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Multi-systems: Large scale processes

• Recycle
• Purge
• Bypass
• System boundaries for multi-systems

Recycle Streams
It is common for the conversion in a
chemical reactor to be less than 100%.
Equilibrium constants for each reaction
dictate the maximum conversion possible.

Consider the following process:

Products
Reactor +
Reactants
Unconverted
Reactants

Conversion < 100%


In this processes there is a significant wastage
of unconverted reactants. If conversion was
60% then 40% of the feed would be wasted.
This makes for poor process economics.

The obvious solution is to recycle the


unconverted reactants back to the reactor until all
is converted. I.e. the stream leaving the reactor is
passed through a separator where the products are
separated and the unreacted feed is recycled back
into the reactor.

Feed
Reactor Separator

Products
Recycle stream
(unreacted feed)

Note: If we do an overall mass balance,


all feed is converted to product.
Simple example:
Consider a reaction in which A → B
and a reactor conversion of 60% .

CASE 1:

100 mol A X mol A


Reactor Y mol B

Component balances:
A: 0 = 100 – X + 0 – 100 x 0.60 X = 40mol
B: 0 = 0 – Y + 100 x 0.60 x 1/1 – 0 Y = 60mol

CASE 2:

Reactor Separator
100 mol A 100 mol B

Recycle stream
X mol A
Y mol B

Reactor Separator
100 mol A 100 mol B

W mol A
Balance on the separator:
B: 0 = Y – 100 Y = 100 mol
Balance on the reactor:
B: 0 = 0 – 100 + (100 +W) x 0.60 x 1/1
W = 66.67 mol
Balance on the separator:
A: 0 = X – 66.67 X = 66.67 mol
66.67 mol A
100 mol B

Reactor Separator
100 mol A 100 mol B

66.67 mol A
Note:
• Same amount of feed: 100 mol A
• Improved reagent to product conversion
with recycle
• Larger reactor volume with recycle
• Requires a separator with recycle
CASE 1:
40 mol A
100 mol A
Reactor 60 mol B

Single pass conversionof A = (100 − 40) ⋅ 100% = 60%


100

CASE 2:
Reactor Separator
100 mol A 100 mol B

66.67 mol A
Overall conversionof A = (100 − 100) ⋅ 100% = 100%
100
REACTOR

Conversion around reactor is


60% This is called the single-
pass conversion

Conversion around overall system is 100% -


This is called overall conversion.
Purge streams
In previous examples of Recycle of unreacted
chemicals, overall conversion is 100%.

For example: water shift reaction

CO + H 2 O H 2 + CO 2
CO, H2O

CO,
Feed H2O
Reactor Separator
H2O H2
CO CO

Products: H2, CO2

If equimolar amounts of CO and H2O are placed


in the feed (i.e. in the right stoichiometric ratio),
then 100% overall conversion is possible.
However, what if the amounts of CO and
H2O are not equimolar (i.e. not in their
stoichiometric ratio)?
Consider feeding 100% excess of H2O:

Feed Product
50 mol CO CO2, H2
100 mol H2O

Element balance:
C: moles (CO 2) out = 50 mol

H: moles (H 2) out = 100 mol Not possible

O: moles (CO2) out = 75 mol

The excess H2O will continue to be recycled


as well as being continuously fed and not all
of it will be converted.
∴ H2O must be removed from the system as
it will accumulate.
What if inert species (eg. N2) enter with the
feed?

50 mol CO CO2
50 mol H2O H2
10 mol N2

Not possible. N2 (or any other inert compounds)


must be removed or purged from system.

If N2 is not purged, the recycle stream builds up


N2 continuously (accumulates) and steady state
is never achieved.

To remove excess reactants or inert species


from a system (if these species cannot be
removed selectively: separator) usually a
proportion of the recycle stream must be
split off.
Example:

Methanol is synthesized from carbon


monoxide and hydrogen in a catalytic reactor.
The fresh feed to the process contains 32.0%
CO, 64% H2 and 4.0% N2.
This stream is mixed with a recycle stream in
a ratio of 5 mol recycle/mol fresh feed to
produce the feed to the reactor, which
contains 13.0 mol% N2.

