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CHEMICAL REACTION ENGINEERING 1

BKF 2453
SEM II 2015/2016

MINI PROJECT
PRODUCTION OF ETHYLENE FROM METHANE

Name of Lecturer : Dr. Zubaidah Binti Sulaiman


Section : 03 G
Date of Submission : 2ND JUNE 2016
Group Members :

No Name ID

1 Zuraini Binti Hassan KA14133

2 Thye Mei Chin A/p Thye Ah Chai KA14119

3 Nur Ain Binti Zakaria KA14144

4 Thivya Dharshini A/p Chandra KA14148

FACULTY OFCHEMICAL AND NATURAL RESOURCES ENGINEERING


UNIVERSITI MALAYSIA PAHANG
Table of Contents

1.0 Level 1 Decision: Mode of Operation (Introduction)..................................................................2


2.0 Level 2 Decision: Input-Output Structure of the Process Flow Sheet.........................................2
2.1 Variable determination, degree of freedom analysis and management of the unknown
variables............................................................................................................................................2
2.2 Material balance calculation: stoichiometry and yield calculations for various conversions. 2
2.3 Optimization of the process by using the economic potential...............................................2
3.0 Level 3 Decisions........................................................................................................................2
3.1 Decisions on recycle stream of unconverted reactants, intermediates and/or reversible by-
product..............................................................................................................................................2
3.2 Analysis of variables for the material balance and determination of degree of freedom......2
3.3 Development of material and energy balance equations for the case of degree of freedom
greater than zero such as recycle and reactor outlet balance calculation.........................................2
3.4 Decisions on the reactor type and system (based on the reaction kinetics and conditions,
number of recycle streams and heat management of the reactors)..................................................2
3.5 Block flow diagram of the recycle structure...........................................................................2
3.6 Optimization of block diagram by using the economic potential method which includes the
cost of reactor and compressor (if any).............................................................................................2
1.0 Level 1 Decision: Mode of Operation (Introduction)

The mode of operation for our project has been by using Plug Flow Reactor (PFR).
This is because in the 1st level of process decision, 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 natural gas.

2.0 Level 2 Decision: Input-Output Structure of the Process


Flow Sheet

At this 2nd level, it is assumed that there is no recycle stream in this Ethylene
production. The feed (reactant) in this production is 95% of pure Methane and 5% of
Hydrogen. In this context, both of these reactants enter the PFR reactor at temperature of
9000C (1173.15 K) and pressure 1.5 atm. The details of our main product and also the side
valuable products exiting the reactor are shown in Table 2.0 below:

Table 1: Destination Code for Each Reactor-Outlet Component of Process

Component (Symbols) Boiling Point Destination Code


(oC)
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
In this Ethylene process, the reactants are Methane and Hydrogen, while the products
are separated into few categories. For instance, the main product is Ethylene and the side
valuable products in this process are Hydrogen and also Carbon. The purge product in this
reaction which is Methane, Ethane and Acetylene are considered as zero, as they are trace
amount (the amount of purge is very little). The block flow diagram of the process at 2nd level
decisions will be shown as in Figure 1 below.

CH4

CH4
REACTOR C2H4
C2H2
H2
H2
C

FA

FAO REACTOR FC
FD
FEO
FB
FE
FF

Figure 1: Input-Output Structure of Production of Ethylene


2.1 Variable determination, degree of freedom analysis and
management of the unknown variables

The formation of Ethylene is obtained from the elementary pyrolysis reaction of


methane as follow:

The symbols ξ are used to denote the extents of reaction. The mole balance of all
chemicals species are generally computed using the correlation as follows:

Where represents molar flow rate of the species i and  i is the stoichiometric coefficient.

The final flow rates are summarised as in Table 2.1.1:

Table 2: The molar flow rates for each species and their stoichiometric coefficients.

