ISOTHERMAL IDEAL REACTOR DESIGN

MARÍA TERESA ACEVEDO MORANTES

 DESIGN EQUATIONS

• BATCH:
– THE CONVERSION IS A FUNCTION OF THE TIME THE REACTANTS
SPEND IN THE REACTOR.
– WE ARE INTERESTED IN DETERMINING HOW LONG TO LEAVE THE
REACTANTS IN THE REACTOR TO ACHIEVE A CERTAIN CONVERSION
X.

?
?
 DESIGN EQUATIONS

• CSTR:
– WE ARE INTERESTED IN DETERMINING THE SIZE OF THE REACTOR
TO ACHIEVE A CERTAIN CONVERSION X.

? -1/rA
?

X
 DESIGN EQUATIONS

• PFR:
– WE ARE INTERESTED IN DETERMINING THE SIZE OF THE REACTOR
TO ACHIEVE A CERTAIN CONVERSION X.

?
?
-1/rA PBR

Generally, the isothermal tubular reactor volume

is smaller than the CSTR for the same
conversion X
 ISOTHERMAL REACTOR DESIGN

• DESIGN PROCEDURE
– MOLE BALANCE
– RATE LAWS
– STOICHIOMETRY
– COMBINATION OF THE ABOVE THREE PROCEDURES AND SOLVE ODE
– OBTAIN THE VOLUME/REACTION TIME FOR THE REACTOR

Do not forget to add some other time

required!
 REACTOR DESIGN

• BATCH:
– CONSTANT VOLUME, WELL-MIXED

• CSTR:
– CONSTANT VOLUMETRIC FLOW RATE
 DAMKÖHLER NUMBER

– RATIO OF THE RATE OF REACTION OF A TO THE RATE OF CONVECTIVE

TRANSPORT OF A AT THE ENTRANCE TO THE REACTOR
– ESTIMATION OF THE DEGREE OF CONVERSION IN A CONTINUOUS
REACTOR
• FIRST ORDER IRREVERSIBLE RXN:

• SECOND ORDER IRREVERSIBLE RXN:

– DA = 0.1 ~ X = 10% ; DA = 10.0 ~ X = 90%

 EXAMPLE, CONST.-V, BATCH, 2ND ORDER
RXN, ISOTHERMAL

• mole balance
• rate laws
• Stoichiometry
• combination
Example 4-1
It is desired to design a CSTR to produce 200 million pounds of ethylene
glycol per year by hydrolyzing ethylene oxide. However, before the design
can be carried out, it is necessary to perform and analyze a batch reactor
experiment to determine the specific reaction rate constant, k. Because the
reaction will be carried out isothermally, the specific reaction rate will need
to be determined only at the reaction temperature of the CSTR. At high
temperature there is a significant by-product formation, while at temperature
below 40°C the reaction does not proceed at a significant rate; consequently,
a temperature of 55°C has been chosen. Because the water is usually present
in excess, its concentration may be considered constant during the course of
the reaction. In the laboratory experiment, 500 ml of a 2 M solution of
ethylene oxide in water was mixed with 500 ml of water containing 0.9 wt%
sulfuric acid, which is a catalyst. The temperature was maintained at 55°C.
The concentration of ethylene glycol was recorded as a function of time,
determine the specific reaction rate at 55°C.
Because water is present in such excess, the concentration of water at any
time t is virtually the same as the initial concentration and the rate law is
independent of the concentration of H2O. (CB≈CB0)
The reaction is first-order in ethylene
oxide:
Batch design equation:

Rate law:
Stoichiometr no volume change, V=V0
y

Combinatio
n
 ?

slope = -k = -0.311 min-1

EXAMPLE, LIQUID PHASE CSTR, 1ST ORDER
RXN, ISOTHERMAL
or
• mole balance
• rate laws
• Stoichiometry
• combination or

