1

50000 Metric Tonnes per Annum Production

of Ethylene from Reaction of Methane and
Formaldehyde
2

























3

1.0 Introduction
One of the ethylene synthesis routes is from the hydrocarbon of methane. From the annual
production capacity, about 223.2142 kmol/hr ethylene can be computed using the 8000
operating hours for a year as about 760 hr of the rest time is for the plant turnaround works.
According to the information from the literature, the gaseous reactions involved in the process
are as follows:

CH
4
+ CH
2
O C
2
H
4
+ H
2
O

CH
2
O + C
2
H
4
CH
3
CH
2
CHO (1.1)

Whilst yield and conversion of a reaction are defined as:-




(Error! No text of specified style in
document..1)




(Error! No text of specified style in
document..2)




Table 1.1: Species and its respective symbol.
Species Symbol
Methane (CH
4
) M
Formaldehyde (CH
2
O) F
Ethylene (C
2
H
4
) E
Water (H
2
O) W
4

Propionaldehyde (CH
3
CH
2
CHO) P

The amount of ethylene produce annually is 50,000 MTPA. Hence,
50,000 MT x 1 yr x 1000kg x 1kmol = 223.2142 kmol/hr = 62.0039 mol/s
yr 8000 hr 1 MT 28.05


Mole Balance :
M = Methane
F = Formaldehyde
E = Ethylene
W = Water
P = Propionaldehyde

dF
m
/ dV = r
m

dF
F
/ dV = r
F
dF
E
/ dV = r
E
dF
W
/ dV = r
W
dF
P /
dV = r
P




Rate Law:
-r
1M
= 10 exp (-1000/T) C
M
C
F
-r
2F
= 10
9
exp (-1000/T) C
F
C
E

Stoichiometry
a) relatives rate:
5

r
1F
=

r
1M
r
1E
= -r
1M
r
1W
= -r
1M

r
2E
= r
2F

r
2P
= r
2F

b) concentration
C
M
= C
TO

, C
F
= C
TO

, C
E
, C
TO
=

, C
W
= C
T0

, C
P
= C
T0

With F
T
= F
M
= F
F
= F
E
= F
W
= F
P

c) combine
- Combine all equation and solve it simultaneously by using ODE solver in polymath
software.










6



The graphical correlation between the yield and selectivity can be seen in Figure 1.1:


Figure 1.1- Selectivity as a function of conversion



Economic Potential Level 1 = (REVENUE RAW MATERIAL)








REVENUE (PRODUCT) : ETHYLENE
50,000/MT $220 = $11,000.00
y = 158.86x
6
- 203.84x
5
+ 103.06x
4
- 26.02x
3
+ 3.4276x
2
- 0.2239x +
0.0062
R = 0.9663
0.00E+00
1.00E-03
2.00E-03
3.00E-03
4.00E-03
5.00E-03
6.00E-03
0 0.1 0.2 0.3 0.4
Y
i
e
l
d

(
m
o
l
e

o
f

E
t
h
y
l
e
n
e
/
m
o
l

o
f

c
o
n
v
e
r
t
e
d

M
e
t
h
a
n
e
)

X
M
F
E
7



RAW MATERIAL:
1)METHANE: (16 kg/mol)
62 mol/s 1 kmol/1000 mol 16 kg/ kmol 3600 s/h 8000 h/ 1 yr 1 MT/ 1000 kg
= 28,569.60 MT/yr
28,569.60 $120 = 3,428,352 $/yr ------------ (1)

2)FORMALDEHYDE : (30 kg/mol)
62 mol/s 1 kmol/1000 mol 30 kg/ kmol 3600 s/h 8000 h/ 1 yr 1 MT/ 1000 kg
= 5,3568 MT/yr
5,3568 $100 = 5,356,800 $/yr ----------- (2)
Let (1) + (2) :
3,428,352 $/ yr + 5,356,800 $/ yr = 8,785,152 $/ yr




EP 1 = REVENUE (PRODUCT) - RAW MATERIAL
EP 1 = $ 11,000,000 - $ 8,785,152 = $ 2,214,848
$ 2,214,848 RM 3.16 / $ 1 = RM 6,998,919.68
Economic Potential Level 1 = RM 6,998,919.68/year





8


9

Economic Potential Level 2





2.0 Input-Output Structure of the Process Flow Sheet

Since the raw materials costs normally falls in the range from 33 to 85% of the total
processing cost, these costs are essential to be estimated before any other detail is added to the
design. As referred to the heuristics of the destination code in Table 5.1-3 of the Douglas
textbook, the destination of products the process are classified based on the boiling point of
all species in the process (see Table 2.1).

