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Introduction to Catalysis

Catalyst

A substance that alters the reaction rate of a particular chemical reaction is called a catalyst.

Chemically unchanged at the end of the reaction.

Positive Catalyst (catalyst): Increases the rate of reaction

Negative Catalyst (Inhibitors): Decreases the rate of reaction

How does a catalyst change rate of reaction???

By providing alternative pathway or mechanism to lower/higher activation energy

E a A + B ΔG E a ′ A + B + catalyst ΔG
E a A + B ΔG
E a
A + B
ΔG
E a ′ A + B + catalyst ΔG
E
a ′
A + B +
catalyst
ΔG

k(T) = k 0 e -Ea/RT E a ′ < E a k 0 ′ > k 0

k′ > k

R T E a ′ < E a k 0 ′ > k 0 k′ >

ΔG = ΔG

C

C + catalyst

uncatalyzed

catalyzed

Role of Catalysis in a National Economy

24% of GDP from Products made using catalysts Fuels, Clothes, Polymers, Drug, Agro-chemicals)

> 90 % of petro refining & petrochemicals processes use catalysts

90 % of processes & 60 % of products in the chemical industry

> 95% of pollution control technologies

Catalysis in the production/use of alternate fuels (NG,DME, H 2 , Fuel Cells, biofuels…)

(Food,

Three Scales of Knowledge Application

Three Scales of Knowledge Application

Types of Catalysts

(1) Homogeneous Catalysts

(2) Heterogeneous Catalysts

(3) Auto-Catalysts

(1) Homogeneous Catalysts:

Catalyst with the same phase as reactants.

Usually in aqueous phase or gaseous phase.

Ex: Oxidation of I - with S 2 O 8 2- with Fe 3+ ion as a catalyst

2I - + S 2 O 8 2-

==> I 2 + 2SO 4 2-

-----------------------------------------

--

2I - + 2Fe 3+ ==> 2Fe 2+ + I 2 2Fe 2+ + S 2 O 8 2- ==> 2Fe 3+ + 2SO 4 2-

(2) Heterogeneous Catalysts

Catalyst with different phase as reactants. Usually Catalyst in solid form and reactants in aqueous or gaseous form.

Ex: SRM, POX , CDM, Hydrogenation of ethane (Ni as catalyst), CNT

aqueous or gaseous form. Ex: SRM, POX , CDM, Hydrogenation of ethane (Ni as catalyst), CNT

CNT

Hydrogenation of ethane

aqueous or gaseous form. Ex: SRM, POX , CDM, Hydrogenation of ethane (Ni as catalyst), CNT

6

(3) Auto-Catalysts

The product in the reaction acts as a catalyst of the reaction. This product is called auto-catalyst.

Ex: 2MnO 4 - + 16H + + 5C 2 O 4 2- ==> 2Mn 2+ + 8H 2 O + 10CO 2

Applications of catalysts:

(1) Chemical Industries (2) Catalytic converters in automobile exhaust (3) Biological catalysts as enzymes (fermentation, baking)

(2) Catalytic converters in automobile exhaust

(2) Catalytic converters in automobile exhaust 8

Heterogeneous Catalytic Reactors

Packed Bed (single or multi-tube)
Packed Bed
(single or multi-tube)
Catalytic Reactors Packed Bed (single or multi-tube) Fluidized Bed Slurry Reactor • Design goals – rapid

Fluidized

Bed

Reactors Packed Bed (single or multi-tube) Fluidized Bed Slurry Reactor • Design goals – rapid and
Reactors Packed Bed (single or multi-tube) Fluidized Bed Slurry Reactor • Design goals – rapid and

Slurry

Reactor

Design goals

– rapid and intimate contact be tween catalyst and reactants

– ease of separation of product s from catalyst Catalyst Recycle Reactor
– ease of separation of product
s from catalyst
Catalyst
Recycle
Reactor

Rates of Catalytic Reactions

Pseudo-homogeneous reaction rate

r = moles / volume · time

reaction rate  r = moles / volume · time  Mass-based rate  r ′

Mass-based rate

r= moles / mass cat · time

r= r / ρ cat



Heterogeneous reactions happen at surfaces

Area-based rate

r′′ = moles / area cat · time

r′′ = r/ SA,

SA = area / mass

· time  r ′′ = r ′ / SA, SA = area / mass 

Heterogeneous reactions happen at active sites

Active site-based rate

Turn-over frequency TOF = moles / site · time

TOF = r′′ / ρ site

/ site · time  TOF = r ′′ / ρ s i t e TOF
/ site · time  TOF = r ′′ / ρ s i t e TOF

TOF (s 1 )

Hetero. cats.