Species Symbol Inlet Change Outlet


Methane A FA0 -ξ1 FA 0
Ethane B 0 ½ ξ1 – ξ2 FB 0
Ethylene C 0 2 -3 FC (30,000 m3)
Acetylene D 0 3 - 4 FD 0
Hydrogen E FE0 ½ ξ1 + ξ2 + ξ3 + 4 FE
Carbon F 0 24 FF

There are total of 4 unknown variables in this process. The degree of freedom is shown
below.
Numbers of unknown (FA0, FE0, FE, FF) 4
Independent reaction (equation) +4
Ratio of inlet Methane and Hydrogen -1
Equation on extent of reaction -6
Total unsolvable = 1

Yield =

Y=

Y=

Y=

1. Balance of Methane (A):

FA = FA0 + (-ξ1)

0 = FA0 - ξ1

ξ1 = FA0

= FA0
2. Balance of Ethane (B):

FB = FB0 + ½ ξ1 – ξ2

0 = 0 + ½ ξ1 – ξ2

0=½ – ξ2

ξ2 = = ½

3. Balance of Ethylene (C):

FC = FC0 + 2 -3

FC = 0 + 2 -3

FC = ½ -3

3 = ½ - FC

4. Balance of Acetylene (D):

FD = FD0 + 3 - 4

0 = 0 + 3 - 4

4 = 3
=½ - FC.

5. Balance of Hydrogen (E):

FE = FE0 + ½ ξ1 + ξ2 + ξ3 + 4

= 0.05

FE0 = 0.05 FA0 +0.05 FEO

0.95 FE0= 0.05 FA0

FE0 = (FA0)

= 0.0526 ( )

FE = FE0 + ½ ξ1 + ξ2 + ξ3 + 4

= FE0 + ½ ( + (½ + (½ - FC) + (½ - FC)

= FE0 + 2 - 2 FC

= 0.0526 ( )+2 - 2 FC

6. Balance of Carbon (F):

FF = FF0 + 24

FF = 0 + 24

FF = 24
= 2 (½ - FC.)

= - 2FC

Based on the degree of freedom analysis in the diagram above, we can see that there
is 1 matter that cannot be solved. This matter shows that manual calculation cannot be used to
calculate these unknowns. So, Polymath software is used in our mini project reactor design
calculation to solve this unknown.

2.2 Material balance calculation: stoichiometry and yield calculations


for various conversions

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


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

A B + E. So, r1 = k1CA

B C + E. Hence, r2 = k2Cc

C D + E. r3 = k3CB

D 2F + E. r4 = k4CD

1) r1 = 2) r2 =
-r1 = rA1 -r2 = rC2

r1 = rC1 r2 = rB2

r1 = rE1 r2 = rE2

3) r3 = 4) r4 =

-r3 = rB3 -r4 = rD4


r3 = rD3 2r4 = rF4
r3 = rE3 r4 = rE4

Thus,

rA = -r1 (1)
= - k1CA
rB = rB2 + rB3
= ½ r 2 – r3 (2)
= ½ k2Cc – k3CB

rC = rC1 + rC2 (3)


= ½ r 1 – r2
= ½ k1CA – k2Cc
rD = rD3 + rD4 (4)
= r 3 – r4
= k3CB – k4CD
rE = rE1 + rE2 + rE3 + rE4 (5)
= ½ r 1 + ½ r2 + r 3 + r4
= ½ k1CA – ½ k2Cc + k3CB + k4CD
rF = rF4 (6)
= 2r4
= 2 k4CD

Selectivity = (7)

Yield = (8)

Substitute the rate equations (1) to (6) into the selectivity equation (7). Then combine
the mole balance and the selectivity equation. Subsequently, calculate the selectivity and
conversion of hydrogen by using the Ordinary Differential Equation (ODE) in Polymath.
Thus, we obtain the graph by using Selectivity vs Conversion of Hydrogen (Figure 2.1) using
Excel by substituting the value calculated in Polymath.

The selectivity equation (7) 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
hydrogen to methane.