Table 2.1 Destination Code for Production of Ethylene
COMPONENT BOILING POINT (C) DESTINATION CODE
Methane -161.5 Recycle
Formaldehyde -104 Recycle
Ethylene 49 Primary Product
Propionaldehyde 98 Side Product
Water 100 Side Product


As a rule of thumb in process design, it is desirable to recover more than 99% of all valuable
materials. Thus at the second level of decision, the mole balances are calculated for the
overall system in which the limiting reactant is 100% converted (various conversions are
evaluated inside the process and would appear in the third level of decision). Figure 2.1
depicts the input-output structure of the process.
10



Figure Error! No text of specified style in document..1 Input-Output Stream and the
Respective Nomenclatures of the process




2.1 Mole Balances in Term of Extent of Reaction

Analysis of mole balance follows the extent of reaction method. The symbols
1
and
2
are
used to denote the extents of reaction for the first and second reactions (Eq. 1.1), respectively.
The mole balance of all chemical species are generally computed using the correlation as
follows

11

Where

am molar flow rate of the species i and v

I
is the stoichiometric coefficient. Hence,
the final flow rate from Figure 2.1 can be summarised as in Table 2.2

Table 2.1 Mole Balance for the Second Level of Decision
SPECIES INLET CHANGE OUTLET
Methane F
F
- 1 0
Formaldehyde F
M
- 1 - 2 0
Ethylene 0 1 - 2 P
E

Propionaldehyde 0 2 P
P

Water 0 1 F
W


Po = 10 bar
CH
4
+ CH
2
O C
2
H
4
+ H
2
O 1
CH
2
O + C
2
H
4
CH
3
CH
2
CHO 2

In total, other than F
E
, there are 7 unknown variables. Information available to solve those
variables can be detailed out as follows, based on the material and energy balance textbook
(Felder & Rousseau, 2005)

Number of variables in the process
The specific production rate
7
-1
2 Independent reactions
Selectivity between desired and undesired
Yield equation
Impurity composition of CH
4
in the feed
+2
+1
-1
-1
5 equation of extent of reactions
Production rate of ethylene, P
E
-5
-1
Total (Variables can be calculate specifying two more information available) 2


12


The remaining information is obtained from the purge composition which will determine the
ratio of excess for the whole process and design variable of the reactor which would be
optimized based on the economic analysis. This purge composition is actually governing the
feed ratio too through the mole balance of reactive unit.

2.1.1 Yield and Reaction Stoichiometry

As previously defined, the yield is the fraction of ethylene converted in the reactor that
corresponds to the methane flow at the reactor outlet. Also, this methane is all recovered and
removed (100% separation efficiency for the second level of decision) from the process.
Hence, for a production of P
M
mol/hr (223.2142kmol/hr), the Methane fed to the process F
FM

must be

(Error! No text of specified style in document..3)

Also, from the stoichiometry (Eq. 1.1), the amount of methane produced P
R, CH4
must be

(Error! No text of specified style in document..4)

If a fraction Y of methane is converted to ethylene, a faction 1-Y must be lost to
Propionaldehyde. However, from the stoichiometry of the reactions, the amount of
Propionaldehyde produced P
D
must be

(Error! No text of specified style in document..5)

Since the methane stream contains no impurities (99% pure), the methane fresh feed rate and
the propionaldehyde by-product flow rate can be found in terms of yield from the reaction
stoichiometry and the given production rate. A relationship between yield and conversion is
given in Eq. 1.4.


2.1.2 Recycle and Purge

13

The stoichiometry indicates the amount of methane required for the reaction. If an excess
amount of formaldehyde is needed, F
FEXCESS
, into the process, this methane will leave with the
purge stream. Thus the total amount of formaldehyde fed to the process will be

(1-Y)

(3.4)

which is equal to the amount of formaldehyde in the make up gas stream y
FF
F
G
. Similarly, the
water flow rate leaving the process will be the amount of water entering the process, (1-
y
FF
)F
G
, plus the amount of water produced by the P
R,water
= P
E
/S, or in total

(Error! No text of specified style in document..6)

The total purge flow rate P
W
will then be the excess CH
2
O, F
FEXCESS
, plus the total water P
w
or

(3.6)

Rather than using the excess formaldehyde feed F
F
as a design variable, the purge
composition of reactant, y
PF
, is used where

(3.7)

The ratio of purge and recycle is governed by the feed molar ratio between formaldehye and
methane to the reactor that would be appeared in the third level of decision. Hence, the purge
composition will be identical both in the recycle and the purge, varies between zero and unity.
Expressions can further be developed for the water rate F
W
and the purge rate P
G
explicitly in
terms of the purge composition of reactant y
PF
either by using equation

to
eliminate F
E
from equation

and

or by writing
balances or the formaldehyde and water and then combining them. That is, the amount of
formaldehyde in the feed must supply the net reaction requirements as well as the purge loss

