30,000 Metric Tonnes Per Annum Production

of Methacrolein from Isobutylene and

Oxygen



Subject : BKF 2453 CHEMICAL REACTION ENGINEERING
Section : 01
Prepared by :
TAN YONG CHAI KA 11206
LEE HON KIT KE 11182
JOSHUA KAU MUN KIT KA 11164
NG TECK HUAI KA 11193
TAN KAH HOAY KA 11067
CINDY LAU CHIN YEE KE 11007

Table of Contents
1. Introduction 2-3
2. Level 1 Decision: Batch Versus Continuous 3-4
3. Level 2 Decision : Input- Output Structure of The Process Output ......................... 5-9
4. Level 3 Decision 9-11
5.Reference 11
6.Appendix 12






1. Introduction
One of the Methacrolein synthesis routes is from oxidation of isobutylene. From the
annual production capacity, about 428571.4286 kmol/yr benzene can be computed using
8000 operating hours for a year as about 760 hours of the rest time is for the plant
turnaround works. According to the information from the literature, the reactions involve in
the process are as follow:
Isobutylene + Oxygen Methacrolein + H
2
O
Isobutylene + 6O
2
4 Carbon Dioxide + 4H
2
O (Eq. 1.1)
While yield and conversion of a reaction are defined as:
Yield, Y



Conversion, X



For an adiabatic reactor with the inlet temperature > 50
o
C and the reactor pressure 20 bar,
the yield of the isobutylene oxidation reaction,

for the conversion, X < 0.95. The graphical correlation between the yield and selectivity can
be seen in Figure 1.1.

0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
Yield, Y
Conversion, X
Yield Vs Conversion
Figure 0.1: Selectivity as a Function of Conversion
No catalyst is necessarily used for this reaction. The purity of the main product,
Methacrolein, required by the consumers is a minimum of 99%. The easily-available cheap
raw materials are pure isobutylene and oxygen with purity of 99%.

2. Level 1 Decision: Batch Versus Continuous
As referred to heuristic guidelines, for the process synthesis and flow sheeting, this process
is worth continuous mode. The reasons of the decision are mainly based on the capacity and
the nature of the reaction. This process produces more than 5,000 tons per annum and the
raw materials are only two: isobutylene and methanol. The reactions are not too complex
that would not require the use of well-controlled batch reactors. The demand is
considerably consistent and do not change much with years as it is free from any seasonal
difficulties.
At this level, the mole balance would be equated in algebraic terms and calculated through
the outmost boundary of the plant as can be seen in Figure 2.1 along with the gross
profitability analysis.
1. Isobutylene Methacrolein + H
2
O(desired)
O
2
CO
2
+ H
2
O (undesired)
Figure 2.1: Overall mole balance for the production
2.1. Economic Potential
The reactions just only need one condition and can be conducted without any catalyst. At
this level, based on the stoichiometry of Eq. 1.1, for 428571.4286 kmol/yr methacrolein, at
least about 428571.4286 kmol/yr of isobutylene and 428571.4286 kmol/yr of oxygen
makeup are required for as the raw material. According to the literature, the production of
side product, carbon dioxide can be neglected for a rough calculation at this level as
compared to other species. The prices of products and raw materials based on their
available purities in the global market are listed in Table 2.1.
Process


Species Purity Price
Isobutylene 99% $40/MT
Methacrolein 99% $188/MT
Table 2.1: Prices of chemical species

1 Isobutylene + 1 1 Methacrolein + 1 H2O

According to stoichiometry,1 mol of methacrolein requires 1 mol of isobutylene feed.
Feed:

Therefore the potential of economics (EP1) at the first level would be as follows:

From the result of the economic potential analysis above, it clearly implies that the 30,000
metric tonnes per annum production of benzene is feasible (EP1>0) at the continuous mode
of operation. We assumed that there is 100 per cent yield, conversion and separator
efficiency upon this level. Side reaction is not taken into consideration.
3. Level 2 Decision : Input- Output Structure of The Process Output
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 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 3.1
depicts the input-output structure of the process
Figure 3.1: Input-Output Stream and the Respective Nomenclatures of the Isobutylene
Oxidation
3.1 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

where

is molar flow rate of the species i and

I
is the stoichiometric coefficient. Hence, the final
flow rate from Figure 3.1 can be summarised as in Table 3.2

