Beruflich Dokumente
Kultur Dokumente
BKF 2453
SEM II 2015/2016
MINI PROJECT
PRODUCTION OF ETHYLENE FROM METHANE
No Name ID
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.
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:
CH4
CH4
REACTOR C2H4
C2H2
H2
H2
C
FA
FAO REACTOR FC
FD
FEO
FB
FE
FF
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.
Table 2: The molar flow rates for each species and their stoichiometric coefficients.
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=
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
FC = FC0 + 2 -3
FC = 0 + 2 -3
FC = ½ -3
3 = ½ - FC
FD = FD0 + 3 - 4
0 = 0 + 3 - 4
4 = 3
=½ - FC.
FE = FE0 + ½ ξ1 + ξ2 + ξ3 + 4
= 0.05
FE0 = (FA0)
= 0.0526 ( )
FE = FE0 + ½ ξ1 + ξ2 + ξ3 + 4
= FE0 + 2 - 2 FC
= 0.0526 ( )+2 - 2 FC
FF = FF0 + 24
FF = 0 + 24
FF = 24
= 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.
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 =
Thus,
rA = -r1 (1)
= - k1CA
rB = rB2 + rB3
= ½ r 2 – r3 (2)
= ½ k2Cc – k3CB
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.
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.
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.
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:
Fc
= Fc Pc PA
Y
Where:
The prices of materials and fuel value for cost estimation are as tabulated in table 4 below.
Y = A – B*C, where the value of A, B and C are obtained from polymath result’s.
Hence, using Polymath software to calculate this value, we obtained the trend of
Economic Potential of Ethylene vs. conversion of product, Xa as follows:
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]
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 this Level 3 case, there are 3 unknowns to be solved. The degree of freedom is shown
below.
Numbers of unknown ( ) 7
Mass balance:
Extent of reaction
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.
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.
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
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,
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.
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.
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: $1 = RM4.10
Installation cost (%) = 45
Based on Figure 3.2 above, it can be seen that there are no recycle stream that is being
considered. This is because the amounts of side product, which is Methane, Ethane and
Acetylene, are very little. So, they are only being purged, and not being recycled back.
Hence, that is why there is no recycle stream considered in this process.
Design of reactor
The plug flow reactor is designed by the desired production rate where the feed is changed by
the conversion of acetylene. The algorithm of reactor for multiple reactions is thus employed
here with several molar flow rates calculated from the conversion specified.
Reactor Design
Mole balance
The plug flow reactor cost estimation follows the shell and tube method. From the graph of purchased cost
versus tubes surface area ¼ inches schedule 40 pipes in Figure 15-13(Peters &Timmberhaus, 1991), the
following correlation (readily included inflation for 2014 was obtained
Purchased cost,
cAO = 125933V+651508
EP3 ($/Yr) = EP2 - 125933V+651508
Reference(s)