3V(−∆Hrxn 3)) + (r4V(−∆Hrxn 4))
=
(Fa ∗ Cpa) + (Fb ∗ Cpb) + (Fc ∗ Cpc) + (Fd ∗ Cpd) + (Fe ∗ Cpd) + (Ff ∗ Cpf)

1
From the various conversions, obtained from the algorithm (can refer Appendix D)
−𝑟𝑎

is plotted can be seen in Figure 7

Levenspiel Plot
1000.00
900.00
800.00
700.00
600.00
!/-ra

500.00
400.00
300.00
200.00
100.00
0.00
0.00 0.01 0.01 0.02 0.02 0.03 0.03 0.04
Conversion, Xa

Figure 7 Levenspiel plot

3.4 Economic Potential

Economic Potential
120000000

100000000

80000000
EP3

60000000

40000000

20000000

0
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000
Conversion, Xa

Figure 8 : Economic Potential for Level 3

18
The provious economic analysis for the input-output structure consider only the
stream cost. At second level decision, the reactor system is only consider the
production price and the reactant price. At third level decision, the reactor system
consider the production price, reactant price, and also reactor cost. Thus the economic
potential can be considered as

EP3 ($/Yr) = EP2 - Reactor Cost

The plug flow reactor cost estimation follow the shell and tube method. Thus the
purchased cost,

Ca0= 125933V+651508

Thus, the economic potential can be consider as

EP3 ($/Yr) = EP2 - 125933V+651508

References

Gases - Specific Heats and Individual Gas Constants. (n.d.). Retrieved from The
Engineering Toolbox:
http://www.engineeringtoolbox.com/specific-heat-capacity-gases-d_159.html

Solid Heat Capacity. (n.d.). Retrieved from The Engineering Toolbox:

http://www.engineeringtoolbox.com/specific-heat-solids-d_154.html

Fogler, H. S. (2006). Element of Chemical Reaction Engineering . Pearson

Publication .

19
Appendix A

# mole balance
d(Ca)/d(t) = rA # methane
Ca(0) = 0.05832
d(Cb)/d(t) = rB # B ethane
Cb(0) = 0
d(Cc)/d(t) = rC # C ethylene
Cc(0) = 0
d(Cd)/d(t) = rD # D acetylene
Cd(0) = 0
d(Ce)/d(t) = rE # E hydrogen
Ce(0) = 0.00306
d(Cf)/d(t) = rF # F carbon
Cf(0)=0
t(0)= 0
t(f)= 3600

# Rate Law
r1 = k1*Ca
r2 = k2*Cb
r3 = k3*Cc
r4 = k4*Cd
k1 = 4.5*(10^13)* exp (-381000/(R*T))
k2 = 9.0*(10^13)* exp (-289000/(R*T))
k3 = 2.57*(10^8)* exp (-167000/(R*T))
k4 = 1.7*(10^3)* exp (-126000/(R*T))
rA = -r1
rB = (1/2)*r1-r2
rC = r2-r3
rD = r3-r4
rE = (1/2)*r1+r2+r3+r4
rF = 2*r4

# Selectivity
S=(r2-r3+0.00001)/( (1/2)*r1+r2+r3+r4+2*r4+0.00001)

# yield
Y= (r2-r3+0.00001)/(r1+0.00001)

Xa= 1- (Ca/Ca0)
Nt= (Ca+Cb+Cc+Cd+Ce+Cf) *V
V= 1

20
Nto= (Ca0+Cb0+Cc0+Cd0+Ce0+Cf0)*V
Ca0= 0.05832
Cb0= 0
Cc0= 0
Cd0=0
Ce0=0.00306
Cf0=0
R= 8.314
T=900+273.15
Po= 1.5*101325
Cto= Ca0+Cb0+Cc0+Cd0+Ce0+Cf0
Ct= Ca+Cb+Cc+Cd+Ce+Cf
Appendix B

Model: Y = 0.2599603+B*Xa^C

Variable Initial guess Value 95% confidence

B 1. 0.5556662 0.0102293

C 1. 1.841617 0.0484971

Nonlinear regression settings

Max # iterations = 64

Precision
R^2 0.9935786

R^2adj 0.9935131

Rmsd 0.0009742

Variance 9.685E-05

General
Sample size 100

Model vars 2

Indep vars 1

Iterations 8

21
Appendix C

# mole balance
d(Na)/d(t) = rA*V
Na(0) = 0.05832
d(Nb)/d(t) = rB*V
Nb(0) = 0
d(Nc)/d(t) = rC*V
Nc(0) = 0
d(Nd)/d(t) = rD*V
Nd(0) = 0
d(Ne)/d(t) = rE*V
Ne(0) = 0.00306
d(Nf)/d(t) = rF*V
Nf(0)=0
V=V0*(Nt/Nt0)
V0=1

