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Appendix C

Your task is to design an optimal reactor to produce 30,000 metric tons per year of maleic anhydride from partial oxidation of n-butane using a VPO catalyst. The reaction involves 3 steps. You must synthesize an appropriate process flow diagram considering the optimum size and heat effects of the reactor. Cost effects should be included in the evaluation. The specifications of the VPO catalyst and a potential tubular reactor design are also provided.

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Appendix C

Your task is to design an optimal reactor to produce 30,000 metric tons per year of maleic anhydride from partial oxidation of n-butane using a VPO catalyst. The reaction involves 3 steps. You must synthesize an appropriate process flow diagram considering the optimum size and heat effects of the reactor. Cost effects should be included in the evaluation. The specifications of the VPO catalyst and a potential tubular reactor design are also provided.

Uploaded by

Ahmad Faiz
Copyright
© © All Rights Reserved
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
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Appendix C

Your task is to design an optimum reactor to produce 30,000 metric ton per annum of maleic anhydride
(C4H2O3) via partial oxidation of n-butane (C4H10) using a vanadium-phosphorous-oxide (VPO) catalyst. The
reaction route has 3 reactions as follows:-

1. C4H10 + 7/2 O2 ⃗
k1
C4H2O3 + 4H2O
2. C4H10 + 13/2 O2 ⃗2
k 4CO2 + 5H2O
3. C4H2O3 + 2O2 ⃗
k3
2CO2 + 2CO + H2O

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 n-butane and air.

At the 2nd level of process decision, the input of the process, n-butane will be supplied in pure grade (99%)
which incurs the cost of about RM1364/ton (as in 2016) and oxygen will be supplied from surrounding air
which contains 22% oxygen and 78% nitrogen. The destination of respective components exiting the
reactor will be routed from the reactor as summarised in Table 1.

Table 1: Destination of reactor outlet materials from the process

Components (subscript) Boiling Point (oC) Destination


n-butane (b) -1 Recycle
Oxygen (o) -183 Purge
Nitrogen (n) -196 Purge
Maleic anhydride (ma) 202 Main product
Water (w) 100 Discharge
Carbon dioxide (co) -57 Purge
Carbon monoxide (co2) -192 Purge

The output of the process will be oxygen, nitrogen maleic anhydride, water and carbon dioxide. Oxygen,
nitrogen and carbon dioxide can be combined in a purge stream, maleic anhydride will be flowed as an
individual main product with 99% purity (worth RM6827/ton in 2016) and water will be discharged as
waste water. Thus, the block flow diagram of the process at level 2 decisions will be as depicted in Figure
1.

Air: O2 and N2 CO, CO2, O2 and N2


Maleic Anhydride
Process
n-butane Water

Figure 1: Input-output structure of the process

The distribution of chemical can be estimated by using the rate laws proposed by Centi et al. (1985) as
follows:-

1
' ' k ' 1 K b Cb C0.23
o
−r b 1=r ma 1=
1+ K b Cb
k ' 2 0.23
−r ' b 2 = C
4 o
C 0.63
−r ma 3=k ' 3 C ma o1.15
'

Cb
Where

k'1 = rate constant for the first reaction, mol0.67 L0.23 g-1 s-1
k'2 = rate constant for the second reaction, mol 0.67 L0.23 g-1 s-1
k'3 = rate constant for the third reaction, mol 0.52 L0.48 g-1 s-1
Kb = adsorption equilibrium constant for n-butane = 2616 L mol-1
C = concentration, mol L-1

The value of rate constants is shown in Table 2.


Table 2: Values of rate constant at different temperatures

Temperature (oC) k'1 × 107 k'2 × 107 k'3 × 108


300 3.357 2.001 4.4
320 4.621 4.364 6.606
340 6.23 9.04 9.658

The activation energy of each reaction is given in Table 3.


Table 3: Activation energy of each reaction

Activation energy Ea1 Ea2 Ea3


Value, kJ mol-1 45.1 110.0 57.4

The reactions occur at 1.5 atm.

At the third level, the recycle stream of n-butane is in gas phase at room temperature. Thus a blower type
compressor is needed to elevate the pressure up to 1.5 atm. You have to synthesise an appropriate
process flow in block diagram which considers the optimum size and heat effect of reactor. Include cost
effect (economic potential) in your evaluation.

The following specifications are necessary to estimate catalyst weight and reactor size.

VPO catalyst:-
Particle diameter, Dp = 5 mm
Void fraction,  = 0.5
Bulk density = 1300 kg m-3
Price = RM10,000/kg
If tubular reactor is used, the internal diameter is 4.07 cm
Assume viscosity and parameter gc are identical to air.

Reference

2
Centi, G., Fornasari, G., and Trifiro, F., n-Butane oxidation to maleic anhydride on vanadium-phosphorous
oxide: Kinetic analysis with a tubular flow stacked-pellet reactor, Ind. Eng. Chem. Prod. Res. Dev.
(1985). Vol. 24 (1)

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