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Distribution of Chemicals (Cont’d)

Heuristic 6: By-products that are produced in reversible reactions,


in small quantities, are usually not recovered in
separators or purged. Instead, they are usually
recycled to extinction. Reference: Seider, Chapter 7
Often small quantities of chemicals are produced in side-reactions.

• 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:

(a) the CO2 produced is not recovered and not recycled.

(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

(a) At 800 oC, the two chemical equilibrium equations are:

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

Element Balance Functional Diagram


Carbon balance: 15 = nCH4+ nCO+ nCO2 Methane

Oxygen balance: 90= nH2O+ nCO+ 2nCO2

Hydrogen balance: 2(90)+ 4(15) = 240 = 2nH2+ 4nCH4 + 2nH2O

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

Carbon balance: 15 + nCO2= nCH4+ nCO+ nCO2


Oxygen balance: 90+ 2nCO2= nH2O+ nCO+ 2nCO2
Hydrogen balance: 2(90)+ 4(15) = 240 = 2nH2+ 4nCH4 + 2nH2O
Distribution of Chemicals
Recycle to Extinction - atomic balance

Continuous CO2 emissions No CO2 emissions (Recycled CO2 in Equilibrium)


Distribution of Chemicals
Heuristic 6 - Recycle to Extinction Based on Species Molar Balances

• In addition to elemental balances, species molar balances can be used to


solve for species effluents for systems involving chemical reaction.
• The species molar balance can be defined in terms of fractional conversion
of a key component (Xk) or in terms of the molar extent of reaction (ξ).
• For a given chemical reaction, the fractional conversion, Xk, of reactant k is
defined as:
(1)

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)

where Δnij is the change in the number of moles of reactant j due to


reaction i, and νij is the stoichiometric coefficient of reactant j in reaction i.
Distribution of Chemicals
Heuristic 6 - Recycle to Extinction Based on Species Molar Balances

• 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)

where i refers to the ith reaction, and j=1,…,C


Distribution of Chemicals
Recycle to Extinction - Species Molar Balances
(a)No recycle.
Solution:

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

Do the same calculation for K2


𝑛𝐶𝑂2 𝑛𝐻
𝑝𝐶𝑂2 𝑝𝐻2 ሺ𝑥𝐶𝑂2 𝑃𝑡𝑜𝑡 )ሺ𝑥𝐻2 𝑃𝑡𝑜𝑡 ) 𝑛𝑡𝑜𝑡 𝑃𝑡𝑜𝑡 ሺ𝑛 2 𝑃𝑡𝑜𝑡 ) 𝑛𝐶𝑂2 𝑛𝐻2
𝑡𝑜𝑡
𝐊𝟐 = = = 𝑛𝐻2𝑂 = = 0.929
𝑝𝐶𝑂 𝑝𝐻2𝑂 ሺ𝑥𝐶𝑂 𝑃𝑡𝑜𝑡 )ሺ𝑥𝐻2𝑂 𝑃𝑡𝑜𝑡 ) 𝑛𝐶𝑂 𝑛𝐶𝑂 𝑛𝐻2 𝑂
𝑛𝑡𝑜𝑡 𝑃𝑡𝑜𝑡 ሺ 𝑛 𝑃𝑡𝑜𝑡 )
𝑡𝑜𝑡

Where ni are in kmol/hr.


Since these two equations contain five unknowns, additional extent of reaction equations
are needed. They are:
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances

(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

Plugging these expressions into the equilibrium constant expressions yields:

3
𝑛𝐶𝑂 𝑛𝐻 𝑃𝑡𝑜𝑡 2 ξ1 – ξ2 ∗ ሺ3ξ1 + ξ2 )𝟑 12.2 𝑎𝑡𝑚
2

𝑛𝐶𝐻4 𝑛𝐻2 𝑂 𝑛𝑡𝑜𝑡
) = 𝑲𝟏 = ∗ሺ )2 = 𝟏𝟐𝟔. 𝟖
15 − ξ1 ∗ ሺ90 − ξ1 – ξ2) 105 + 2ξ1 𝑘𝑚𝑜𝑙/ℎ𝑟

𝑛𝐶𝑂2 𝑛𝐻2 ξ2 ∗ ሺ3ξ1 + ξ2 )


𝑛𝐶𝑂 𝑛𝐻2𝑂
= 𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1 – ξ2 ) ∗ ሺ90 − ξ1 – ξ2)
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances

(a)No recycle.