~10 1

Enzymes

~10 6

· time  TOF = r ′′ / ρ s i t e TOF (s −

Adsorption and Reaction at Solid Surfaces

Physisorption: weak van der Waals attraction of a fluid (like N 2 gas) for any surface

E ads ~10 – 40 kJ/mol

Low temperature phenomenon

Exploited in measuring gross surface area

Chemisorption: chemical bond formation between a fluid molecule (like CO or ethylene) and a surface site

E ads ~ 100 – 500 kJ/mol

Essential element of catalytic activity

Exploited in measuring catalytically active sites

Measuring Concentrations in Heterogeneous Reactions Kinetics

Fluid concentrations

Traditionally reported as pressures (torr, atm, bar)

Surface concentrations

as pressures (torr, atm, bar)  Surface concentrations  “Coverage” per unit area  n j

“Coverage” per unit area

n j = moles j / area

Maximum coverage called monolayer

Metal particle surface

1 ML: n j,max = ~ 10 15 molecules / cm 2

1 ML: n j , m a x = ~ 10 1 5 molecules / cm

Fractional coverage

θ j = n j / n j,max

0 ≤ θ j ≤ 1

θ j = 1/6

Catalysts Characterization

Characteristics

Methods

Surface area, pore volume & size

N 2 Adsorption-Desorption Surface area analyzer (BET and Langmuir)

Pore size distribution

BJH (Barret, Joyner and Halenda)

Elemental composition of catalysts

Metal Trace Analyzer / Atomic Absorption Spectroscopy

Phases present & Crystallinity

X-ray Powder Diffraction TG-DTA (for precursors)

Morphology

Scanning Electron Microscopy

Catalyst reducibility

Temperature Programmed Reduction

Dispersion, SA and particle size of active metal

CO Chemisorption, TEM

Acidic/Basic site strength

NH 3 -TPD, CO 2 TPD

Surface & Bulk Composition

XPS

Coke measurement

Thermo Gravimetric Analysis, TPO

Catalyst Activity Testing

Activity to be expressed as:

- Rate constants from kinetics

- Rates/weight

- Rates/volume

- Conversions at constant P,T and SV.

- Temp required for a given conversion at constant partial & total pressures

- Space velocity required for a given conversion at constant pressure and temp

2D & 3D C AD Solids Modeling Micro-scale Design Modules Process Multiscale Tran sport Engineering
2D & 3D C
AD Solids
Modeling
Micro-scale
Design Modules
Process
Multiscale Tran
sport
Engineering
Control
Flow
Simulation &
Optimization
Systems
Patterns

Flowsheet

Synthesis

& Optimization Systems Patterns Flowsheet Synthesis Tools, Fabrication & Assembly Micro-process Components
& Optimization Systems Patterns Flowsheet Synthesis Tools, Fabrication & Assembly Micro-process Components

Tools, Fabrication & Assembly

Micro-process

Components

Materials of Construction

Micro Systems Engineering

Component Integr ation

Micro Systems Engineering Component Integr ation Multi-scale Transp ort Micro Process Plant Raw Materials

Multi-scale Transp ort

Micro Process Plant
Micro Process Plant
Raw Materials & Feedstocks Chemistry & Catalysis Catalyst Characterization Reaction Kinetics Reaction
Raw Materials &
Feedstocks
Chemistry &
Catalysis
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Characterization
Reaction
Kinetics
Reaction Pathways &
Mechanisms
Reaction Kinetics Reaction Pathways & Mechanisms Micro Analyzers (GC, LC, MS, TOF) Micro Process Analytical

Micro Analyzers (GC, LC, MS, TOF)