 
or

 
EXAMPLE, LIQUID PHASE CSTR, 2ND ORDER
RXN, ISOTHERMAL

• mole balance
• rate laws
• Stoichiometry
• combination or

or

or
 CA0
CA1
CA2
CSTRs in series, 1st order rxn, isothermal

• mole balance
• rate laws
• Stoichiometry  

• combination

...
 CA0
CA1
CA2
 

 
 FA01
FA0
FA02 CSTRs in parallel, isothermal
.
.
• mole balance
same T, V, v

total
volume
total molar flow
rate
 CSTRS IN SERIES

• CONSTANT FLOW RATE

• CONVERSION AS A FUNCTION OF THE NUMBER OF TANKS IN
SERIES TWO EQUAL-SIZED CSTRS IN SERIES WILL GIVE A
HIGHER CONVERSION THAN TWO CSTRS IN PARALLEL OF THE
SAME SIZE WHEN THE REACTION ORDER IS GREATER THAN
ZERO.
 CSTRS IN PARALLEL
• CONSTANT CONVERSION AND RATE OF
REACTION IN EACH TANK
• THE SUM OF THE VOLUME OF THE TANKS EQUALS THE
TOTAL VOLUME OF A SINGLE LARGE CSTR.
• THE CONVERSION ACHIEVED IN ANY ONE OF THE
REACTORS IN PARALLEL IS IDENTICAL TO WHAT WOULD
BE ACHIEVED IF THE REACTANT WERE FED IN ONE
STREAM TO ONE LARGE REACTOR OF VOLUME V.
• CONSIDERING THE DEGREE OF MIXING AND THE ROOM
REQUIRED, A LARGE TANK MIGHT NOT BE APPROPRIATE.
Example 4-2 Close to 12.2 billion metric tons of ethylene glycol (EG) were
produced in 2000, which ranked it the twenty-sixth most produced chemical in the
nation that year on a total pound basis. About one-half of the ethylene glycol is used
for antifreeze while the other half is used in the manufacture of polyesters. In the
polyester category, 88% was used for fibers and 12% for the manufacture of bottles
and films. The 2004 selling price for ethylene glycol was $0.28 per pound. It is
desired to produce 200 million pounds per year of EG. The reactor is to be operated
isothermally. A 1 lb mol/ft3 solution of ethylene oxide (EO) in water is fed to the
reactor (shown in Figure E4-2.1) together with an equal volumetric solution of water
containing 0.9 wt% of the catalyst H2SO4. The specific reaction rate constant is
0.311 min-1, as determined in Example 4-1.

The specified ethylene glycol (EG) production rate:

(a) If 80% conversion is to be achieved, determine the necessary CSTR volume.

CSTR Design equation ：

Rate law ：
Stoichiometry ：

Combination
:
(b) If two 800-gal reactors were arranged in parallel, what is the corresponding
conversion?
CSTR Design equation ：

Rate law ：
Stoichiometry ：

Combination:

The conversion exiting each of the CSTRs in parallel is 81%.

(c) If two 800-gal reactor were arranged in series, what is the corresponding conversion?

The two equal-sized CSTRs in series will give a higher conversion than two
CSTRs in parallel of the same size when the reaction order is greater than zero.
 PFR
• GAS-PHASE REACTIONS ARE CARRIED OUT
PRIMARILY IN TUBULAR REACTORS WHERE
THE FLOW IS GENERALLY TURBULENT.
• ASSUMING NO DISPERSION AND THERE ARE NO
RADIAL GRADIENTS IN EITHER TEMPERATURE,
VELOCITY, OR CONCENTRATION.
• SHOULD BE AWARE OF THE CHANGE OF THE
VOLUME.
N.B.
The majority of gas-phase reactions are catalyzed by passing the reactant through
a packed bed of catalyst particles.
PFR, 2ND ORDER RXN, LIQUID PHASE,
ISOTHERMAL
No pressure drop
• mole balance No heat exchange

• rate laws
• Stoichiometry
• combination

or

Damköhler number for 2nd-order

 PFR, 2ND ORDER RXN, GAS PHASE,
ISOTHERMAL
No pressure drop
• mole balance No heat exchange
• rate laws
• Stoichiometry

• combination
Example 4-3 Ethylene ranks fourth in the Unite States in total pounds of chemicals
produced each year, and it is the number one organic chemical produced each year.
Over 50 billion pounds were produced in 2000, and it sold for $0.27 per pound.
Sixty-five percent of the ethylene produced is used in the manufacture of fabricated
plastics, 20% for ethylene oxide, 16% for ethylene dichloride and ethylene glycol,
5% for fibers, and 5% for solvents.
Determine the plug-flow reactor volume necessary to produce 300 million pounds of
ethylene a year from cracking a feed stream of pure ethane. The reaction is
irreversible and follows an elementary rate law. We want to achieve 80% conversion
of ethane, operating the reactor isothermally at 1100 K at a pressure of 6 atm.

The activation energy is 82 kcal/g mol.

