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CRE1 PAPER - Alif - Farhandi - Hannah
CRE1 PAPER - Alif - Farhandi - Hannah
Based on:
GROUP 5
FACULTY OF ENGINEERING
UNIVERSITY OF INDONESIA
DEPOK 2017
TABLE OF CONTENTS
I.2.1 Conversion
Part 2: Stoichiometry
I.4.1.5 Microreactor
LITERATURE REVIEW
Rate of reaction describes the speed of a number of moles of a certain chemical species being
consumed in a reaction to form the product chemical species. Chemical reaction happened
whenever lost their identity and assumed new form of identity is several ways such as
decomposition, combination, and isomerization. The reaction rate is defined as the rate of
appearance of a product or rate of disappearance of a reactant.
Reactant concentrations
Reaction temperature
Catalyst presence
Surface area of reactants of catalysts
Rate of reaction (-rA), is the number of moles of A reacting or disappearing per unit time
volume (mol/dm3s)
dC A
rA = dt
Mole balance on species j any period of time (t), can be defined as:
Used for small scale operations and not suitable for slow reactions.
It has the advantage of high conversions that can be obtained by leaving the reactant
in the reactor for long periods of time.
It has the disadvantages of high labor costs per batch, the variability of products from
batch to batch, and the difficulty of large-scale production.
General mole balance equation of an ideal batch reactor, since batch reactor has no inflow nor
outflow of reactants or products therefore:
[rate or reactant loss due to chemical reaction] = [rate of accumulation of reactant in the reactor]
dN A
( rA )V = dt
Integral form of the mole balance on a batch reactor with boundary t = 0, NA = NAO and t = t1,
NA = NA1
CSTR is used primarily for liquid phase reaction and operated at steady state. In
CSTR process it is assumed that the mixture of chemical species are perfectly mixed -
where each variable is the same at any point in the mixture.
PFR illustration
FA0dXA = (-rA)dV
V X Af
dX A
dV
F A0 = rA
0 0
PBR is used for heterogenous reaction. The reaction takes place on the surface of the
catalyst. The reaction rate of PBR is based on mass solid catalyst (W). The mass of
solid is used because the amount of catalyst is what is important to the rate of product
formation.
PBR illustration
The integral form of the PBR design equation to calculate catalyst weight is as follows
I.2.1 Conversion
NA = NA0 - NA0X
dN A
dt = rA V (1)
Equation (1); mole balance for batch reactor, substituted into the time-differentiated equation
resulting in:
The equation above is the design equation for batch reactor in terms of conversion
I.2.3 Flow Reactors Design Equation
In a continuous flow reactors system, the conversion is a function of reactor volume (V). The
general mole balance equation can be defined as:
Where the rearranged equation is also equivalent with the equation below:
FA0 = CA0 V0
Substituted with the flow reactor design equation in terms of conversion, resulted in
the design equation in terms of conversion for CSTR
F A0 X
V = rA
2.3.2 Plug Flow Reactor
Equation 3 substituted into equation 1, resulted in the design equation for PFR in
terms of conversion
dX
F A0 dV = rA
Equation above integrated with limit V=0 when X=0
X
V = F A0 dX
rA
0
With any given rate of function in terms of conversion, with levenspiel plot any type of
reactor can be sized and the volume of reactors can be found. Volume of the reactors is
represented by the shaded area in the levenspiel plot.
In irreversible reaction, the rate usually the biggest at the initial of the reaction, that is when
the concentration is at its peak. For reversible reaction, the maximum conversion is the
equilibrium conversion. At equilibrium the reaction rate is zero.
F A0 F Ai
Xi = F A0 rearranged FAi = FA0
- FA0 . Xi
In - Out + Generation = 0
Reactor 2:
In - Out + Generation = 0
The overall conversion of two PFRs in series is the same as one PFR with the same
total volume.
X2 X1 X2
dX
F A0 r
A
= dX
F A0 r
A
+ dX
F A0 r
A
0 0 0
Reactor 2: PFR
X2
F A0
V2 = rA2 dX
X1
Reactor 3: CSTR
F A0 (X 3 X 2 )
V3 = rA3 dX
Space Velocity
Defined as:
V0 1
SV = V =
Before going to the definition of rate law, some types of reactions need to be known. A
homogeneous reaction is one that involves only one phase. A heterogeneous reaction is one
that involves more than one phase, and the reaction usually occurs at the interface between
phases. An irreversible reaction is ones that proceeds in only one direction and continues in
that direction until the reactants become exhausted. A reversible reaction can proceed in
either direction, depending on the concentration of reactants and products relative to the
corresponding equilibrium concentrations. An irreversible reaction behaves as if there is no
equilibrium condition exists.