Table 0.1 Mole Balance for the Second Level of Decision
Process
1. Isobutylene

2 Oxygen

3 Methacrolein (desired)

4 Carbon Dioxide, Oxygen, Water

Process
F
A
F
B
P
M
P
D
(a)

(b)

Species Symbol Inlet Change Outlet
Isobutylene A F
A
-
1
-
2
P
A
Oxygen B F
B -
1
- 6
2
P
B
Methacrolein C 0
1
P
c
Carbon Dioxide D 0
4
2
P
D

Water E 0
+
1
-+4
1
P
E

In total, other than P
B
, there are 6 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 unknown variables in the process 6
2 Independent reactions +2
5 equation of extent of reactions -5
Composition of Ratio of Isobutylene to Oxygen in the feed -1
Total (Variables can be calculate specifying two more information available) 2

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.
3.1.1. Yield and Reaction Stoichiometry
XY Methacrolein+Water (desired)
X Carbon Dioxide+Water (undesired)
IB
(1-X) IB
Table 3.1.1: Probability Sketch of the Process

Table 0.2 Mole Balance in terms of conversion and yield for the Second Level of Decision
Species Symbol Inlet Change Outlet
Isobutylene A F
A
F
A
[-XY+X(1-Y)] F
A
[1-X]

Oxygen B F
B
F
A
[-XY+6X(1-Y)]

F
A
[6-6X+5XY]

Methacrolein C 0 F
A
[XY]

F
A
[XY]

Carbon Dioxide D 0

F
A
[4X(1-Y)]

F
A
[4X(1-Y)]
Water E 0

F
A
[XY+4X(1-Y)]

F
A
[XY+4(1-Y)]

Total F
A
+ F
B
F
A
(7+X-XY)


From the probability sketch, we can obtain:

Ratio of

Isobutylene to Oxygen=1:6

Simplify

By Using Excel solver,


3.2. 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
(

)
(

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.2 0.4 0.6 0.8 1
Yield, Y
Conversion, X
Yield Vs Conversion
As the result of the calculation, from the graph EP ($/yr) versus conversion in Figure 3.2, the
profit can be obtained at relatively high conversion.
As this economic potential is the annual profit that does not have to pay anything for capital
costs and utilities costs, all the analyses are just catering the sale of products (including by-
products) and the purchasing of raw materials. The next level of decisions would use the
range obtained from this level.

4. Level 3 Decision
At Level 3, we consider the cost of reactor installation, compressor installation and operation. Then,
we calculate the Economic Potential at this level.
4.1. Reactor Design

Using Excel To Intergrate with Simspon 3/8 Rules, to obtain graph as below.
-6000000
-5000000
-4000000
-3000000
-2000000
-1000000
0
1000000
2000000
3000000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
EP2($)
Conversion, X
EP2 Vs Conversion


4.1.2. Reactor Cost
The Cost of Reactor, V is the volume of the reactor.
Plug Flow Reactor, $
PFR
= (1.345V + 854.8) 375


4.2. Compressor Design and Costs

The cost of Compressor, F is the molar flow rate of the stream
Installation Cost, $
InstallComp
= 375x4.5F
0.93

Operation Cost, $
OperaComp
= 45x4.5F
0.5

4.3. Economical Potential
0
10
20
30
40
50
60
0 0.2 0.4 0.6 0.8 1
Volume of PFR
(litre)
Conversion
Volume of PFR vs Conversion
The previous economic analysis for the input-output structure considered only the stream
costs, i.e., products plus by-products minus raw material costs.
(

)





5.Reference
http://link.springer.com/article/10.1007%2FBF00811806#page-1
Felder, R. M., & Rousseau, R. W. (2005). Elementary Principles of Chemical Processes (3 ed.). New
York: John Wiley & Sons.
Peters, M. S., & Timmberhaus, K. D. (1991). Mass Transfer and Reactor Equipment - Design and Costs.
In J. J. Carberry, J. R. Fair, W. P. Schowalter, M. Tirrell & J. Wei (Eds.), Plant Design and
Economics for Chemical Engineers (4th ed.). New York: McGraw Hill.
Rase, H. F. (1977). Chemical Reactor Design for Process Plants Case 104. New York: John Wiley &
Sons.