Micro Process Analytical

Integrated

Sensors

Sampling

Sensors

Data handling & Chemometrics

Micro PAT Systems Integration

Heterogeneous Reactions

Heterogeneous Reactions The complications of rate equations: More than one phase is present: Movement of material

The complications of rate equations:

More than one phase is present: Movement of material from phase to phase

For rate expression: Apart form chemical kinetics term mass transfer is also incorporated

To get the overall rate expression, write the individual steps on the same basis

expression, write the individual steps on the same basis In terms of Volume In terms of

In terms of Volume

In terms of Weight

In terms of Surface

(Or)

write the individual steps on the same basis In terms of Volume In terms of Weight

(Or)

write the individual steps on the same basis In terms of Volume In terms of Weight

Rearrange the mass transfer and reaction steps into same rate form

the mass transfer and reaction steps into same rate form (Or) If the steps are in

(Or)

the mass transfer and reaction steps into same rate form (Or) If the steps are in

If the steps are in series,

If the steps are in parallel,

the mass transfer and reaction steps into same rate form (Or) If the steps are in
the mass transfer and reaction steps into same rate form (Or) If the steps are in

Complications :

Consider reaction steps in series:

If all the steps are linear in concentration then it is easy to combine them.

If any of the steps is non-linear in concentration then it will be difficult to get a overall rate expression.

In such cases, approximate the rate equation (vs.) concentration curve by a first-order expression.

It is hard to know the concentration of materials at intermediate steps.

So, these concentrations are eliminated during combining the rates.

Overall reaction rate for a linear process:

Dilute A diffuses through a stagnant liquid film onto a plane surface consisting of B, reacts to produce R which diffuses back into the mainstream. Develop the overall rate expression for this first order L/S reaction.

A (l) + B(s) R(l)

into the mainstream. Develop the overall rate expression for this first order L/S reaction. A (l)

By diffusion, the flux of A to the surface is,

By diffusion, the flux of A to the surface is, (1) Since this reaction is first-order

(1)

Since this reaction is first-order w.r.t A, based on unit surface,

this reaction is first-order w.r.t A, based on unit surface, (2) At steady state, the flow

(2)

At steady state, the flow rate to the surface is equal to the reaction at surface (steps in series)

unit surface, (2) At steady state, the flow rate to the surface is equal to the
unit surface, (2) At steady state, the flow rate to the surface is equal to the
unit surface, (2) At steady state, the flow rate to the surface is equal to the

from which the intermediate (C As )can be determined as,

which the intermediate (C A s )can be determined as, (3) Replacing eq. (3) into either

(3)

Replacing eq. (3) into either eq. (1) or eq. (2), gives

which the intermediate (C A s )can be determined as, (3) Replacing eq. (3) into either

Contacting patterns for two-phase systems

Contacting patterns for two-phase systems Ideal contacting patterns for two flowing fluids 23

Ideal contacting patterns for two flowing fluids

Pore diffusion resistance combined with surface kinetics

Pore diffusion resistance combined with surface kinetics Consider a single cylindrical pore of length (L), with

Consider a single cylindrical pore of length (L), with reactant A diffusing into the pore, and reacting on the surface by a 1 st order reaction.

The reaction is taking place at the walls of the pore and the product is diffusing out of the pore.

Representation of a single cylindrical pore

Now, check with flow of materials into and out of any section of the pore can be shown as:

Now, check with flow of materials into and out of any section of the pore can

At study state a material balance for reactant A for this elementary section :

Output – Input + Disappearance by reaction = 0

By Substituting the output, input and disappearance by reaction terms we get:

output, input and disappearance by reaction terms we get: For our convenience divide the above equation

For our convenience divide the above equation by (-Πr 2 D (∆x))

and disappearance by reaction terms we get: For our convenience divide the above equation by (-

26

Now apply limit as ∆x approaches Zero the obtained equation changes to:

as ∆x approaches Zero the obtained equation changes to: The 1 s t order chemical reaction

The 1 st order chemical reaction is expressed in terms of unit surface area of the wall of the catalyst pore

Therefore, K ” will have the unit of length per time

In general the interrelation b/w rate constants on different basis is given by:

In general the interrelation b/w rate constants on different basis is given by: Hence for cylindrical

Hence for cylindrical catalyst pore:

In general the interrelation b/w rate constants on different basis is given by: Hence for cylindrical

27

Thus in terms of volumetric units the final equation takes the form:

terms of volumetric units the final equation takes the form: The above eq. is a linear

The above eq. is a linear differential eq. whose general solution is:

eq. is a linear differential eq. whose general solution is: Where, M 1 & M 2

Where,

a linear differential eq. whose general solution is: Where, M 1 & M 2 are constants

M 1 & M 2 are constants and we need two boundary conditions to evaluate them.

First boundary condition (x=0), (Pore entrance)

First boundary condition (x=0), (Pore entrance) Second boundary condition (x=L), (Pore exit) According to the given

Second boundary condition (x=L), (Pore exit)

According to the given model, there is no pore exit and there is no flux or movement of the material through the interior end of pore.

movement of the material through the interior end of pore. With the appropriate mathematical manipulations of

With the appropriate mathematical manipulations of C A and boundary Conditions:

through the interior end of pore. With the appropriate mathematical manipulations of C A and boundary

29

Hence the concentration of reactant (C A /C As ) with in the pore is :

of reactant (C A /C A s ) with in the pore is : There is

There is a progressive drop in concentration on moving into the pore.

And this dependent on the dimensionless quantity mL (or) M T called

as Thiele modulus.

Effectiveness factor (Ɛ) is introduced to measure how much the reaction rate is decreased because of the resistance to pore diffusion.

(Ɛ) is introduced to measure how much the reaction rate is decreased because of the resistance

Distribution and Avg. value of reactant concentration within a catalyst pore as a function of the parameter mL = L √(k/D)

and Avg. value of reactant concentration within a catalyst pore as a function of the parameter

The effectiveness factor (Vs)Thiele Modulus

For small mL (<0.4), Ɛ ~ 1,

the conc. Of the reactant does not

drop within the pore pore diffusion offers negligible resistance

For large mL (> 4), Ɛ ~ 1/mL,

the conc. Of the reactant drops rapidly

within the pore pore diffusion Strongly influences the reaction rate. (Strong pore resistance)

This graph can easily show the effectiveness Pore diffusion on modification of the rate of reaction and it depends on whether mL is large or small

Porous Catalyst Particles Main steps involved in heterogeneous catalytic reactions

Main steps involved in heterogeneous catalytic reactions 1. Transport of the reactants from the bulk of
Main steps involved in heterogeneous catalytic reactions 1. Transport of the reactants from the bulk of

1. Transport of the reactants from the bulk of a mixture to a catalyst particle

2. Transport of the reactants in the pores of the catalyst particles to an active site

3. Adsorption of the reactants to the active site

4. Reaction of reactants to form an adsorbed product

5. Desorption of the product from the active site

6. Transport of the products in the pores of the catalytic particle out of the particle

7. Transport of the products from the particle to the bulk of the mixture

The results of a single pore can approximate the behavior of particles of various shapes (spheres, cylinders, flat plates etc.) for these systems,

1. Use of proper diffusion coefficient

Replace the molecular diffusion coefficient D by the effective diffusion coefficient of the fluid in the porous structure.

2. Proper measure of particle size To find the effective distance penetrated by the gas to get all the interior surfaces we should define a characteristic size of particle.

distance penetrated by the gas to get all the interior surfaces we should define a characteristic

3. Measures of reaction rates The rate of reaction can be expressed in many equivalent ways.

3. Measures of reaction rates The rate of reaction can be expressed in many equivalent ways.

4. Finding pore resistance effects from experiment

Define a modulus which only includes observable and measurable quantities.

This is known as Wagner-Weisz-Wheeler Modulus (Wagner Modulus).

is known as Wagner-Weisz-Wheeler Modulus (Wagner Modulus). 5. Pore resistance limits M T < 0.4 or

5. Pore resistance limits

M T < 0.4 or M W < 1.15

resistance limits M T < 0.4 or M W < 1.15 Reactant fully penetrates the particle

Reactant fully penetrates the particle and reaches all its surface. Then the particle is in the diffusion free regime.

