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• When the reaction proceeds irreversibly, small quantities of by-products must be purged, particularly with
recycle, otherwise they will buildup in the process continuously until the process must be shut down.
• In many chemical processes, the main reaction is accompanied by one or more side reactions that produce
byproducts. When the main reaction is irreversible or has a large chemical-reaction equilibrium constant,
but one or more of the side reactions are reversible reactions with chemical-reaction equilibrium
constants on the order of one or less, the possibility of increasing the overall yield of the desired product(s)
from the main reaction by eliminating the net production of byproduct(s) exists.
• This is accomplished by applying a concept sometimes referred to as recycle to extinction.
• The concept must be applied with care and must be supported by main reaction rates that are sufficiently
high. This is particularly true when the main reaction is catalyzed because the catalyst may not support the
side reaction(s).
• Experimental verification is essential.
Distribution of Chemicals (Cont’d)
Heuristic 6: Recycle to extinction - atomic balance
Example: Steam Reforming of Methane
The fresh feed to a steam reformer is 15 kmol/hr of methane (CH4) and 90 kmol/hr of steam. Two reactions take place in the steam reformer: 1) the primary steam
reforming reaction, 2) the water gas shift reaction.
Methane
The outlet conditions of the reactor are 800 oC and 12.2 atm and chemical equilibrium is achieved for both the steam reforming and water-gas shift reactions. The
chemical reaction equilibrium constant for the main reaction is 126.8 and that of water gas shift reaction is 0.929. Determine the kmol/hr of synthesis gas (H2 & CO)
produced when:
(b) the CO2 is recovered from the reactor effluent and recycled to extinction.
Assumptions: (1) Need to determine the expression for equilibrium constant for each reaction
(2) Consider atomic balances
(3) Problem contains multiple unknowns and multiple equations . Use Mathcad to solve the equations
Distribution of Chemicals
Recycle to Extinction - atomic balance
Solution:
Function Diagram
2 Equations
5 unknowns
K1
CH4 + H2O <--> CO + 3H2
Do the same calculation for K2
𝑷𝑪𝑶2 𝑷𝑯2 ሺ𝒙𝑪𝑶2 𝑷𝒕𝒐𝒕 )ሺሺ𝒙𝑯2 𝑷𝒕𝒐𝒕 ቁ 𝒏𝑪𝑶2 𝒏𝑯2 𝑷2𝒕𝒐𝒕 𝒏2𝒕𝒐𝒕
= = ∗
𝑷𝑪𝑶 𝑷𝑯2 𝑶 𝒙𝑪𝑶 𝑷𝒕𝒐𝒕 )ሺ𝒙𝑯2𝑶 𝑷𝒕𝒐𝒕 𝒏𝑪𝑶 𝒏𝑯2𝑶 𝑷2𝒕𝒐𝒕 𝒏2𝒕𝒐𝒕
K2
CO + H2O <--> CO2 + H2
Where p is the partial pressure in atm, Ptot=12.2 atm, xi are the mole fractions and ni are in kmol/hr. Since these two
equations contain five unknowns, three additional atom-balance equations are needed. They are:
Distribution of Chemicals
Recycle to Extinction - atomic balance
5 equations, 5 unknowns
Distribution of Chemicals
Recycle to Extinction - atomic balance
(b) For recycle of CO2 to extinction, the CO2 in the reactor effluent is recycled and added to the fresh feed to give a
combined feed. At chemical equilibrium, the flow rate of CO2 in the reactor effluent is the same as that in the
combined feed. The two chemical equilibrium equations remain the same, but the three atom balance equations
become:
Methane
where nk,in and nk,out are the moles of k entering and leaving the reactor.