-1E+09
-9E+08
-8E+08
-7E+08
-6E+08
-5E+08
-4E+08
-3E+08
-2E+08
-1E+08
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
EP3
Conversion, X
EP3 Vs Conversion
6.Appendix




X Y f(x,y) EP2($) rA -1/rA F
A0
F(A)/-rA V(litre) Reactor Cost
Compressor
installation
compressor
operation
EP3($)
0.0875 0.870396 0.00E+00 -5010974 406.4409 0.0025 195116.3572 480.0608 7.701385246 324434.3862 857349858.2 360867.1837 -863046134.1
0.1375 0.867106 0.00E+00 -2191763 390.0046 0.0026 124636.0715 319.5759 12.28278074 326745.1275 565110852.7 236657.835 -567866018.6
0.1875 0.863554 0.00E+00 -877352 373.2916 0.0027 91775.8115 245.8555 15.64754462 328442.2303 425130453.3 189145.4608 -426525393.4
0.2375 0.859700 0.00E+00 -117496 356.2756 0.0028 72779.3990 204.2784 18.371723 329816.2378 342651653.1 162307.3415 -343261272.6
0.2875 0.855497 0.00E+00 376981.8 338.9257 0.0030 60417.4540 178.2617 20.70891746 330995.0602 288181441.7 144536.7484 -288279991.6
0.3375 0.850887 0.00E+00 723858.5 321.2058 0.0031 51745.5378 161.0978 22.79512226 332047.2898 249509312.8 131690.746 -249249192.3
0.3875 0.845797 0.00E+00 980082.2 303.0728 0.0033 45339.9452 149.6008 24.71361256 333014.9283 220654241.7 121873.8413 -220129048.3
0.4375 0.840131 0.00E+00 1176517 284.4750 0.0035 40429.0693 142.1182 26.52111526 333926.5875 198339922.8 114081.3214 -197611413.5
0.4875 0.833766 0.00E+00 1331301 265.3492 0.0038 36559.4767 137.7787 28.26033441 334803.8062 180623782.1 107726.0955 -179735011.1
0.5375 0.826537 0.00E+00 1455735 245.6168 0.0041 33448.6168 136.1821 29.96698104 335664.5961 166286368.9 102441.0528 -165268739.2
0.5875 0.818215 0.00E+00 1557154 225.1781 0.0044 30913.1556 137.2831 31.67459132 336525.872 154531943 97985.79687 -153409300.9
0.6375 0.808477 0.00E+00 1640410 203.9035 0.0049 28831.7508 141.399 33.41888802 337405.6516 144832158.3 94198.87535 -143623352.9
0.6875 0.796838 0.00E+00 1708664 181.6189 0.0055 27125.3995 149.3534 35.2432333 338325.8058 136843688.5 90972.37965 -135564322.7
0.7375 0.782537 0.00E+00 1763740 158.0813 0.0063 25748.5048 162.8814 37.20766349 339316.6153 130372001.6 88239.31318 -129035817.7
0.7875 0.764282 0.00E+00 1806095 132.9327 0.0075 24689.6367 185.7303 39.40752688 340426.1714 125378661.4 85970.61933 -123998963.6
0.8375 0.739637 0.00E+00 1834113 105.6054 0.0095 23989.1700 227.1586 42.02080301 341744.2425 122067237.1 84184.3566 -120659052.5
0.8875 0.703198 0.00E+00 1841250 75.0915 0.0133 23810.7463 317.0896 45.46638439 343482.1076 121222672.9 82981.57211 -119807886.5
0.9375 0.638878 0.00E+00 1801274 39.2223 0.0255 24810.1502 632.5529 51.29182912 346420.3163 125947715.6 82672.40113 -124575534.3