Stoichiometry for systems involving recycles

Stoichiometry
When chemical reactions occur, in contrast with physical changes of material such as
evaporation or dissolution, you want to be able to predict the mass or moles required for the
reaction(s), and the mass or moles of each species remaining after the reaction has occurred.
Reaction stoichiometry allows you to accomplish this task. The word stoichiometry (stoi-ki-
om-e-tri) derives from two Greek words: stoicheion (meaning "element") and metron (meaning
"measure"). Stoichiometry provides a quantitative means of relating the amount of products
produced by chemical reactions to the amount of reactants.
The following expressions are widely used in stoichiometry:
1. Stoichiometric coefficients:
The numbers that are precede the chemical substances involved in the chemical reaction
equation are known as " stoichiometric coefficients". These coefficients represent quantity of
any reactant that is theoretically required for complete conversion of other reactants.
2. Stoichiometric ratios:
The ratio between any stoichiometric coefficients in a balanced chemical equation is known as
" stoichiometric ratio".
As an example the reaction of nitrogen and hydrogen to produce ammonia:
N2 + 3H2 → 2NH3
The stoichiometric ratios of N2/H2 =1/3, N2/NH3= 1/2 and H2/NH3=3/2

Limiting and Excess Reactants:

In most industrial processes, the quantities of reactants input are not in exact stoichiometric
proportions as fixed by the reaction equation. It is generally desirable that some of the reacting
materials be present in excess quantity over the amounts theoretically required for combination
with other reactants.

a. The limiting reactant: Is the species in a chemical reaction that would theoretically run out
first (would be completely consumed) if the reaction were to proceed to completion according
to the chemical equation and it has smallest maximum extent of reaction
b. The excess reactant: Is the reactant that is present in excess amount over the stoichiometric
requirement equivalent to that of the limiting reactant and it has highest maximum extent of
reaction that of the limiting reactant. If the reaction does not proceed to completion, all the
reactants called excess reactants.
Percent excess: It is the excess quantity of any reactant expressed as a percent of the
stoichiometric amount theoretically required to react completely with the limiting reactant
according to the chemical equation.
% excess
=
amount of the excess reactant feed − amount of the excess reactant required to react with the limiting reactant
amount of the excess reactant required to react with the limiting reactant
×100

𝐹𝑒𝑒𝑑−𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑

% excess = ×100
Theoretical amount required

Extent of Reaction (ᶓ):

The extent of reaction is calculated by dividing the change in the number of moles of a species
that occurs in a reaction, for either a reactant or a product, by the related stoichiometric
coefficient.

ni  nio
ᶓ 
vi

where n i  moles of species i present in the system after the reaction occurs
n io  moles of species i present in the system when the reaction starts
vi  coefficient for species i in particular chemical reaction equation
(moles of species i produced or consumed per moles reacting)

Note:
The products of the reaction have positive signs and the reactants have negative signs
Example 1:
If 20 moles of CO are fed to a reactor with 10 moles of O2 and form 15 moles of CO2, calculate
the extent of reaction?
2CO + O2 → 2CO2
Solution:
The value of the change in the moles of CO2 is: 15-0 = 15. The value of the stoichiometric
coefficient for the CO2 is 2 mol/mol reacting.
The extent of reaction =
(15  0) mol CO2
 7.5 moles reacting
2 mol CO2 / mol reacting
Example 2:
If you feed 10 grams of N2 gas and 10 grams of H2 gas into a reactor:
a. What is the maximum number of grams of NH3 that can be produced?
b. What is the limiting reactant?
c. What is the excess reactant?
Solution:
The chemical reaction is:
N2 + 3H2 → 2NH3
NH3

Reactor 10g H2
10g N2

Next, write down the chemical equation, and get the molecular weights:
N2(g) + 3H2(g) → 2NH3(g)
Given g: 10 10 0
MW: 28 2.016 17.02
Calcd, gmol 0.357 4.960 0
The next step is to determine the limiting reactant by calculating the maximum extent of
reaction based on the complete reaction of N2 and H2
0.357mol N 2
 max (based on N 2 )   0.357 moles reacting
1mol N 2 / moles reacting
4.960mol H 2
 max (based on H 2 )   1.65moles reacting
3mol H 2 / moles reacting

You can conclude that N2 is the limiting reactant and H2 is the excess reactant:

4.960 –3(0.357)
% excess (H2) = ×100= 363.12 %
3(0.357)

The maximum amount of NH3 that can be produced is based on assuming complete conversion
of the limiting reactant
Since, 1 mole of N2 = 2 moles of NH3
Therefore 0.357 moles will produce 0.714 moles of NH3
1 mole NH3 = 17.02 g NH3
0.714 moles of NH3 = 12.2 g NH3
Recycle
Recycling is the act of taking one stream in a process and reusing it in an earlier part of the
process rather than discarding it. It is used in a wide variety of processes.

