KC32203 Chemical

Reaction Engineering
Previous Lecture:

PART 1: Mole Balances in Terms of Conversion

(Cont…)

4.4 Tubular Reactors

4.5 Pressure Drop in Reactors
4.5.1 Pressure Drop and the Rate Law

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Today’s Lecture:

PART 1: Mole Balances in Terms of Conversion (Cont…)

4.5 Pressure Drop in Reactors
4.5.2 Flow Through a Packed Bed
4.5.3 Pressure Drop in Pipes
4.5.4 Analytical Solutions for Reaction with Pressure Drop

Part 2: Mole Balances in Terms of Concentration & Molar

Flow Rates
4.7 Mole Balances on CSTRs, PFRs, PBRs and Batch
Reactors
4.7.1 Liquid Phase
4.7.2 Gas Phase
4.8 Microreactors
4.9 Membrane Reactors
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 PART 1:
Mole Balances in Terms
of Conversion

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 4.5.2 Flow Through a Packed Bed

Catalyzed by passing reactant

through a packed bed of catalyst
particles

To calc pressure drop in packed bed

Ergun Equation:

Turbulent flow
Laminar flow
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How to calc the pressure drop??
At steady state (i.e. equation of continuity), mass flow rate at any point in the
reactor = entering mass flow rate

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From Eqn 3-41,

Combine Eqn 4-22 and 4-23

Simplify

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Where

Catalyst weight (at distance z),

Cross sect. area

Bulk density of catalyst, b = c(1-)

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From Eqn 4-26 use relationship of z and W to express Ergun Eqn in terms of W

Simplify

Let y = P/Po

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Where

For a single reaction packed-bed reactor (it is easier to express Ergun Eqn in X),

Recall Eqn 3-43,

Divide by FTo

Where, as before,

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Substitute FT/FTo, Eqn 4-28 can now be written as •  < 0, P is less
than  = 0
•  > 0 , P is
greater than  =
0

For isothermal, Eqn 4-30 becomes

Recall Eqn 4-21 (for the combined mole balance, rate law & stoichiometry)

We need to use software packages & numerical methods to solve

Eqn 4-31 & 4-21 simultaneously

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Analytical Solution
For isothermal operation with  = 0,

Equation 4-30 becomes

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Taking the square root for both sides,
Can be used to
substitute for P in
the rate law, for
the mole balance
(function of X and
Where, W)

Also, if we wish to express P in terms of reactor length, z

Use Eqn 4-26 to substitute W in Eqn 4-33

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 4.5.3 Pressure Drop in Pipes

For flow in pipes, pressure drop;

Replace u = G/ & combine with Eqn 4-23 (constant T & molar flow rate FT) ,

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Integrate with P = Po when L = 0 (assume f does not vary)

Neglect the 2nd term on the right hand side & rearrange to obtained,

Where Example 4-4: P is small

(10%) for the flow
conditions (1000 ft length
of 1 ½ in schedule 40 pipe).
BUT for HIGHER volumetric
flow rate, P may be
significant!
 Example 4-4 Calculating P in a
Packed Bed

• 60 ft length of 1 ½ -in schedule 40 pipe packed with catalyst pellets ¼-in in diameter
• 104.4 lbm/h of entering gas
• T constant (260 °C)
• Void fraction,  = 45% (0.45)
• Properties of gas similar to air at respective T
• Pinlet = 10 atm
From Eqn 4-34
Plot the pressure drop & vol. flow rate profile
(against the length, z)?
Solution:

At the end of reactor, z = L

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Evaluating the P parameters

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Substitute these values to solve for βo in Eqn 4-25

Term 2 is
dominant!
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 Change unit:
1 atm/ft = 333
kPa/m

Solve,

Use the data to plot P and v profiles.

Recall Eqn 3-41

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For the case  = 0, T = To

Construct Table E4-4.1 by using Eqn 4-34 & E4-4.8

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Also, calculate

By using Table E4-4.1, plot Figure E4-4.1

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4.5.4 Analytical Solutions for Reaction with Pressure Drop

When there is P, reactant concentration & reaction rate

smaller than the case without P, hence X will also be smaller
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Now that we have expressed pressure as function of catalyst weight, W (Eqn 4-33)

Consider the following 2nd order isothermal reaction to relate conversion

(X) and catalyst weight (W)

Again, recall;

1. Mole balance:

2. Rate law:

3. Stoichiometry (Gas phase isothermal recation ( T= To) with  = 0. From

Eqn (3-45),  = o/y):

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Substitute y in Eqn 4-33 to obtain

4. Combine:

5. Separate variables:

Integrate with limits X = 0 when W = 0, substitute for FAo = CAoo yields

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Solve for X

Catalyst weight for 2nd order

reaction in PFR with P

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Example 4-5 Effect of P on the
Conversion Profile

• Reconsider packed bed in Example 4-4

2A  B + C

• 20 meters of 1 ½ -in schedule 40 pipe packed with catalyst

• Flow & packed bed properties remained the same (converted to SI units)
• Pinlet = 10 atm = 1013 kPa

And

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 Change particle size to see effect on the conversion profile
Assume k is constant

(a) Calculate X in the absence of P

(b) Calculate X accounting for P
(c) Determine how answer in (b) would change if the catalyst particle
diameter were doubled

Entering conc, CAo = 0.1 kmol/m3 and

Solution:

From Eqn 4-38

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(a) Calculate X in the absence of P (i.e.  = 0)
1

Hence, o = 0

And  = 0

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(b) Calculate X accounting for P

Recall from Eqn 4-29 &

Solve for X:

X reduced from
0.82 to 0.693 due
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(a) Determine how answer in (b) would change if the catalyst particle diameter were
doubled

From Eqn E4-4.4, 2nd term is dominant

Therefore from Eqn 4-25

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From the condition given by Eqn E4-4.4, pressure drop parameter inversely proportional
with the particle diameter

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 Conversion increase with
increasing particle diameter.
But not for all cases!