The relative rates of reaction of the various species involved in a reaction can be obtained
from the ratio of stoichiometric coefficient.
A + ab B ac C + ad D
For every mole of A that is consumed, c/a moles of C appear. In other words,
r c = ac ( r A ) = ac r A
The relationship can be expressed directly from the stoichiometry of the reaction .
aA+bB cC+dD
rA rB rc rD
For which,
a = b = c = d
-rA = [kA(T)][fn(CA,CB,Cn)]
The number of n, which is the reaction order, is any positive integer, that could be from zero,
one, two, three, etc. When n equals zero, it means the reaction ha a zero-order reaction. In
zero-order reaction, the concentration of reactants do not affect the reaction rate, in other
words, the rate is independent to the concentration. In this paper, only the zero, first, and
second order reaction will be explained. A first order reaction is when the concentration
doubles, then the rate will be also doubles, and for second order reaction, when the
concentration is doubled, the rate is 4 times larger. Further differences will be elaborated on
Quantity k is referred to as the specific reaction rate or the rate constant. It is almost always
dependent on temperature and depends on it is whether or not a catalyst is present and in gas
phase reaction it may be a function of total pressure.
Arrhenius Equation
Arrhenius suggested that the temperature dependence of the specific reaction
rate kA could be correlated by the equation
E a /RT
k = Ae
Where A represents the pre-exponential factor or frequency factor, EA is the activation energy
in J/mol, R is the gas constant (commonly use 8.314 J/mol.K) and T is the temperature (in
kelvin).
Activation Energy
The activation energy is a energy level that reactant molecules must overcome before a
reaction can occur. Molecules need energy to distort or stretch their bonds so that they break
them and thus, form a new bonds. Steric and electron repulsion forces must be overcome as
the reacting molecules come close together.
The Reaction coordinates: denote the potential energy of the system as a function of the
Activation energy can be determined by carrying out the reaction with different temperature.
Part 2: Stoichiometry
Before going further to the explanations for batch and flow systems stoichiometry, a basic
concept will be explained first. This concept will be useful for the next two points in this
section.
Stoichiometric Table presents the stoichiometric relationships between reacting molecules for
a single reaction. It tells us how many molecules of one species will be formed during a
chemical reaction when a given number of molecules of another species disappears.
Batch reactors are primarily used or the production of specialty chemicals and to obtain rate
date in order to determine the reaction rate laws and the law parameters such as k, the specific
reaction rate.
NA=NA0-NA0X=NA0(1-X)
NT = NT 0 + dN A0 X
Batch Concentration
The form of stoichiometric table for continuous flow reactor is virtually identical to the batch
one, except that the difference in symbols, Nj0 is replaced by Fj0, Nj is replaced by Fj.
Fa M oles/time M oles
CA = v = Liters/time = liter
For liquids, volume change with reaction is negligible when no phase are taking place.
V=V0
Gas Phase Concentration
In a gas phase reaction, the volume is varied. The concentration of component can be
determined by expressing v as a function of conversion as:
P V = Z NT R
T
T = Temperature, K
Z = Compressibility Factor
R = Gas Constant
At complete conversion
The temperatures and pressures will not change significantly during the course of the
reaction. Therefore we can assume Z Z0.
The design structure for isothermal reactors in term of conversion combines the fourth
chapter with the knowledge from the previous three chapters explained above. For simpler
illustration, the diagram below outlines the overall steps for all reactors in the most
straightforward way.
Calculation for isothermal reactor design requires the use of algorithm, which is described
chronologically by five general steps:
1. Mole Balance:
Establish the appropriate mole balance equation, depending on the type of reactor
2. Rate Law:
3. Stoichiometry:
4. Law Combination:
Substitute the rate law and stoichiometry into the mole balance equation
5. Evaluation:
In batch operation system, the assumption is the absence of inlet and outlet flow. With
constant volume, the mole balance equation for batch reactor is written in terms of
concentration,
1 dN A dC A dC A
V ( dt ) = dt = rA or dt = rA
By applying the algorithmic steps, the mole balance equation can be evaluated in
order to achieve the equation of time needed for the operation within the reactor,
1. Mole Balance
2. Rate Law
3. Stoichiometry
4. Law Combination
5. Evaluation
The integration yields the equation of operating time for batch reactor,
The complete algorithms that also cover the second-order reaction is provided in the
table below:
I.4.1.2 Continuous-Stirred Tank Reactor
1. Mole Balance
v 0 C A0 X = rA V
2. Rate Law
rA = kC A
3. Stoichiometry
C A = C A0 (1 X )
4. Law Combination
= 1k ( 1X
X
)
5. Evaluation
C A0 k
CA = 1+ k and X = 1 + k
In prior to designing CSTR, the degree of conversion has to be identified by
calculating Damkohler Number (Da) i.e. a dimensionless value that serves quick
estimation for degree of conversion. Da 0.1 results < 10% conversion while Da 10
leads > 90% conversion. Thus, Da is directly proportional to the resulting conversion.