Uses and Benefit of Recycle

The use of recycle makes a great deal of environmental and economic sense, for the following
reasons among others:
 Using recycle lets a company achieve a wider range of separations
This will be demonstrated in the next section. However, there is a tradeoff: the more dilute or
concentrated you want your product to be, the lower the flowrate you can achieve in the
concentrated or dilute stream.
 By using recycle, in combination with some sort of separation process, a company can
increase the overall conversion of an equilibrium reaction.
You may recall from general chemistry that many reactions do not go to completion but only
up to a certain point, because they are reversible. How far the reaction goes depends on the
concentrations (or partial pressures for a gas) of the products and the reactants, which are
related by the reaction stoichiometry and the equilibrium constant K. If we want to increase the
amount of conversion, one way we can do this is to separate out the products from the product
mixture and re-feed the purified reactants in to the reactor. By Le Chatlier's Principle, this will
cause the reaction to continue moving towards the products.
 By using recycle, it is possible to recover expensive catalysts and reagents.
Catalysts aren't cheap, and if we don't try to recycle them into the reactor, they may be lost in
the product stream. This not only gives us a contaminated product but also wastes a lot of
catalyst.
 Because of the previous three uses, recycle can decrease the amount of equipment
needed to get a process meet specifications and consumer demand.
For example, it may improve reaction conversion enough to eliminate the need for a second
reactor to achieve an economical conversion.
 Recycle reduces the amount of waste that a company generates.
Not only is this the most environmentally sounds way to go about it, it also saves the company
money in disposal costs.
 Most importantly, all of these things can save a company money.
By using less equipment, the company saves maintenance as well as capital costs, and probably
gets the product faster too.
Because reactions seldom go to completion, a recycle stream is often introduced to recover and
reuse unreacted reactants. Two definitions of reactant conversion are used in the analysis of
chemical reactors with product separation and recycle of unconsumed reactants:

𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑝𝑟𝑜𝑐𝑒𝑠𝑠−𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑜𝑢𝑡𝑝𝑢𝑡 𝑓𝑟𝑜𝑚 𝑝𝑟𝑜𝑐𝑒𝑠𝑠

Overall conversion = × 100
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑝𝑟𝑜𝑐𝑒𝑠𝑠

𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 −𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑜𝑢𝑡𝑝𝑢𝑡 𝑓𝑟𝑜𝑚 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

Single-pass conversion = × 100
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

Recycle stream
It is part of the product stream (either similar or different composition) that is separated and
returned to mix again with inlet stream (fresh feed) for economic considerations. The gross
product (G) leaving the process is commonly separated by suitable separation technique such
as distillation, filtration, extraction etc. into the net product (P) and recycle stream (R); whereas
the inlet feed (T) input to the process is made up by mixing the fresh feed (F) and recycle
stream (R) as shown in the following block diagram.

The recycle ratio, sometimes called reflux ratio, is widely used in recycle calculations. It is the
ratio between the amount of recycle to that of the net product, i.e. (R/P).

The recycle stream allows operation of the reactor at low single‐pass conversion, while still
achieving high overall conversion for the system.

Consider the Reaction A→ B, with the process scheme shown below:

 100 − 0
Overall conversion = × 100 = 100%
100

100 − 25
Single-pass conversion = × 100 = 75%.
100

The advantage gained by obtaining 100% conversion (and thus not wasting costly reactants)
may be offset by the additional costs of separation and recycle equipment. This is an
optimization problem.

Example 3

A distillation column separates 10,000 kg/hr of a mixture containing equal mass of benzene
and toluene. The product D recovered from the condenser at the top of the column contains
95% benzene, and the bottom W from the column contains 96% toluene.
The vapor V entering the condenser from the top of the column is 8000 kg/hr. A portion of the
product from the condenser is returned to the column as reflux R, and the rest is withdrawn as
the final product D. Assume that V, R, and D are identical in composition since V is condensed
completely. Find the ratio of the amount refluxed R to the product withdrawn D.

Overall Process
Total Balance: 10,000 = D + W
Benzene Balance: 10,000(0.50) = D(0.95) + W(0.04)
Solving simultaneously, D = 5050 kg/hr; W = 4950 kg/hr
Total balance around the separator:
8000 = R + D
R = 2950 kg/hr
Ratio (R/D) = (2950/5050) = 0.58
Tutorial question
1. A schematic diagram of a steady process is shown below. The fresh feed (F) to the
reactor consists of 96 mol % reactant A and 4 mol % inert. The stoichiometry of the
reaction A→C. A part of the reactor effluent is recycled. The molar flow rate of the
recycle stream is 0.3F. the product stream P contains 50 mol % C. The percentage
conversion of A in the reactor is based on A entering the reactor at point 1 in the figure
below
2. Two elemental gases (A and B) are reacting to form a liquid C in a steady state process
as per the reaction A + B→C. The single-pass conversion of the reaction is only 20 %
and hence recycle is used. The product is separated completely in pure form. The fresh
feed has a 49% of A and B each along with 2 mol% impurities. The maximum allowable
impurities in the recycle stream is 20 mol%. Calculate the amount of purge stream (in
moles) per 100 moles of fresh feed.
3. Methanol is synthesised from carbonmonoxide and hydrogen in a catalytic reactor by
the reaction CO+ 2H2 → CH3OH. If recycle to feed ratio is 5. Calculate the single pass
conversion