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1.0 INTRODUCTION

A fluidized bed is formed by passing a fluid usually a gas upwards through a bed of particles supported on a distributor. Fluidization is one of the methods available for contacting granular solids with fluids. The main advantages of fluidized bed are greater interfacial surface area of contact, high rates of heat transfer, avoidance of hot spots and ease in solid handling. Fluidized beds also find applications in chemical reactions. When a fluid passes upward through a bed of solids, there will be a certain pressure drop across the bed required to maintain the fluid flow.

As the bed velocity is gradually increased, a certain velocity is reached when the bed starts expanding. At this point the pressure drop across the bed equals the mass per unit area of the bed. This point is known as point of minimum fluidization or incipient fluidization. The movement of solids is at superficial velocities far below the terminal settling velocities of the solid particles and the process corresponds to a situation, which is approximately equivalent to hindered settling.

Acrylonitrile produced from the oxidation process of propylene with the ammonia.

The process required catalyst (eg: Bi2O3.MoO3 which has being used by the Sohio[1]) at which the catalyst must be multifunctional and also possessed redox properties. The equation of the ammoxidation was

1.0 INTRODUCTION A fluidized bed is formed by passing a fluid usually a gas upwards through

Figure 1.1 Oxidation of o-xylene

The synthesis reaction can be conducted in either the liquid phase or gas phase and must utilize a catalyst to achieve high product selectivity. The reaction is highly exothermic and a means ofdissipating the evolved heat must be incorporated into the reactor design.

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In PAN production, the raw materials are o-xylene and air. The o-xylene feed is vaporized by vaporizer. Air can be assumed contain only O 2 and N 2 , is mixed with recycle, if there is any recycle, and heated. The hot air and vaporized o-xylene are mixed and sent to a fluidized bed reactor and oxidized in the presence of a catalyst, vanadium pentoxide at 340˚C - 385˚C.In this reactor most o-xylene is reacted and goes to form PAN but some complete and incomplete combustion of o-xylene occurs, some maleic anhydride is formed and a heavy impurities also formed.

2.0 THEORY

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The phthalic anhydride synthesis reaction is a network of five parallel reactions: the partial oxidation of o-xylene to phthalic anhydride, the partial oxidation of o-xylene to maleic anhydride; the partial oxidation of o-xylene to phthalide; the partial oxidation of o-xylene to o-tolualdehyde and the complete oxidation of o-xylene to carbon dioxide and water. Each reaction is highly exothermic. All the reactions involved are carried out in vapour phase and all the reactions are irreversible:

Main reaction

Reaction 1

Other by-products reactions:

Reaction 2

Reaction 3

Reaction 4

Reaction 5

Rate of disappearance of phthalic anhydride, r PA

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Rate of disappearance of phthalide, r P

Rate of disappearance of o-tolualdehyde, r OT

Rate of disappearance of carbon oxides, r CO

Where K O , K A and K B are the adsorption constants with units of atm 3 and the specific reaction rate, k has units of mol/g.h.atm 2 .

The total of rate disappearance of all components for parallel reactions can be expressed

Where r A ’ is the total rate disappearance of all components that produced in our process. Therefore, according to the Engineering Chemical Journal, it is difficult to find kinetic rate expressions for reaction 5 (maleic anhydride). In the Calderbank kinetics (Boger&Menegola, 2005), kinetic value for maleic anhydride can be eliminated according to typical yields in order of 0.0-2wt%. According to hysis, there is only 0.06wt% of maleic anhydride. Therefore, reaction 5 was eliminated due to kinetically insignificant. Equation 1

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Whereby Kinetic rate equation given by Arhenius Law;

Equilibrium adsorption equation is given by;

Partial pressure of o-xylene

Partial pressure of oxygen

√ √ √ √ √ Whereby Kinetic rate equation given by Arhenius Law; Equilibrium adsorption equation

Equation 1 can be simplified to Equation 2 as follows;

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Equation 2

Given the conversion of o-xylene data as follows and entering molar flow rate of gas mixture F AO =1760kmol/h

X

OX

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-r A

83.36

73.34

63.19

52.95

42.71

22.76

20.12

13.49

The rate of disappearance of phthalic anhydride over vanadium pentoxide catalyst is given by;

Whereby the value of entering molar flow rate of o-xylene is 46.71×10 3 mol/h.

3.0 CALCULATION

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3.1 Determining the volume of reactor and amount of catalyst

In determining the volume of the reactor, we assume that the fluidized bed reactor is behaving as CSTR reactor. Even though there is no stirrer in the reactor, but there is a movement of particle in the reactor that can mixed the fluid completely.

As stated in CSTR modeling formula, volume can be determine by

There are several methods to calculate the volume of reactor, one of them is by plotting the graph of F AO /-r A against X OX and taking the area under the graph as a volume of reactor.