(3.8)


and the water in the feed plus the water produced must all leave with the purge

(3.9)
14


Adding these expressions gives

(Error! No text of specified style in document..7)

As a result, F
G
can be solved as follows

(3.11)


In summary, those variables can be tabulated as in Table 3.3:

Table 3.3
STREAM 1 2 3 4 5
Methane (FM) 0

0 0 0
Formaldehyde (FF) F
F
0 0 0

Water (FW) F
w
0 0 0
F
M
+

Propionaldehyde (FP) 0 0 0 F
M
(1-Y) 0
Ethylene (FE) 0 0 P
E
0 0

Where the general equation:
Ethylene Methane Formaldehyde
P
E
+ P
E
(1-Y) -

(F
F
+ F
FEXCESS
)
And,
Y = 158.86x
6
-203.84x
5
+103.06x
4
-26.2x
3
+3.4276x
2
-0.2239x+0.0062
*(from the graph of Selectivity versus Conversion (x)) in EP 1


15


2.2 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 equated in
term of design variables. The potential of economics at the second level is therefore
EP ($/yr) = Ethylene value + Propionaldehyde value (Methane value + Formaldehyde
value) (3.12)

Apart from the product and raw material prices in Table 1.1, the prices for fuel value for cost
estimation are also required as tabulated in Table 3.4

Table 3.4: Price Data
MATERIAL PRICES
Ethylene $220/MT
Methane $120/MT
Formaldehyde $100/MT
Propionaldehyde $35/MT


16




Figure 2: Economic Potential-level 2
The economic potential in Eq 3.12 would finally be
E
P2
= 223.21($6.16) 223.21(2.03)- (223.31/Y)($1.92) (223.21/Y)($3) (3.13)

Based on the rule of thumb, the optimum conversion rate can be taken at x=0.8. therefore,
based on graph plotted in figure , EP 2 was found to be RM 5,152,862.89










0
1000000
2000000
3000000
4000000
5000000
6000000
0 0.2 0.4 0.6 0.8 1 1.2
R
M
/
Y
E
A
R

X
Economic Potential Level 2
17

Level 3 Decision: Recycle Structure of the Flowsheet
At the third level, the reactive unit is detailed out. A compressor, as the major utility (due to
its significant cost), is necessary here to recycle the unconverted methane. The main route of
formaldehyde is the first reaction in Eq. 1.1, whereas the second one is the accompanying side
reaction after ethylene appears in the reactive system. Therefore both reactions occur in the same
reactor at the isothermal temperature of 500 K and the pressure 10 bar.
As the process involves series (consecutive) reactions, the information about yield and
selectivity are thus necessary to get the optimum design parameter. The value of excess use of
methane in this process would ensure the completeness of the reaction conversion which is
preferable due to suppression on the second undesired reaction while it is cheaper than
formaldehyde. There is no rule of thumb for the ratio of the feed, O
M
, as it is normally determined by
selectivity analysis. This ratio, which based on the Rase study (Rase, 1977) is 2, would govern the
amount of recycle through the compressor from the purge stream.



Figure Error! No text of specified style in document..2: Formaldehyde with Liquid and Gas
Recycle Streams
Separator Reactor
Compressor
Formaldehyde recycle
Toluene Feed
CH
4
Feed
Methane Recycle
Purge
Ethylene
Propionaldehyde
P
F
and y
PF
P
B
P
D
F
F
(1-X)

F
F
(1-X)
F
FF

F
M

F
F

O
M
(F
F
)
R
M
and y
FM
1
2
18




Mole Balances for the Reactor
The degree of freedom of the reactor is analysed as follows:-
Unknown variables (F
F
, O
M
, X, P
P,
R
M
and P
F
) 6
2 independent reactions +2
5 species with extent of reaction - 5
Specific molar feed ratio (O
M
= 2) - 1
Total (leaving 2 design variable, X and y
PH
) 2

There are two mixing points before the reactor which contribute mole change in the stream of the
feeds. The analysis of degree of freedom is started from the stream containing the limiting reactant
as the key component for calculating the recycle stream (at Junction 1). From Figure 4.1, the degree
of freedom at Junction 2 is analysed as follows:-
Unknown variables (F
F
, X, F
FF
) 3
F
FF
= P
E
/Y and Y(X) equations -1
F
F
= F
FF
+F
F
(1-X) equation -1
Total (leaving 1 design variable, X) 1
From the equation of F
T
above,
F
F
= F
FF
/X
The analysis of degree of freedom for the mixing point number 1 can be written as follows:-
Variables (O
M
, y
FM
, y
PF
F
G
, R
G
, F
T
) 5
Specific molar feed ratio (O
M
= 2) -1
Composition of H
2
O I the CH
4
gas makeup -1
Equation of F
G
as in Eq. 3.11 -1
Total (leaving 2 design variables, X and y
PF
2
19