• The extent of reaction for reaction i is defined as:
(moles/time)
(2) j=1,…,C
(Unitless)
• For a system with a single reaction, the species balance for species j in
terms of fractional conversion of species k is:
(-vj)j + (-vk)k <--> vxx
(3)
nk,in – nk,out
• The species balance for j in terms of the extent of reaction is:
(4)
• For a system with R parallel reactions, the overall species balance for
species j, in terms of extent of reaction, is:
(5)
Methane
At 800 oC, the two chemical equilibrium equations are:
𝑛𝐶𝑂 𝑛𝐻
𝑝𝐶𝑂 𝑝𝐻32 ሺ𝑥𝐶𝑂 𝑃𝑡𝑜𝑡 )ሺ𝑥𝐻2 𝑃𝑡𝑜𝑡 )3 𝑃 ሺ 2 𝑃 )3 3
𝑛𝐶𝑂 𝑛𝐻 𝑃𝑡𝑜𝑡 2
𝑛𝑡𝑜𝑡 𝑡𝑜𝑡 𝑛𝑡𝑜𝑡 𝑡𝑜𝑡 2
𝐊𝟏 = = = 𝑛 𝑛 = ሺ ) = 126.8
𝑝𝐶𝐻4 𝑝𝐻2𝑂 ሺ𝑥𝐶𝐻4 𝑃𝑡𝑜𝑡 )ሺ𝑥𝐻2𝑂 𝑃𝑡𝑜𝑡 ) 𝐶𝐻4 𝐻 𝑂
𝑃𝑡𝑜𝑡 ሺ 2 𝑃𝑡𝑜𝑡 ) 𝑛𝐶𝐻4 𝑛𝐻2𝑂 𝑛𝑡𝑜𝑡
𝑛𝑡𝑜𝑡 𝑛𝑡𝑜𝑡
(a)No recycle.
Functional Diagram
Methane: nCH4 = 15 - ξ1 Methane
Reaction 1
H2O: nH2O = 90 - ξ1 – ξ2
H2: nH2 = 3ξ1 + ξ2 Reaction 2
CO: nCO= ξ1 – ξ2
CO2: nCO2 = ξ2
Total: nT = 105 + 2ξ1
3
𝑛𝐶𝑂 𝑛𝐻 𝑃𝑡𝑜𝑡 2 ξ1 – ξ2 ∗ ሺ3ξ1 + ξ2 )𝟑 12.2 𝑎𝑡𝑚
2
ሺ
𝑛𝐶𝐻4 𝑛𝐻2 𝑂 𝑛𝑡𝑜𝑡
) = 𝑲𝟏 = ∗ሺ )2 = 𝟏𝟐𝟔. 𝟖
15 − ξ1 ∗ ሺ90 − ξ1 – ξ2) 105 + 2ξ1 𝑘𝑚𝑜𝑙/ℎ𝑟
(a)No recycle.
ξ2 ∗ ሺ3ξ1 + ξ2 )
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1 – ξ2 ) ∗ ሺ90 − ξ1 – ξ2)
𝜉2 ∗ ሺ42.63 + 𝜉2 )
𝑲𝟐 = = 0.929
ሺ14.21 − 𝜉2 ) ∗ 75.79 − 𝜉2
Using the quadratic formula and choosing a reasonable value, ξ2 = 7.89 kmol/hr.
Distribution of Chemicals
Species Molar Balances
(a)No recycle.
ξ2 ∗ ሺ3ξ1 + ξ2 )
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1 – ξ2 ) ∗ ሺ90 − ξ1 – ξ2)
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances
b)recycle to extinction
CO2/in/recycle ∗ ሺ𝟑ξ1)
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1) ∗ (90 − ξ1)
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances
Since we only know T = 157.03 kmol/hr, we need to solve for CO2/recycle/in given
T, and substitute it into the simpler K2 expression as below:
CO2/in/recycle ∗ ሺ𝟑ξ1)
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1) ∗ (90 − ξ1)
Then,
5.071𝜉1 − 72.48 = 0
𝝃𝟏 = 𝟏𝟒. 𝟐𝟗 𝒌𝒎𝒐𝒍/𝒉𝒓
Since we now know ξ1, we can simply plugging this value into the species
molar balances.
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances
• Summary (recycle to
extinction)
Reactor Feed Reactor Effluent
Component
(kmol/hr) (kmol/hr)
Methane 15 0.71
Water 90 75.71
Hydrogen 0 42.87
Carbon
0 14.29
Monoxide
Carbon Dioxide 23.45 23.45
TOTAL 128.45 157.03
M = 15 - ξ1
W = 90 - ξ1
H = 3ξ1
CO= ξ1
CO2 = CO2/in/recycle
T = 105 + 2ξ1 + CO2/recycle/in= 157.03 kmol/hr (Given)
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances
• Since the equilibrium constant of the desired reaction is much greater than
the side reaction, it might make sense to recycle the by-product E to
extinction.
E
Distribution of Chemicals
Recycle to Extinction
Species Molar Balance/Extent of Reaction Example:
• First, we consider the equilibrium constants to give us the following 2
equations (assuming isothermal, isobaric reactor):