Table 3.1.1 Data given for graph F AO /-r A against X OX

X

OX

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-

               

r A (kmol/m 3 .hr)

83.36

73.34

63.19

52.95

42.71

22.76

20.12

13.49

F AO /-r A (m 3 )

21.113

23.999

27.853

33.239

41.208

77.329

87.475

130.467

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F AO /-r A vs X OX

0.4 0 0.3 0.5 0.2 0.1 0.9 0.7 0.8 0.6 0 F AO /-r A (m
0.4
0
0.3
0.5
0.2
0.1
0.9
0.7
0.8
0.6
0
F AO /-r A (m 3)
20
40
60
80
100
120
140
  • X OX

Figure 3.1.1 Graph F AO /-r A against X OX

The volume calculated is the volume of fluid in reactor before supplying the flow of gas. The best assumptions to calculate the volume of the reactor is by assume the reactor is 150% from the volume of fluid in the reactor.

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Amount of catalyst

(

 

)

[

(√

)

(√

)]

 

 

(46.7

0 3 )

0.65

 

7.

63

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3.2 Fluidized Bed Reactor Design

Regarding a situation to start a design, a several assumption had been developed. A catalyst use is considered as a spherical particle within the group of A due to the several justifications. The flow of particle is assumed as turbulent flow.

In order to start the design, first, the value of Uo, Umf and Vtneeds to be calculate and make sure that the value is in the exact range. The properties of material are listed as below.

O 2 [fluid] Molecular mass, Mr Melting point Boiling point Density, ρ f Viscosity, µ

= 48 = -218.4 o C = -183 o C = 1.426 = 18.6 x 10 -6 Pa.s

Vanadium pentoxide / oxide [particle/catalyst]

Molecular mass, Mr Melting point Boiling point Density, ρ p

= 181.88 = 690 o C = 1750 o C = 3.357

From standard market size, assuming diameter particle, d p = 75 µm By using Beayens&Geldart [1974], for d p < 100 µm

Minimum fluidized velocity, U mf

(

)

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By using Curve for C D Re T 2 as function of Reynolds number

The value of Re T is 2.5

(

)

So value of terminal velocity, V T can be determined.

For calculating the height of reactor, the best assumption that can be stated is order to calculate the diameter and the height of reactor

. In

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Make sure the value of U o is between U mf and V T and check the value from TDH equation for fine particle. In this case, U o = 0.25m/s.

TDH value show that the height of fluidized feed to the top of reactor, and the design is valid since TDH < height of reactor.

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3.3 Calculation of the Cost Involved in Designing the Reactor

The bare module equipment cost represents the sum of direct and indirect costs. The conditions specified for the base case are

  • 1. Unit fabricated from most common material

  • 2. Unit operated at near ambient pressure

For designing the reactor, stainless steels material is used, which is in common used

material. Furthermore, the operating pressure is 2.4 atm which is near to ambient pressure. The assumptions are listed as below

  • 1. Consider stainless steels process vessels

  • 2. Assume vertical process vessels

Calculate value C P o , use volume as parameter

Value is takingfrom Figure A.19 ((Richard Turton, 2009), since the assumption state to

use stainless steels vertical process vessel, the identification number is 20 which give .

use

For

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Substitute the all the value to calculate the cost bare module

Note: all the value and formula can be refer at appendix section

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4.0 DISCUSSION

The phthalic anhydride synthesis reaction is a network of five parallel reactions: the partial oxidation of o-xylene to phthalic anhydride, the partial oxidation of o-xylene to maleic anhydride; the partial oxidation of o-xylene to phthalide; the partial oxidation of o- xylene to o-tolualdehyde and the complete oxidation of o-xylene to carbon dioxide and water. Each reaction is highly exothermic. All the reactions involved are carried in vapour phase and all the reactions are irreversible.

Graph F AO /-r A vs. X (flow rate/rate of reaction vs. conversion) is plotted and the working volume is determined by area of the graph. In order to find the volume of the bed, the working volume is multiply by factor 1.5. It is because to avoid flooding occur in the reactor and also to avoid the entrainment of particle to occur.

Catalyst that used in this experiment is vanadium oxide. This catalyst can be assumed as Group A particle (aerated). The reason why it is assumed as Group A particle because this catalyst has a good quality and smooth for fluidization. Gas bubbles are in limited size, so it can break down in at high velocity and give good gas/solid contact. So when it well mixed, it can produce a better CSTR.

Before design a fluidized bed reactor, diameter, height, minimum fluidized velocity (U mf ) , superficial gas velocity(U o ), and terminal velocity (V T ) must be determined. To find the height and diameter of the bed, it is assuming that 3D=H and this assumption were referred from the pattern of bed in industries. U mf and V T are determining as shown in calculation section respectively. From the average of these two values, the value of U o can be determined. To check whether the U o is suitable for the bed, the TDH value must be determined. Supposedly the value of TDH must be lower than height of bed.