# Rate Law
r1 = 4.5*(10^13)* exp (-381000/(R*T))*Ca
r2 = 9.0*(10^13)* exp (-289000/(R*T))*Cb
r3 = 2.57*(10^8)* exp (-167000/(R*T))*Cc
r4 = 1.7*(10^3)* exp (-126000/(R*T))*Cd
rA = -r1
rB = (1/2)*r1-r2
rC = r2-r3
22
rD = r3-r4
rE = (1/2)*r1+r2+r3+r4
rF = 2*r4
Ca=Na/V
Cb=Nb/V
Cc=Nc/V
Cd=Nd/V
Ce=Ne/V
Cf=Nf/V

Nt=Na+Nb+Nc+Nd+Ne+Nf
Nt0=Na0+Ne0
Na0 = 0.05832
Ne0 = 0.00306
R=8.314
P0=1.5
Xa= 1- (Na/Na0)

#Energy Balance9
d(T)/d(t)=((r1*V*(-Hrxn1))+(r2*V*(-Hrxn2))+(r3*V*(-Hrxn3))+(r4*V*(-Hrxn4)))/((Na*Cpa)+(Nb*C
pb)+(Nc*Cpc)+(Nd*Cpd)+(Ne*Cpe)+(Nf*Cpf))
Hrxn1=32610
Hrxn2=136330
Hrxn3=174970
Hrxn4=-227480
Cpa=560.1168
Cpb=52.6225
Cpc=42.9165
Cpd=44.0076
Cpe=28.64
Cpf=8.59597
T(0)=1173

t(0)=0
t(f)=100000

23
Appendix D

# mole balance
d(Fa)/d(V) = rA # methane
Fa(0) = 74.40476
d(Fb)/d(V) = rB # B ethane
Fb(0) = 0
d(Fc)/d(V) = rC # C acetylene
Fc(0) = 0
d(Fd)/d(V) = rD # D
Fd(0) = 0

24
d(Fe)/d(V) = rE # E
Fe(0) = 3.91604
d(Ff)/d(V) = rF
Ff(0)=0
V(0)=0
V(f)=130

# Rate Law
r1 = 4.5*(10^13)* exp (-381000/(R*T))*Ca
r2 = 9.0*(10^13)* exp (-289000/(R*T))*Cb
r3 = 2.57*(10^8)* exp (-167000/(R*T))*Cc
r4 = 1.7*(10^3)* exp (-126000/(R*T))*Cd
rA = -r1
rB = (1/2)*r1-r2
rC = r2-r3
rD = r3-r4
rE = (1/2)*r1+r2+r3+r4
rF = 2*r4
R=8.314
Ca=Ct0*(Fa/Ft)*(T0/T)
Cb=Ct0*(Fb/Ft)*(T0/T)
Cc=Ct0*(Fc/Ft)*(T0/T)
Cd=Ct0*(Fd/Ft)*(T0/T)
Ce=Ct0*(Fe/Ft)*(T0/T)
Cf=Ct0*(Ff/Ft)*(T0/T)
P0=1.5*101325
X=1-Fa/Fa0
Ft=Fa+Fb+Fc+Fd+Fe+Ff
F0=Fa0+Fe0
Ct0=P0/(R*T0)
Fa0=74.40476
Fe0=3.91604
T0=1273

#Energy Balance9
d(T)/d(V)=((r1*V*(-Hrxn1))+(r2*V*(-Hrxn2))+(r3*V*(-Hrxn3))+(r4*V*(-Hrxn4)))/((Fa*Cpa)+(Fb*
Cpb)+(Fc*Cpc)+(Fd*Cpd)+(Fe*Cpe)+(Ff*Cpf))
Hrxn1=32610
Hrxn2=136330
Hrxn3=174970
Hrxn4=-227480
Cpa=560.1168
Cpb=52.6225
Cpc=42.9165

25
Cpd=44.0076
Cpe=28.64
Cpf=8.59597
T(0)=1273

26