Given ξ1 = 14.21 kmol/hr,

We can then use the simpler K2 expression to obtain ξ2 by plugging in ξ1.

ξ2 ∗ ሺ3ξ1 + ξ2 )
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1 – ξ2 ) ∗ ሺ90 − ξ1 – ξ2)

𝜉2 ∗ ሺ42.63 + 𝜉2 )
𝑲𝟐 = = 0.929
ሺ14.21 − 𝜉2 ) ∗ 75.79 − 𝜉2

ሺ𝜉2 )2 +42.63𝜉2 = 0.929[ 𝜉2 2


− 90𝜉2 + 1076.98]
0.071ሺ𝜉2 )2 + 126.24𝜉2 − 1000.51 = 0
𝒌𝒎𝒐𝒍 𝒌𝒎𝒐𝒍
𝝃𝟐 = 𝟕. 𝟖𝟗 𝒐𝒓 𝟏, 𝟕𝟖𝟓. 𝟗𝟏𝟗 𝒉𝒓
𝒉𝒓
(Since ξ2 cannot be greater than the feed molar rate or cannot be less than zero, the other answer, -
1785.919 kmol/hr, cannot be selected as a valid answer.)

Using the quadratic formula and choosing a reasonable value, ξ2 = 7.89 kmol/hr.
Distribution of Chemicals
Species Molar Balances
(a)No recycle.

• Summary (no recycle)


Component Reactor Feed (kmol/hr) Reactor Effluent (kmole/hr)

Methane 15 0.79 𝒏𝑪𝑯𝟒 = 𝟏𝟓 − 𝝃𝟏

Water 90 67.9 𝒏𝑯𝟐 𝑶 = 𝟗𝟎 − 𝝃𝟏 − 𝝃𝟐

Hydrogen 0 50.52 𝒏𝑯𝟐 = 𝟑𝝃𝟏 + 𝝃𝟐

Carbon Monoxide 0 6.32


𝒏𝑪𝑶 = 𝝃𝟏 − 𝝃𝟐

Carbon Dioxide 0 7.89 𝒏𝑪𝑶𝟐 = 𝟏𝟓 − 𝝃𝟏

TOTAL 105 133.42


Distribution of Chemicals
Recycle to Extinction - Species Molar Balances

(a)No recycle. 2 equations, 2 unknowns


The problem can also be solved directly without knowing ξ1
By solving for ξ1 𝒂𝒏𝒅 𝝃𝟐 𝒅𝒊𝒓𝒆𝒄𝒕𝒍𝒚 from the two system of
equations in Wolfram Alpha:
ξ1 – ξ2 ∗ ሺ3ξ1 + ξ2 )𝟑 12.2 𝑎𝑡𝑚
𝑲𝟏 = ∗ሺ )2 = 𝟏𝟐𝟔. 𝟖
15 − ξ1 ∗ ሺ90 − ξ1 – ξ2) 105 + 2ξ1 𝑘𝑚𝑜𝑙/ℎ𝑟

ξ2 ∗ ሺ3ξ1 + ξ2 )
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1 – ξ2 ) ∗ ሺ90 − ξ1 – ξ2)
Distribution of Chemicals
Recycle to Extinction - Species Molar Balances

b)recycle to extinction

Determine the molar flow rates of all of the


components in the reactor effluent when CO2 is
recycled to extinction, given that the total
reactor effluent flow rate is 157.03 kmol/hr

Note CO2 = CO2in/recycle + ξ2


therefore ξ2 = 0 No extent of reaction (in equilibrium)
Methane
Reaction 1
Methane: nCH4 = 15 - ξ1
H2O: nH2O = 90 - ξ1 Reaction 2
H2: nH2 = 3ξ1
CO: nCO= ξ1
CO2: nCO2 = CO2/in/recycle
Total: nT = 105 + 2ξ1 + CO2/recycle/in= 157.03 kmol/hr (Given)

Plugging into the either equilibrium constant expressions yields:

ξ1 ∗ ሺ3ξ1 )𝟑 12.2 𝑎𝑡𝑚


𝑲𝟏 = ∗ሺ )𝟐 = 𝟏𝟐𝟔. 𝟖
15 − ξ1 ∗ (90 − ξ1) 105 + 2ξ1 + CO2/in/recycle 𝑘𝑚𝑜𝑙/ℎ𝑟

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:

T = 105 + 2ξ1 + CO2/recycle/in = 157.03 kmol/hr


CO2/recycle/in = 52.03 – 2ξ1

CO2/in/recycle ∗ ሺ𝟑ξ1)
𝑲𝟐 = = 𝟎. 𝟗𝟐𝟗
ሺξ1) ∗ (90 − ξ1)

Then,

52.03 − 2𝜉1 ∗ ሺ3𝜉1 )


= 0.929
ሺ𝜉1 ) ∗ 90 − 𝜉1
156.09𝜉1 − 6 𝜉1 2 = 83.61𝜉1 − 0.929 𝜉1 2

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

Extent of Reaction Method


(recycle to extinction)
The same solution can be found by solving 𝑲𝟏 for ξ1
(MATLAB, Wolfram, Calculator, or by hand)
ξ1 ∗ ሺ3ξ1 )𝟑 12.2 𝑎𝑡𝑚
𝑲𝟏 = ∗ሺ )𝟐 = 𝟏𝟐𝟔. 𝟖
15 − ξ1 ∗ (90 − ξ1) 105 + 2ξ1 + CO2/in/recycle 𝑘𝑚𝑜𝑙/ℎ𝑟
Distribution of Chemicals
Recycle to Extinction
Species Molar Balance - Another Example
• Consider the conversion of carbon monoxide and hydrogen to
methanol, as shown below:
(6)

• Assume an initial feed of 100 kmol/hr CO and 600 kmol/hr H2.


• Given that the conversion (Xk) of CO is 70%, calculate the
molar flow rates of the three species, eq (3) slide 49, in the
reactor effluent.
Distribution of Chemicals
Recycle to Extinction
Species Molar Balance/Extent of Reaction Example:

• Again, consider the conversion of carbon monoxide and


hydrogen to methanol, as shown below:

• Assume an initial feed of 100 kmol/hr CO and 600 kmol/hr H2.


• Given that the extent of reaction ,ξi, is 70 kmol/hr, calculate
the molar flow rates of the three species in the reactor
effluent.
Distribution of Chemicals
Recycle to Extinction
Species Molar Balance/Extent of Reaction - Another Example:

• For recycle to extinction problems, in addition to the chemical equilibrium


constants K, it is sometimes simpler to consider species molar balances
using the molar extents of reaction, ξi, instead of atomic balances.
• Consider the (dummy) reaction of A and B to desired product D, byproduct
E, given by the system of reactions shown below:

• 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.

Ain , Bin Reactor A+B+C+D


Separator

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):

where the “out” subscripts have been dropped, for simplicity.


• Next, we consider the species molar balances for each species, in terms of
the extents of reaction (ξ1 and ξ2).
Ain , Bin A+B+C+D
Reactor Separator

where we have noted that the inlet concentration of by-product E equals


the outlet.
Distribution of Chemicals
Recycle to Extinction
Species Molar Balance/Extent of Reaction Example:

• This gives a well-defined system of 7 equations (5 species


balances, 2 equilibrium constants) and 7 unknowns (5 species
effluents and 2 extents of reaction), assuming the feed
concentrations are given.
• However, since the inlet concentration of by-product E equals
the outlet due to recycle, the extent of reaction for reaction
two (ξ2) equals zero.
• In fact, for any recycle to extinction problem, the extent of
reaction for all side reactions is 0, since there is no net
production of byproduct.
Distribution of Chemicals
Recycle to Extinction
Species Molar Balance/Extent of Reaction Example:
• Setting ξ2 equal to zero simplifies the system to:

• Substituting these into the equation for K1 allows for an


analytical solution of ξ1 to be found, as shown below:

• The value of ξ1 can be used to find A, B, C, and D directly, while


the equation for K2 can then be used to solve for E. Choose ξ1
so that ξ1 is less than the inlet molar flow rate.