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 Calculating X in a Reactor
Example 4-6
with P

Calculate the catalyst weight necessary to achieve X = 0.6 when ethylene oxide is
made from vapor-phase catalytic oxidation of ethylene with air

• Isothermal, 260 °C
• Ethylene fed = 0.30 lb mol/s at P = 10 atm
• 10 banks of 1 ½ –in diameter schedule 40 tubes packed with catalyst with100
tubes/bank
• Molar flow rate of each tube = 3 x 10-4 lb mol/s
• Properties of reacting material identical to those of air
• Density of ¼-in catalyst particles = 120 lbm/ft3
•  = 45% (0.45)

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Solution:

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 The combined steps can be evaluated by:
1. Analytical
2. Graphical
3. Numerical
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4. Software
5. Parameter evaluation per tube (i.e. divide feed rates by 1000)

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 KC32203 Chemical
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6. Summary (Combine Eqn (E4-6.1 & E4-6.8) and summarize)

Boundary conditions W = 0, X = 0 and y = 1.0 and Wf = 60 lbm

Guessing that X = 0.6, with 60 lbm weight (W) of catalyst. BUT continue if
its not achieve guess higher value of X and recalculate.

OR use softwares (Mathlab/Polymath) – page 194-195 (Textbook)

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 Catalyst weight (W)
considering the P =
44.5 lbm with X = 0.6

Say there is no pressure drop, y = 1

From Fig. E4-6.2, for 35 300 lbm total (35.3 lbm/tube),

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 PART 2:
Mole Balances in Terms
of Concentration &
Molar Flow Rates
• Membrane reactors, multiple reactions, unsteady state - easier to work
in no of moles (N) & molar flow rates (F)
• Modify algorithm (conc for liquids & molar flow rates for gases)

X algorithm Molar flow rates/concentration

- Mole balance algorithm
only for 1 species - Mole balance for each and
every species

1. Write mole balance on all species

2. Write the rate law
3. Relate mole balance to another by relative
rates of reaction
4. Relate the conc. in the rate law to the
molar flow rates
5. Relate the conc. in the rate law to the
molar flow rates
6. Combine by ODE solver (Polymath)

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 KC32203 Chemical
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 4.7 Mole Balances on CSTRs, PFRs, PBRs and Batch Reactors

4.7.1 Liquid Phase

When there is no vol. change, conc. is the preferred variables
Mole balances (Table 4-5) for the generic reaction

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4.7.2 Gas Phase

Given in terms no of moles (batch) or molar flow rates (Table 4-6)

Molar flow rates obtained from mole balance (each species), for example for PFR

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From power rate law

To relate the conc. to molar flow rates, use Eqn (3-42) with y = P/Po

To account for pressure drop, from Eqn (4-28)

Total molar flow rate is

Combine all
information
as shown in
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Table 4-6!
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 KC32203 Chemical
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 4.8 Microreactors

• High surface area in their microstructured regions (tubes/channels)

• Reduced/eliminated heat and mass transfer resistance, increase surface catalyzed
reactions, hot spots in exothermic reactions eliminated, high exothermic reactiosn
can be carried out isothermally.
• In the production of toxic/explosive intermediates (leak/microexplosion will cause
minimal damage)
• Shorter residence times & narrower residence times distributions

Example 4-7! (see

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textbook pg 204)
Reaction Engineering
 4.9 Membrane Reactors
- To increase conversion if the reaction is thermodynamically limited & multiple
reactions occurring
- Thermodynamically limited (equilibrium lies far to the reactant side) or little
conversion
- Different types of reactor configurations that contain a membrane
- Barrier
- Contain reactive sites
- Catalyst

Figure 4-13: Membrane reactors

(a) Photo of ceramic reactors
(b) Cross section of IMRCF

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 Figure 4-13: Membrane reactors
(c) cross section of CRM
(d) schematic of IMRCF for mole
balance

Example 4-8! (see

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textbook pg 211)
Reaction Engineering
 PART A: Mole Balances SUMMARY for PART B: Mole Balances in
in Terms of Conversion Terms of Concentration &
CHAPTER 4
Molar Flow Rates

- Design structure for - Mole balances (CSTR,

isothermal reactors Use knowledge in PFR, PBR, & Batch)
- Scale up liq phase batch Chap 1, 2 & 3. - Liquid phase
reactors to design CSTR Combine them in - Gas phase
- Design CSTR (Single, CRE algorithm to - Microreactors
Series, Parallel, 2nd solve CRE - Membrane reactors
order reaction) problems
- Tubular Reactor
- Pressure Drop

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