Auto catalytic reactions

In autocatalyst reaction, the product which is formed acts as

catalyst and it increase the rate of reaction, we cannot add any
external catalyst

Introduction:In an autocatalytic reaction, however, the rate at the start is low

because little product is present; it increases to a maximum as product is
formed and then drops again to a low value as reactant is consumed. Figure
6.18 shows a typical situation.Reactions with such rate-concentration curves
lead to interesting optimization problems. In addition, they provide a good
illustration of the general design method presented in this chapter. For these
reasons let us examine these reactions in some detail. In our approach we deal
exclusively with their 1/(r,) versus X, curves with their characteristic minim.
 Example of autocatalyst reaction

The most important examples of autocatalytic reactions are the broad class of
fermentation reactions which result from the reaction of microorganism on an organic
feed. When they can be treated as single reactions, the methods of this chapter can be
applied directly. Another type of reaction which has autocatalytic behavior is the
exothermic reaction (say, the combustion of fuel gas) proceeding in an adiabatic
manner with cool reactants entering the system. In such a reaction, called autothermal,
heat may be considered to be the product which sustains the reaction. Thus, with plug
flow the reaction will die. With backmixing the reaction will be self-sustaining because
the heat generated by the reaction can raise fresh reactants to a temperature at which
they will react.
Design equation
The designing equation of autocatalyst reactor is same as in
recycle reactor
𝑉 𝑋𝐴𝑓 𝑅+1
❶ ɿ 𝐶𝑎𝑜 = = ‫ (𝑓𝐴𝑋∗𝑅=𝑖𝐴𝑋׬‬−𝑟𝐴 dXA)
𝐹𝐴𝑜 𝑅+1
𝑋𝐴𝑓 1
=(R+1)‫׬‬ 𝑅∗𝑋𝐴𝑓( dXA)
𝑋𝐴𝑖= −𝑟𝐴
𝑅+1

❷ The other method is the differential method, but we use

the integral method by using the graph to perform the
calculation.
 Sizing curves when there is no recycle

By using these graphs we can

imagine what type of the size
reactor is best so, if we see the
graph (1/-ra) vs XA and see if
we use the mixed flow reactor
the area is larger because all
rectangle, but when we use
the plug flow reactor we save
the area because the area
under the curve.
 Plug flow Versus mixed Flow
Reactor, No Recycle
For any particular rate concentration curve a comparison of areas in Fig. 6.19 will show
which reactor is superior (which requires a smaller volume) for a given job. We thus find
1. At low conversion the mixed reactor is superior to the plug flow reactor.
2. At high enough conversions the plug flow reactor is superior.
These findings differ from ordinary nth-order reactions (n > 0) where the plug flow reactor is
always more efficient than the mixed flow reactor. In addition, we should note that a plug
flow reactor will not operate at all with a feed of pure reactant. In such a situation the feed
must be continually primed with product, an ideal opportunity for using a recycle reactor.
Sizing curves when recycle is use
First thing which you remember first is that , when we use the recycle
ratio(R) what is the ratio we want to set . Which is the Optimum recycle
Ratios. To set this ratio there are two methods Differential method and
other graphical (integral method) .At here we discuss the Graphical
method. So, lets start.
Advantage and Disadvantage
Let we have an auto catalyst reaction.
H2+I2 2HI
In this reaction the hydrogen iodide which is formed act as auto catalyst.
This is the gas phase reaction. So first we Calculate the production capacity.
H2 I2 HI
2 253.8088 256.18
2/256.18 253.80/256.18 256.18/256.18
0.0079 0.99 1
1000* 0.0079 1000* 0.99 1000*1
7.9kg 990kg 1000kg
This is the elemenrty gas phase autocatalytic
reaction
So we first find the (Ea)
𝑃𝑟𝑜𝑑𝑢𝑐𝑡 −𝑟𝑒𝑐𝑡𝑎𝑛𝑡𝑠 2−2
Ea = = =0
𝑟𝑒𝑐𝑡𝑎𝑛𝑡𝑠 1