From the equation, the selectivity of ethylene increases as conversion of methane


increases. Since at 300oC reacting mixture in both reaction 1 and 2 will be in gaseous state,
the assurance of maintaining high selectivity of ethylene lies on the ratio of feed of methane
and hydrogen. Providing just sufficient hydrogen for reaction 1 to occur will increases the
selectivity of ethylene produced, hence limiting the hydrogen required to initiate reaction.

An analysis using a batch reactor was done to delineate the effects of feed ratio of
methane to hydrogen. From calculations using ODE in Polymath, the results are summarised
and presented in Figure 2.1.1. Selectivity clearly shows that it increases with hydrogen
conversion, Xa. However, increasing ratios of methane to hydrogen will favour high
selectivity of ethylene as limiting hydrogen concentrations will place reaction 1 as priority
compared to reaction 2. This is imperative in order to prevent reaction 2 to occur. Therefore,
the feed ratio of methane to hydrogen at above 2:1 was chosen for this process as this is the
limit at which hydrogen acts as the limiting reactant.
Figure 2.1.1: Selectivity as function of hydrogen conversion.

From the Figure 2.1.1, selectivity inclines with the increase of hydrogen conversion,
XM. In other words, hydrogen will become the limiting reactant in this reaction. We choose to
run the reaction with excess of methane supply at lower conversion of hydrogen to maximize
the selectivity of ethylene production.

Overall Yield =

As previously defined, the yield is the fraction of hydrogen converted in the reactor
that corresponds to the aqueous ethylene flow at the reactor outlet. Also, this aqueous
ethylene is all removed (100% separation efficiency for the second level of decision) from the
process. Using the same calculation method as selectivity by substituting the equation from
(1) and (3) into equation (8) to calculate for the yield of ethylene and conversion of hydrogen.
The equation of the yield against the conversion can be derived by using the Regression
Function in Polymath on the data of the results from the batch reactor algorithm (Appendix
A). Obtain the graph of yield versus conversion of hydrogen (Figure 2.1.2) using Excel by
substituting the value calculated in Polymath.

Figure 2.1.2: Yield as function of hydrogen conversion.


From the graph above, the yield will increase rapidly with the increasing of
conversion of hydrogen. The trend is quite the same as the selectivity graph. We run the
reaction in low conversion of hydrogen .The yield will increase with excess supply of
methane.The yield is the fraction of hydrogen converted in the reactor that corresponds to the
aqueous ethylene flow at the reactor outlet.

Hence, from the plot shown it is proved that this production has the reasonable yield
at high conversion. Methane with too much excess will increase the size of unit operations.
Nevertheless, this can be analysed further by including economic factors. Thus we decide to
stick to this ratio for the sake of discussion.

2.3 Optimization of the process by using the economic potential

Since the practical values of the design variables depend on the process economics, the
stream costs are calculated where all of the costs of all raw materials and product streams are
equated in term of design variables. The economic potential (EP) of the process can be
calculated as follows:

EP (RM/year) = 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

The prices of materials and fuel value for cost estimation are as tabulated in table 4 below.

Table 3: Prices and fuel value for cost estimation of materials

Component (Symbols) Prices


Methane (A) RM0.337/ kJ
Ethylene (C) RM4,500/ton
Acetylene (D) RM0.337/ kJ
Hydrogen (E) RM3000/ton

The yield of Ethylene is calculated using equation below.

Y = A – B*C, where the value of A, B and C are obtained from polymath result’s.

Y = 0.0212131 + 0.1452015 XA3.002048

Hence, using Polymath software to calculate this value, we obtained the trend of
Economic Potential of Ethylene vs. conversion of product, Xa as follows:

Graph : Economic Potential (EP) vs reactant conversion, X.


From the graph obtained, we can found that the trend of economic potential was
increasing directly proportional with conversion of reactant. This is so exact with the fact that
Malaysia is one of the largest plastics producers in Asia, with over 1,550 manufacturers,
employing some 99,100 people working in this chemical industry. The country’s plastic
products are exported worldwide including the EU, China, Hong Kong, Singapore, Japan and
Thailand.