Formula of Da is further divided into first and second order of irreversible reaction:
First-Order Reaction
Second-Order Reaction
The series arrangement of two CSTRs below are said to be in the first order of
reaction with liquid-phase components (v = v0).
The operating temperature for the example above is different for each CSTR.
Meanwhile in the next example illustrated below, equally-sized CSTRs are operated
at the same temperature i.e. k is the equal for all reactors.
In the case of n equal-sized CSTRs, the equation in the red box regarding the
concentration leaving the last reactor can also be expressed in terms of conversion.
Conversion plot as a function of number of reactor for a first order reaction is shown
As for the CSTR in parallel arrangement according to the picture below:
The formula for individual reactor volume,
The reactors have equal size and temperature, which leads to the same conversion and
reaction rate for each reactor. Then the molar flow rate and volume can be substituted.
For a second-order liquid-phase reaction that takes place in CSTR, the combination of
rate law and CSTR design equation yields,
v = v 0 , C A = C A0 (1 X ) , and F A0 X = v 0 C A0 X
The equations for tubular reactors are categorized in accordance to the phase of
substances inside the reaction, which is either liquid-phase or gas-phase.
Fluid flow through packed beds is accompanied by substantial pressure drop across
the bed. For liquid-phase reactions, slight changes in pressure do not affect
concentration and consequently does not affect the reaction rates. Meanwhile in the
case of gas-phase reactions, the concentration is a function of pressure. Reduction in
pressure implies reduction in concentration as well as the reaction rates.
The relationship between concentration and pressure in different phase reactions are
categorized into several cases:
Case I: Liquid-phase reactions
Concentration is independent of pressure, so pressure is unnecessary to be included
in the calculation of conversion.
v = v0 =constant
Case II: Gas-phase reactions
For isothermal reactor, (P/P0) may vary along the reactor length.
s = sphericity
= porosity
= density (kg/m 3 )
uo =
superficial velocity (m/s)
N RE = Dp uo /
Differential equation for pressure drop in spherical-packing bed reactor:
The packing characteristic such that the porosity and particle diameter are considered
invariant toward reactor length, so the parameters that will be evaluated as a function
of reactor length is the viscosity, density and operating parameter G.
G = 0 u0 = u
Where the unit of G is defined to be the mass flow rate per unit area (kg/ m2 -s).
Evaluating Viscosity
iscosity of gases are weak function of pressure. We can assume the gas mixture
V
viscosity to be independent of pressure. The viscosity of gases depends on the mixture
composition. In a reactor, mixture composition will change, the gas mixture viscosity
will also change.
Evaluating Density
Density of gases depend on pressure. There are two ways of handling the pressure
terms, in terms of inlet density, P/Po, T/To. In terms of local P, T and composition
I.4.1.5 Microreactors
PROBLEM SOLVING
Question
Table 3-11 gives the initial rate data [-d(B2H6)/dt] reported for the gas phase reaction of
diborane and aceone at 114oC: B2H6 + 4 Me2CO 2(Me2CHO)2BH. If a rate expression is of
the form
Rate = k P nB 2 H 6 P M
m
e2 CO6
Solution
Rate = k P nB H6
m
PM e CO
2 2 6
ln (Rate) = ln k + n ln P nB 2 H 6 + m ln P M
m
e2 CO6
variables rate. The results of the gives these values for the coefficients.
Question
The reaction 2N OCl 2N O + Cl2 is studied at 200oC, The concentration of NOCl initially
consisting of NOCl changes as follows:
Solution
Rearranging the 2nd order rate equation and integrating with the boundary condition at t = 0,
CA = CAO and at t = t, CA = CA, gives
Plot of 1/CA versus t gives a straight line with the slope = k = 0.06661/gmol.s. The program
PROG1 determines the rate constant for a second order rate of reaction. Equation 3-285 is of
the form 1/Y = A + BX where the slope B is the rate constant k. The results of the computer
program are shown in Table 3-14.
Question
Huang and Dauerman (1969) have studied the acetylation of benzyl chloride in dilute
solution at 102oC. Using equimolal concentrations of sodium acetate and benzyl chloride
(0.757 kmol/m3), Table 3-16 lists reported data on the fraction of benzyl chloride remaining
unconverted versus time. Determine the order of the reaction and the reaction rate constant at
this temperature.