The molar flow rate of ethylene (B):
PFR design equation ：

Rate law
(elementary) ：
Stoichiometry ：

Combination:
(b) It was decided to use a bank of 2-in. schedule 80 pipes in parallel that are
40 ft in length. For pipe schedule 80, the cross-section are, Ac, is 0.0205 ft2.
The number of pipes necessary is
 PRESSURE DROP IN REACTORS

• IN GAS-PHASE REACTIONS, THE CONCENTRATION OF

THE REACTING SPECIES IS PROPORTIONAL TO THE
TOTAL PRESSURE AND PROPER ACCOUNTING FOR
THE EFFECTS OF PRESSURE DROP ON THE REACTION
SYSTEM CAN BE A KEY FACTOR IN THE SUCCESS OR
FAILURE OF THE REACTOR OPERATION (E.G. PBR).
• WHEN ACCOUNTING FOR THE EFFECTS OF PRESSURE
DROP, THE DIFFERENTIAL FORM OF THE MOLE
BALANCE MUST BE USED.
 PBR, 2nd order rxn, gas phase, isothermal

• mole balance
• rate laws
• Stoichiometry

• combination

or

What is the relationship between X and P? If PBR: Ergun equation

 Polymath
Matlab

  Polymath
 
Matlab
 
   Polymath
 
Matlab

  Solución
Analítica

   

   
 Ergun equation
• Pressure drop in a porous bed:
Dominant for turbulent
flow

Dominant for laminar

constant mass flow flow
rate
 ERGUN EQUATION (CONT.)

Pressure drop in terms of Catalyst

weight:
 PBR, 2nd order rxn, gas phase, isothermal

• mole balance
 
• rate laws
• Stoichiometry

• combination
 

 
Reactor PBR
 

 
 
 

 
 

 
  

• mole balance
• rate laws  

• Stoichiometry
     

• combination  

 
SPHERICAL PACKED-BED REACTORS

• WHEN SMALL CATALYST PELLETS ARE REQUIRED, THE

PRESSURE DROP CAN BE SIGNIFICANT, AND THUS THE
CONVERSION DECREASES.
• ONE TYPE OF REACTOR THAT MINIMISES PRESSURE DROP
AND IS ALSO INEXPENSIVE TO BUILD IS THE SPHERICAL
REACTOR, CALLED AN ULTRAFORMER.
• SPHERICAL REACTOR: THE CROSS-SECTIONAL AREA AND
THE WEIGHT OF CATALYST ARE FUNCTIONS OF THE
POSITION.
• IN ADDITION TO THE HIGHER CONVERSION, THE
SPHERICAL REACTOR HAS THE ECONOMIC BENEFIT OF
REDUCING THE PUMPING AND COMPRESSION COST
Liquid phase – mole balance
 ALGORITHM - GAS PHASE

• GAS PHASE
– FOR GAS-PHASE REACTIONS IN WHICH THERE IS VOLUME CHANGE,
MOLAR FLOW RATE IS THE PREFERRED VARIABLE.
– THE TOTAL MOLAR FLOW RATE IS GIVEN AS THE SUM OF THE FLOW
RATE OF THE INDIVIDUAL SPECIES.
– A MOLE BALANCE ON EACH SPECIES HAS TO BE SPECIFIED.
Gas phase – mole balance
 PBR, gas phase, isothermal, no ΔP

• mole balance
• rate laws
• Stoichiometry

• combination

Solve
 MICROREACTORS

• HIGH SURFACE AREA-TO-VOLUME RATIO

• REDUCE OR ELIMINATES HEAT AND MASS TRANSFER
RESISTANCES
• SHORTER RESIDENCE TIMES & NARROWER RESIDENCE TIME
DISTRIBUTIONS
• PRODUCTION OF LAB-ON-A-CHIP, CHEMICAL SENSORS
• ASSUME PFR OR IN LAMINAR FLOW
 THERMODYNAMICALLY LIMITED
RXNS

• CATALYTIC MEMBRANE REACTORS CAN BE

USED TO INCREASE THE YIELD OF REACTIONS
THAT ARE HIGHLY REVERSIBLE OVER THE
TEMPERATURE RANGE OF INTEREST.
• THE MEMBRANE CAN EITHER PROVIDE A
BARRIER TO CERTAIN COMPONENTS, WHILE
BEING PERMEABLE TO OTHERS, PREVENT
CERTAIN COMPONENTS SUCH AS PARTICULATES
FROM CONTACTING THE CATALYST, OR CONTAIN
REACTIVE SITES AND BE A CATALYST IN ITSELF.
 MEMBRANE REACTORS