Picture 1: Comparison between total exports of plastic products within years in Malaysia
.
The table below shows that there is 15.48% increment in total exports of plastic products
in 2011 compared with 2010. This scenario shows a positive economic potential and hence
gives Malaysia a tremendously positive profit in this chemical sector. [2]

3.0 Level 3 Decisions

3.1 Decisions on recycle stream of unconverted reactants,


intermediates and/or reversible by-product.

There is no recycle stream in this process. This is because based on the table of
destination code for each reactor-outlet component of process (Table 2.0, page 2), there is no
product that is recycled back. The recycle process is only done if and only if the amount of
product is big. But, the entire product is only being purged. This is because the purge
products which are Methane, Ethane and Acetylene are very little. So, they are being purged
only, and even they are being purged in a very little amount, until the purge amount is
assumed zero (0).
3.2 Analysis of variables for the material balance and determination
of degree of freedom

Methane, FA

Ethane, FB

Ethylene, FC

Acetylene, FD
Methane, FA0 Hydrogen, FE
Hydrogen, FE0 Carbon, FF
Reactor

In the feedstock, 95% methanol and 5% hydrogen is fed to a reactor. Unconverted


methane, ethane and acetylene will be purged. Leaving as final products are Ethylene,
Hydrogen and Carbon.

In this Level 3 case, there are 3 unknowns to be solved. The degree of freedom is shown
below.

Numbers of unknown ( ) 7

Independent reaction (equation) +4


Ratio of inlet Methane and Hydrogen -1
Equation on extent of reaction -6
Information from 2nd level -1
Total unsolvable = 3

3.3 Development of material and energy balance equations for the


case of degree of freedom greater than zero such as recycle and
reactor outlet balance calculation.
We are required to design a reactor that produce 30000 metric ton per annum of
ethylene. That is equal to:

Mass balance:

Extent of reaction

Atomic Species Balances

C balance:

H Balance:
The packed bed reactor is designed, using the desired production rate that is the input of the
reactant changing with the conversion of hydrogen. As the start of the designation, the
algorithm of the multiple reactions is used here with the molar flow rates calculated.

a) Mole balance of plug flow reactor:

b) The rate laws of the reactions:


c) Energy balance

d) Stoichiometry:
The hydrogen is the limiting reactant due to the selectivity analysis.

Where:

e) Pressure drop:

Where:

3.4 Decisions on the reactor type and system (based on the reaction
kinetics and conditions, number of recycle streams and heat
management of the reactors).
Since the given rate law and the reaction occurs irreversibly in gaseous phase, the best
and economical reactor is the plug flow reactor. According to the result of the
Levenspiel plot in the Figure 3.1, plug flow reactor is the most suitable reactor to
produce high yield with the small volume of reactor compared to stirred reactor.

Based on the result of selectivity and yield analysis, the high concentration of
hydrogen and low concentration of the methane feed will contribute the to high
selectivity and yield. Hence, to ensure all the reactant convert into the product, the
plug flow reactor is used to increase the retention time in the reactor. The scheme of
the reactor is illustrated in Figure 3.2 where the reactant will flow horizontally
through the reactor.

Figure 3.1 Levenspiel Plot of 1/-rA versus Xa

Based on the selectivity analysis, in order to sustain the high selectivity the concentration of ethylene
must be low. By having the continuous flow of ethylene along the reactor length can assure the low
concentration of ethylene. The reactor scheme suggestion can be illustrated in Figure 3.2 below.

FAO
FEO FA, FC, FD, FB, FE, FF

Figure 3.2 Schematic Diagram of Plug Flow Reactor


3.4.1 Thermal Effect
To determine the thermal effect of the reactor, the calculation of the energy balance is done
by using the software polymath. The graph of reactor temperature versus hydrogen
conversion is obtained. For the calculation of the energy changes, the heat capacities of the
component at the particular temperature are obtained from Don W. Green, 2008 as tabulated
in Table 4:

Table 4: Heat Capacities Constant


Component C1 C2 C3 C4 C5
Methane 33298 79933 2086.9 41602 991.96
Ethane 40326 134220 1655.5 73223 752.87
Ethylene 33380 94790 1596 55100 740.8
Acetylene 31990 54250 1594 43250 607.1
Hydrogen 27617 9560 2466 3760 567.6

The heat capacity for each component above are in temperature range of 200K to 1500K. For
the carbon, only one value was given in a certain range. The constants in the table can be
used in the following equation to calculate the ideal gas heat capacity Cp0 , where Cp0 is in
J/kmol.K and T is in K.