Solution
And
dC a dX b
dt
= C BO dt
...(3)
Substituting equation (2) and (3) into the rate equation for component B gives
dX b
( ra ) = C BO dt
= k C 2BO (1 X a )2
[ 1
1X B ]
1 = kC
BO
t
[ 1
C a /C BO ]
1 = k C BO t
k= 1
C BO t [ 1
C a /C BO
1 ]
Table 3-17 shows the calculated values of the rate constant k at various time (t).
Discounting the first and the last two values of rate constant k, the average value of the rate
constant is k = 0.0055 m3 /(mol.sec). This shows that rate of reaction is second order
a. The rule of thumb that the rate of reaction doubles for a 10C increase in temperature
occurs only at a specific temperature for a given activation energy. Develop a relationship
between the temperature and activation energy for which the rule of thumb holds. Neglect
any variation of concentration with temperature.
b. Determine the activation energy and frequency factor from the following data:
Answer:
a. We know that that the rate of reaction doubles for 10 C, and if a reaction rate doubles
for an increase in 10 C, when T = T1 then let k = k1 and when T = T2 = T1 + 10, let k
= k2 = 2k1. Then with k = Ae^-E/RT in general, k1 = Ae^-E/RTi and k2 =
Ae^-E/RT2.
Therefore:
The b part, We obtain k= Ae^(E/RT) From equation 3-18.
From the data, at T1 = 0 C, k= Ae^(E/RT) and T2 = 100 C, k2= Ae^(-E/RT2)
Dividing gives:
Question 4-11B
The gaseous reaction A B has a unimolecular reaction rate constant of 0.0015 min-1 at
80F. This reaction is to be carried out in parallel tubes 10 ft long and 1 in. inside diameter
under a pressure of 132 psig at 260F. A production rate of 1000 lb/h of B is required.
Assuming an activation energy of 25,000 cal/mol, how many tubes are needed if the
conversion of A is to be 90%? Assume perfect gas laws, A and B each have molecular
weights of 58.
Given data:
-rA = kCA
X = 0.90
MB = 1000 lb/hr
Dt = 1 inch (I.D)
L = 10 ft
T = 260F = 720R
number of tubes
Nt =
= 17.21 lb mol/hr
FB =
-rA = kCA(1 X) CA = =
V = FA0 =
FA0 = ln 9() = ln 10
V = ln 10 = = ln 10 = 0.72 ft3
Question 4-15
It is desired to carry out the gaseous reaction A B in an existing tubular reactor consisting
of 50 parallel tubes 40 ft long with a 0.75-in. Inside diameter. Bench-scale experiments have
given the reaction rate constant for this first-order reaction as 0.00152 s-1 at 200F and 0.0740
s-1 at 300F. At what temperature should the reactor be operated to give a conversion of A of
80% with a feed rate of 500 lb/h of pure A and an operating pressure of l00 psig? A has a
molecular weight of 73. Departures from perfect gas behavior may be neglected, and the
reverse reaction is insignificant at these conditions. (Ans: T = 275F.)
Given Data:
2
nt D2 (50)( 0.75
12 )
V = 4
L = 4
(40) = 6.14 ft3
m lb
500 hr
FA0 = M WA = 73 lb = 6.86 lb mol/hr
A lbmol
X
F F A0 RT
FA0
dX 1 1
V = FA0 X rdX = kC AO (1X)
= kCAO ln ( 1X ) = ky A0 P
ln ( 1X )
A AO
0 0
F RT 1
k = V A0y ln ( 1X )
A0 P
E
At T2 = 300F = 759.67R 760R, k1 = 0.0740 = A e RT 2
k2
k1
= exp[ E 1
R (T
1
T 1 )]
2
k T T
ln k2 = E (1
R T
1
T1
) = E ( 2 1)
R T 1T 2
1 2
T 1T 2 k
ln k2 = (660)(760)
E
0.0740
R = T ln 0.00152 = 19500R
2 T 1 1 (100)
E
A = k1 exp[ RT 1
] so k = k1 exp [ E (1
R T
1
T1
)]
From the previous equation above,
F RT 1
k = V A0y ln ( 1X )
A0 P
F RT 1
Thus, k = V A0y ln ( 1X ) = k 1 exp [ E (1 1
)]
A0 P R T T1
F A0 R k1 exp [ E 1 1
R ( T T )]
1
V y A0 P
ln ( 1X ) = T
1
psia f t3
(6.86 lbmol
hr )(10.73 lb molR )
exp[19500( T1 660R
1 )]