• THE MEMBRANE REACTOR IS ANOTHER TECHNIQUE

FOR DRIVING REVERSIBLE REACTIONS TO THE RIGHT
IN ORDER TO ACHIEVE VERY HIGH CONVERSION.
• THESE HIGH CONVERSIONS CAN BE ACHIEVED BY
HAVING ONE OF THE REACTION PRODUCTS DIFFUSE
OUT OF A SEMIPERMEABLE MEMBRANE
SURROUNDING THE REACTING MIXTURES.
• TWO MAIN TYPES
– INERT MEMBRANE REACTOR WITH CATALYST PELLETS ON
THE FEED SIDE (IMRCF)
– CATALYTIC MEMBRANE REACTOR (CMR)
THERMODYNAMICALLY LIMITED
REACTIONS
     

Molar Flux of B
  (mol/m2.s)
k’c = overall mass transfer
coefficient m/s
Membrane surface area per unit volume (a)
  Removal rate of B  
(mol/m3) →
 
Removal rate of A
(mol/m3) →
MEMBRANE REACTOR (PART A)

Conversion (X)→
TUBULAR REACTOR OR PFR (PART B)

Conversion (X)→
 STARTUP OF A CSTR

• DETERMINE THE TIME NECESSARY TO REACH STEADY-STATE

OPERATION:
– CONVERSION DOES NOT HAVE ANY MEANING IN THE STARTUP

– USE CONCENTRATION RATHER. THAN CONVERSION AS THE

VARIABLE IN THE BALANCE EQUATIONS
 CSTR, 1st order rxn, liquid phase
const. .V
• mole balance
• rate laws
• combination
t=0  
 

t = ts  

steady-state concentration
Consider a first order reaction carried out in a CSTR. The volume is 8 kL, the flow rate is 2
lit/s, initial concentration is 1.5 mol/lit and the rate constant is k = 1.5×10 -4 s-1. Determine the
time it takes to come to within 1% of steady state value. Is it possible to reduce this time?

   

 
Batch Reactor

   
 

   

 
 SEMI-BATCH REACTORS

• WHEN UNWANTED SIDE REACTIONS OCCUR AT

HIGH CONCENTRATION OF REACTANT B, OR THE
REACTION IS HIGHLY EXOTHERMIC. EXAMPLES
OF REACTIONS:
– AMMONOLYSIS B
– CHLORINATION
– HYDROLYSIS A
• REACTIVE DISTILLATION: CARRYING OUT THE
TWO OPERATIONS, REACTION AND
DISTALLATION IN A SINGLE UNIT RESULTS IN
LOWER CAPITAL AND OPERATING COSTS. C
– ACETYLATION REACTION
– ESTERFICATION REACTION (REMOVE WATER) A+B
 SEMI-BATCH REACTOR

• WRITE THE REACTOR EQUATIONS IN TERMS OF

CONCENTRATION / NUMER OF MOLES OF EACH SPECIES
• WRITE THE MASS BALANCE OF THE VESSEL
• WRITE THE RATE LAWS

C B
O.D.E solver
+B A
B
Semi-batch, liquid phase
A
• mole balance (A)
• mole balance (B)

• V is not a constant
(overall mole
balance)

• combine
…..
Example 4-9 The production of methyl bromide is an irreversible liquid-phase
reaction that follows an elementary law. The reaction
CNBr+CH3NH2→CH3Br+NCNH2 is carried out isothermally in a semibatch reactor.
An aqueous solution of methyl amine (B) at a concentration of 0.025 mol/dm3 is to
fed at rate of 0.05 dm3/s to an aqueous solution of bromine cyanide (A) contained in
a glass-lined reactor. The initial volume of fluid in a vat is to be 5 dm3 with a
bromine cyanide concentration of 0.05 mol/dm3. The specific reaction rate constant
is k = 2.2 dm3/s⋅mol. Solve for the concentration of bromine cyanide and methyl
bromide and the rate of reaction as a function of time.
Semi-batch reactor design
equation:

Rate law:
Combination:

where
 RECYCLE REACTORS

• THEY ARE USED WHEN THE REACTION IS AUTOCATALYTIC, OR

WHEN IT IS NECESSARY TO MAINTAIN NEARLY ISOTHERMAL
OPERATION OF THE REACTOR OR TO PROMOTE A CERTAIN
SELECTIVITY.
• THEY ARE USED EXTENSIVELY IN BIO-CHEMICAL OPERATIONS.
Xs Xo

R, recycle parameter

• TWO CONVERSIONS: THE OVERALL CONVERSION X0 AND THE

CONVERSION PER PASS XS