The feed ratio of hydrogen

(Error! No text of specified style in document..8)

Thus

)
(Error! No text of specified style in document..9)

Reactor Design
We used packed-bed reactor in this project
The weight of catalyst used is calculated from the equation in the graph, where
W = 31091X
6
62760X
5
+ 51356X
4
18528X
3
+ 4404.2X
2
+1874.7X + 0.5191 (X=0.5)
Volume for PBR, V =

= 3.237 m
3


Reactor Cost
C
R
= $4.57 x 10
4
(V)
0.67

= $4.57 x 10
4
(3.237)
0.67

= $100394.94
= RM (100394.94 x 3.16)
20

= RM 317248.01



Catalyst Cost
We use SAPO-34 as the catalyst since it has highest yield compare to the other sulphur-based catalyst
Catalyst cost = W(X) x $/g
= 1456.46kg x $800/kg
= $1165168
= RM (1165168 x 3.16)
= RM 3681930.88

Compressor Design and Costs
A compressor is required as the process has a gas recycle stream. Compressors are so expensive that
spares are seldom provided for centrifugal units (although reciprocating compressors may have
spares because of a lower service factor). In practice, one standby compressor would also be
purchased to accommodate for any failure and breakdown.
The design equation for the theoretical horsepower (hp) for the centrifugal gas compressor (for
various pressure loads) is as follows

5
3.03 10
1
out
in in
in
P
hp P Q
P

(
| | | |
( =
| |
( \ . \ .

(Error! No text of specified style in document..10)
The brake horse power (bhp) was determined by dividing the isentropic power requirement (hp)
by 0.9. This allows for irreversibilities, such as fluid friction in valves, friction of moving parts and
fluid turbulence. The horse power (hp) was calculated and in doing so it was assumed that there
is no pressure drop across the mixer and heater preceding the reactor, such that Pout = 10 bar
(20885.4342 lb/ft
2
). For the inlet air compressor Pin is specified as 1.01325 bar (2117 lb/ft
2
).
21

However, for the gas recycle compressor Pin was assumed to be 0.8Pout to account for pressure
drops across the reactor and separation system, as this has yet to be designed.



For complex gases CH
4
,
(

) [(

]

Values of that can be used for first estimates are given in Table 3.1
Table Error! No text of specified style in document..2 Values of for respective type of gases
Values of
Monotomic gases 0.40
Diatomic gases 0.29
More complex gases (CO
2
, CH
4
) 0.23
Other gasses R/C
p

Efficiency
At this level, the compressor has 90% of efficiency to account for fluid friction in suction and
discharge valves, ports, friction or moving metal surfaces, fluid turbulence, etc. The driver is also
assumed to have 90% of efficiency to account for the conversion of the input energy to shaft work.
Annualized Installed Cost
A compressor is required for gas recycle process. It has been decided to use centrifugal
compressor as this has few moving parts, high energy efficiency and a small size relative to other
types of compressors. The installed cost of this was calculated using Guthries correlation where
the Marshall and Swift equipment cost index (M & S) for this year is 1525.3 and Fc = 1.00 for
centrifugal compressors (Douglas, 1988). The installed cost was converted to an annualised cost
22

by dividing by a capital charge factor, which is related to the project life, cost of capital and has
been estimated as 3.

bhp = hp/0.9 (Error! No text of specified style in document..11)

Then, Guthries correlation can be used to calculate the installed cost for various types of
compressors:
Installed Cost = ( )
0.82
&
517.5 2.11
280
c
M S
bhp F
| |
+
|
\ .
(Error! No text of specified style in
document..12)
(

= RM 73457.36
Where F
C
is the correction factor and M & S (Marshall and Swift Inflation Index) those are
obtained from Peters Textbook (Peters & Timmberhaus, 1991).
Operating Cost
By dividing the brake horsepower by the driver efficiency, the utility requirement can be calculated.
Then from the utility cost and using 8000 hr/yr, the operating cost can be obtained.



= RM27847.29/yr

23

EP3 = EP1 reactor cost compressor cost catalyst cost
= RM 6,998,919.68 - RM 317248.01 RM(73457.36 + 27847.29) - RM 3681930.88
= RM 2898436.14

References