The reactor effluent goes to a condenser


from which two streams emerge: A liquid
product stream containing all the methanol
formed in the reactor and a gas stream
containing all the H2, CO and N2 leaving the
reactor. The gas stream is split into two
fractions: One is removed from the process
as a purge stream, and the other is the
recycle stream that combines with the fresh
feed to the reactor.
Calculate: (a) production rate of methanol
(mol/h); (b) molar flow rate and composition
of the purge gas; (c) overall and single pass
conversions.
Solution: use element balances
Basis: 100 mol fresh feed
N2
CO
100 mol/h H2
CH3OH
1 2 3 CH3OH
Reactor Condenser
32% CO 4
64% H2 7 5
4% N2 CO 6
H2
N2 Purge

let n(i)j = number of moles of species ‘i’ in


stream ‘j’
now , n(T) 7 = 5n(T)1
= 500 mol/h
∴ balance around mixing point :
Total :
n(T) 2 = n(T) 7 + n(T)1
= 500 + 100
= 600 mol/h
N2 :
n(N 2 ) 2 = n(N 2 ) 7 + n(N 2 )1
⇒ 0.13 × 600 = n(N 2 ) 7 + 0.04 × 100
⇒ n(N 2 ) 7 = 74 mol/hr
∴ mol fraction of N 2 in stream
74
7 is = 0.148
500
The mol fraction of N 2 in streams
5 and 6 must also be 0.148
Mass balanced around the entire system:
As nitrogen is an inert species, we can do an
overall mass balance on N2
N 2 in = N 2 out
⇒ 0.04 × 100 = 0.148 n(T) 6
⇒ n(T) 6 = 27.0 mol/hr

We must do element balances to determine


the flow of H2, CO, CH3OH as these are
reactants/products.
Element Balances:
Around entire system:
Carbon:
C in = C out
⇒ 0.32 × 100 = n(CO)6 + n(CH 3OH) 4 -1
H balance
H in = H out
2n(H 2 )1 = 2n(H 2 ) 6 + 4n(CH 3OH) 4
⇒ 0.64 × 100 = n(H 2 ) 6 + 2n(CH 3OH) 4 -2
n(H 2 ) 6 + n(CO)6 + n(N 2 ) 6 = 27 -3
but n(N 2 ) 6 = 0.148 × 27 = 4.00 mol/hr
∴ n(H 2 ) 6 + n(CO) 6 = 27 - 4 = 23
⇒ n(H 2 ) 6 = 23 - n(CO)6
Note there is no ‘O’ balance. This would be
identical to the ‘C’ balance. C and O appear
in the same ratio (1:1) in the same
components: CO & CH3OH
⇒ n(H 2 ) 6 = 23 - n(CO)6
substitute into equation 2
41 = 2n(CH 3OH) 4 - n(CO)6
Add this to equation 1
73 = 3n(CH 3OH) 4
⇒ n(CH 3OH) 4 = 24.3
⇒ n(H 2 ) 6 = 15.4
⇒ n(CO)6 = 7.6

CO + 2H 2 ↔ CH 3OH
24.3
∴ Overall conversion = × 100 = 76%
32
For single pass conversion, we need to know
amount of CO entering the reactor.
Now , mol fraction of CO in
7.6
Stream 7 is (same as in purge stream)
27
= 0.282
∴ n(CO) 7 = 0.282 × 500
= 141 mol/h
∴ n(CO) 2 = n(CO) 1 + n(CO) 7
= 32 + 141
= 173 mol/h
Amount of CO Converted in
reactor = amount of CH 3 OH
leaving reactor = n(CH 3 OH) 3
= n(CH 3 OH) 4
= 24.3 mol/h
∴ Single pass conversion is
24.3
× 100 = 14%
173
Bypass

Unit
Operation

For reasons of product quality, or other


issues, some times a fraction of a stream will
be diverted around a unit operation only to
rejoin on the other side.
Example:
In the preparation of feedstock to a plant
manufacturing hydrocarbon product, iso-
pentane is removed from a petroleum
stream. Given the data on the below
diagram, what fraction of the petroleum is
passed through the iso-pentane tower?

1 2 Iso-Pentane 5 6 90% n – P
Tower 10% i - P
Feed
80% n - P 4
20% i - P
100% i - P 100% n - P

n – P = n – pentane
i – P = iso-pentane
Basis: Feed Flow of 100 kg
Over Entire System:
Overall Balance:
m(T)1 = m(T) 4 + m(T) 6
⇒ 100 = m(T) 4 + m(T) 6
n - P Balance
0.8(100) = 0 × m(T) 4 + 0.9 m(T) 6
0.8
⇒ m(T) 6 = × 100 = 89 kg
0.9
⇒ m(T) 4 = 100 - 89 = 11 kg
Balance Around Tower :
Overall Balance
m(T) 2 = m(T) 4 + m(T) 5
= 11 + m(T) 5
n - P Balance
0.8 m(T) 2 = m(T) 5
⇒ m(T) 2 = 11 + 0.8 m(T) 2
⇒ 0.2 m(T) 2 = 11
⇒ m(T) 2 = 55 kg

∴ 45 kg of feed by-passes iso-pentane


tower.
∴ 45% of the feed by-passes tower.
55% of the feed passes through the
tower

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