Rate if reaction for autocatalyst reaction

-rH2= KCH2*CI2*CHI^2
When we study the kinetics and calculate the values ,so we can see the value
of Ca anf rate (-rH2) the table is given below.
 Table and Graph (graph is sizing curve )
Ca Rate(-rH2) Xa=Cao-Ca/Cao (-1/rH2) Graph between Ca vs -1/rH2
18.00

0.6 0.06 0.95 16.67 16.00

14.00
1.6 0.08 0.86 12.50
12.00
2.6 0.2 0.78 5.00

(-1/rH2)
10.00

3.6 0.5 0.69 2.00 8.00

6.00
5.6 0.6 0.52 1.67
4.00
7.6 0.25 0.34 4.00 2.00

9.6 0.1 0.17 10.00 0.00

0.00 0.20 0.40 0.60 0.80 1.00
Ca
11.6 0.06 0.00 16.67
 Case study
Case 1: If the molar flow of the rectants is (7.9 mol/hr) and we get the 95% conversion.
What is the volume of the reactor.(Cao=11.6mol/m3)
Graph between Ca vs -
(a). If we use the mixed flow reactor.
1/rH2
(b). If we use the plug flow reactor. 18.00
16.00
solution: 14.00
12.00

(-1/rH2)
(a):So if we use the mixed flow reactor area is the rectangle 10.00
8.00
ɿ= (0.95)*(16.6)= 15.77 hr 6.00
4.00
so in order to find volume (V) 2.00
0.00
ɿ 𝑉 0.00 0.50 1.00
=
𝐶𝑎𝑜 𝐹𝐴𝑜 Ca

V=10.739 m3
 If we use the plug flow reactor
(b): if we use the plug flow reactor then the area under the curve
so, ɿ=Area under the curve= 6.62 hr Graph between Ca vs -1/rH2
so find v 18.00

16.00
ɿ 𝑉
= 14.00
𝐶𝑎𝑜 𝐹𝐴𝑜
12.00
V= 4.50 m3

(-1/rH2)
10.00
So, by using the plug flow reactor we can use less volume as 8.00

Compared to mixed floe reactor. 6.00

4.00
Volumetric flow rate in case of mixed flow=V/ ɿ = 0.68m3/hr
2.00
Volumertic flow rate in plug flow reactor= V/ ɿ=0.68m3/hr 0.00
0.00 0.50 1.00
Ca
 Case 2: If we used the plug flow reactor and recycle is
used then what is the optimum recycle operation. At
what conversion the recycle is just right.
As we can discuss earlier that from the graph we see at what point the recycle is
good.

Graph between Ca vs -1/rH2 Graph between Ca vs - Graph between Ca vs -

20.00 1/rH2 1/rH2
15.00 20.00 20.00
(-1/rH2)

15.00 L 15.00

(-1/rH2)
(-1/rH2)
10.00 P 10.00 10.00
5.00 L 5.00 P 5.00 L P
0.00 M Q 0.00 M 0.00 M Q
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00
Ca Ca Ca

PQ>LM so recycle is no PQ<LM so recycle is no PQ=LM so recycle is just

suitable(recycle to high) suitable(recycle to small) right at conversion 0.30
so, we can find xa1=0.30
𝑅∗𝑥𝑎𝑓
as we know that xa1=( )
𝑅+1
𝑜.95𝑅
0.30= , 𝑅 = 0.462
𝑅+1 Graph between Ca vs -1/rH2
So,area under the curve is 3.22 18.00

ɿ=3.22hr 16.00
14.00
ɿ 𝑋𝐴𝑓 𝑑𝑋𝐻2 𝑉
= (𝑅 + 1) ‫𝐴𝑋׬‬1 ( ) = 12.00
𝐶𝐴𝑜 −𝑟𝐻2 𝐹𝐴𝑜

(-1/rH2)
10.00
𝑋𝐴𝑓 𝑑𝑋𝐻2 8.00
ɿ =‫𝐴𝑋׬‬1 ( ) = 3.22
−𝑟𝐻2 6.00
V= ɿ*Fao(R+1)/Cao= 3.2060m3 4.00
2.00
V=3.21 m3 0.00
0.00 0.20 0.40 0.60 0.80 1.00
Ca
Reactor design for specified production
capacity.