To calculate for adiabatic or non-adiabatic by using heat capacity constants from Table 4,

Table 5: Heat Capacities Constant


Reaction

1 32610 + 642.3793(T-TR)

2 136330 + 124.179(T-TR)
3 174970 + 115.5641(T-TR)

4 -227480 + 81.2436(T-TR)
While using the ODE of polymath, only one variable is allowed for one program run. In the
batch reactor design algorithm, time(t) is the variable selected. To test the heat effect, the
differential equation of the adiabatic reaction, dT/dt(for the batch reactor) in terms of heat
capacities which can be calculated using formulas above is inserted into the previous batch
polymath. In the Figure 3.3, it shows the graph of the conversion of hydrogen,Xa against the
temperature. The result required for determining the heat effect does not involved the reactor
size variables such as retention time or volume. Hence, the batch reactor algorithm can be
used.

Figure 3.3 Graph of Conversion versus Temperature


From the graph, there is a slightly increase in the temperature for the adiabatic reactor. It is
caused by the exothermic reaction. The final temperature is not high as well. Thus, adiabatic
condition is favoured for plug flow reactor due to its simple design and cost incurred.

3.4.2 Costing
The plug flow reactor cost estimation follows the shell and tube method. From the graph of
purchased cost versus tube surface area ¼” schedule 40 pipes in Figure 15-13 (Peter&
Timmberhaus,1991), the following correlation (readily included inflation for 2014) was
obtained.

Purchased cost = $ (125933V +651508), where V=0.0026312m3


= $ (651839.3549)

CR = index ratio of year of reference year design × purchased cost × (1 + installation cost %)
Index ratio can be either Chemical Engineering Plant Cost Index (CEPCI: year 1990 = 355.4
and year 2016 = 2015) or Marshall & Swift Index (M&S) and the installation cost
percentages are shown below:
Currency: $1 = RM4.10
Installation cost (%) = 45

3.5 Block flow diagram of the recycle structure

Figure 3.2: Block Flow diagram of production of Ethylene from Methane

Based on Figure 3.2 above, it can be seen that there are no recycle stream that is being
considered. This is because the amounts of side product, which is Methane, Ethane and
Acetylene, are very little. So, they are only being purged, and not being recycled back.
Hence, that is why there is no recycle stream considered in this process.

3.6 Optimization of block diagram by using the economic potential


method which includes the cost of reactor and compressor (if any)

Design of reactor
The plug flow reactor is designed by the desired production rate where the feed is changed by
the conversion of acetylene. The algorithm of reactor for multiple reactions is thus employed
here with several molar flow rates calculated from the conversion specified.
Reactor Design
Mole balance

The net rate laws are calculated as following


1) r1 = k1CA
2) r2 = k2Cc
3) r3 = k3CB 14
4) r4 = k4CD
Reactor cost

The plug flow reactor cost estimation follows the shell and tube method. From the graph of purchased cost
versus tubes surface area ¼ inches schedule 40 pipes in Figure 15-13(Peters &Timmberhaus, 1991), the
following correlation (readily included inflation for 2014 was obtained

Purchased cost,

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

Reference(s)

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


Article of “Market Watch 2012” The Malaysian Plastic Industry”, by Thomas Brandt and
Schvonne Choo, retrieved from
http://www.malaysia.ahk.de/fileadmin/ahk_malaysia/Market_reports/The_Malaysian_Plastic
_Industry.pdf
Book of Elementary Principles of Chemical Processes (3rd Edition), by Richard M. Felder,
Ronald W. Rousseau, published by New York: John Wiley, Year of 2000.