In order to find the diameter of particle d P , density of particle and fluid must be known. From the particle classification according to Geldart graph, interception between p -ρ f )(kg/m 3 ) and line particle A will give the value of particle size. After the value is obtained, it is then referring to the market to see whether the size is available or not.

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Stainless steels are so called high-alloy steels containing greater than 12wt% chromium and possessing a corrosion-resistant surface coating, also known as a passive coating. Since the operating temperature for the reactor is at 370 o C, by using this material, the corrosion and the reaction between wall of reactor and the fluid can be prevent. At these chromium levels, the corrosion of steel to rusting is reduced by more than a factor of 10. Chemical resistance is also increased dramatically. Although the stainless steel are more costly than carbon steel, but it is suitable and worth to use, in order to produce a good reactor for the reaction.

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5.0 CONCLUSION

Regarding a problem to designing a reactor, first and foremost, the important that need to be consider are the size of reactor, type and size of particle use and a catalyst use and also the flow of fluid to the reactor. Refer to the study that had been carried out, based on all the calculation provided in previous section, it is clearly stated that the reactor are valid due to the valid volume and flow of fluid.

Based on the calculation, the fluidized bed reactor might be present like this

D TDH H
D
TDH
H

H

=

9.75m

D

=

3.25m

TDH

=

6.375m

Figure 5.1.1 Diagram of fluidized bed

and

In calculation, the value for Uo, Umf and Vt are

. Since Umf<Uo<Vt, it can be conclude that the reactor is ideal, usable, and it

show that there is no entrainment and flooding problem will occurs. Furthermore the cost involved also affordable which is $560041.72. As a conclusion, it can state that, the design is usable and can be commercialize to be purchased.

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REFERENCES

  • 1. Fogler, H. S. (2006). Elements of Chemical Reaction Engineering. United States: Pearson Education.

  • 2. Rhodes, M. (2011). Introduction to Particle Technology . Milton Keynes UK: John Wiley & Sons, Ltd.

  • 3. Richard Turton, R. C. (2009). Analysis, Synthesis, and Design of Chemical Processes. United States : Pearson Education.

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APPENDIX

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Figure 1.2 Example of production of Phthalic Anhydride from o-xylene 20

Figure 1.2 Example of production of Phthalic Anhydride from o-xylene

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Utility Costs

Economic Data

Low-Pressure Steam (446 kPa, saturated) Medium-Pressure Steam (1135 kPa, saturated) High-Pressure Steam (4237 kPa, saturated) Natural Gas (446 kPa, 25˚C) Electricity Boiler Feed Water (at 549 kPa, 90°C) Cooling Water available at 516 kPa and 30°C return pressure 308 kPa

$3.00/1000 kg $6.50/1000 kg $8.00/1000 kg $3.00/10 6 kJ $0.05/kW hr $300.00/1000 m 3 $20.00/1000 m 3

return temperature should be no more than 15°C above the inlet temperature, otherwise there is an additional cost of $0.35/10 6 kJ

Refrigerated Water

$200.00/1000 m 3

available at 516 kPa and 10°C return pressure 308 kPa return temperature is no higher than 20°C if return temperature is above 20°C, there is an additional cost of $7.00/10 6 kJ

Equipment Costs (Purchased)

Piping

$/m = 0.7 (dia, in) + 1

Valves

$100 (flow diameter, in) 0.8

Pumps Heat Exchangers

for control valve with orifice plate, double the price $630 (power, kW) $1030 (area, m2) 0.6

If extended surfaces are used, area is that for same size tubing without fins. Then add a 25% surcharge for fins.

Compressors Steam Turbine assume 75% efficiency Fired Heater

$770 (power, kW) 0.96 + 400 (power, kW) 0.6 $2.18×105 (power output, MW) 0.67

$635 (duty, kW) 0.8

assume 80% thermal efficiency

Storage Tank

$1000V 0.6 V = volume, m3

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Equipment Cost Factors

Total Installed Cost = Purchased Cost (4 + material factor + pressure factor)

Pressure

< 10 atm, 0.0

does not apply to vessels, packing, trays or catalyst

(absolute)

10 - 20 atm, 0.6

since their cost equations include pressure effects

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- 40 atm, 3.0

40

- 50 atm, 5.0

50 - 100 atm, 10

 

Carbon Steel

0.0

Stainless Steel

4.0

Graph of minimum fluidization Umf

Bed pressure

drop, p

O

A C B ppp Gas velocity, U U mf
A
C
B
ppp
Gas velocity, U
U mf

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