M T > 4 or M W > 4

the diffusion free regime . M T > 4 or M W > 4 Center of

Center of the particle is starved for reactant and is unused. Then the particle is in strong pore resistance regime.

Shows the limits for negligible and for strong pore diffusion resistances 7. Particles of different

Shows the limits for negligible and for strong pore diffusion resistances

7. Particles of different sizes Comparing the behavior of two particle sizes R 1 and R 2 , we find,

the behavior of two particle sizes R 1 and R 2 , we find, Diffusion free
the behavior of two particle sizes R 1 and R 2 , we find, Diffusion free
the behavior of two particle sizes R 1 and R 2 , we find, Diffusion free
the behavior of two particle sizes R 1 and R 2 , we find, Diffusion free

Diffusion free regime

Strong diffusion resistance

Heat effects during the reaction

Non-Isothermal Effects

When the reaction is so fast that the heat released (or absorbed) in the pellet cannot be removed rapidly to keep the pellet close to the temperature of the fluid, then the non-isothermal effects intrude.

Two different kinds of temperature effects may be encountered:

1. Within- particle ∆T

effects may be encountered: 1. Within- particle ∆T Temperature variation within the pellet 2. Film ∆T

Temperature variation within the pellet

2. Film ∆T

∆T Temperature variation within the pellet 2. Film ∆T The pellet may be hotter (or colder)

The pellet may be hotter (or colder) than the surrounding fluid.

Exothermic reactions

Heat is released and particles are hotter than the surrounding fluid.

Therefore the non-isothermal rate > isothermal rate as measured by bulk conditions.

Endothermic reactions

Heat is absorbed and particles are colder than the surrounding fluid.

non-isothermal rate < isothermal rate

If the harmful effects of thermal shock, or sintering of the catalyst Particles, or drop in selectivity do not occur than one can encourage exothermic reaction.

Non-isothermal effectiveness factor curve for temp. variation with in the particle 40

Non-isothermal effectiveness factor curve for temp. variation with in the particle

The differential form of Eq. (1) is,

The differential form of Eq. (1) is, (2) Integrating over the whole reactor gives, Weight-time and

(2)

Integrating over the whole reactor gives,

differential form of Eq. (1) is, (2) Integrating over the whole reactor gives, Weight-time and volume-time

Weight-time and volume-time terms,

differential form of Eq. (1) is, (2) Integrating over the whole reactor gives, Weight-time and volume-time
differential form of Eq. (1) is, (2) Integrating over the whole reactor gives, Weight-time and volume-time

(3)

Performance equations for reactors containing Porous catalyst particles

For Plug Flow

reactors containing Porous catalyst particles For Plug Flow Elementary slice of solid catalyzed plug flow reactor

Elementary slice of solid catalyzed plug flow reactor

At steady state a material balance for reactant A gives,

Input = output + accumulation

catalyzed plug flow reactor At steady state a material balance for reactant A gives, Input =

(1)

For First-order catalytic reactions,

Plug flow reactor

Mixed flow reactor

catalytic reactions, Plug flow reactor Mixed flow reactor C A i n = C A o
catalytic reactions, Plug flow reactor Mixed flow reactor C A i n = C A o

C Ain = C Ao and Ɛ A 0 ( first order reactions)

Plug flow reactor Mixed flow reactor C A i n = C A o and Ɛ

Experimental Methods for finding rates

The experimental strategy in studying catalytic kinetics usually measuring the extent of conversion of gas passing in steady flow through a batch of Solids.

Any flow pattern can be used, as long as the pattern selected is known. If it is not known then the kinetics cannot be found.

We will discuss on the following experimental devices.

1. Differential flow reactor

2. Integral (plug flow) reactor

3. Mixed flow reactor

4. Batch reactor for both gas and solid

1. Differential (flow) reactor

If we choose to consider the reaction rate to be constant at all points within the reactor then we can have a differential reactor.

Since reaction rates are concentration-dependent this assumption is usually reasonable for small conversions or for small reactors.

For each run in a differential reactor the plug flow performance equation becomes:

reactor the plug flow performance equation becomes: Thus each run gives directly a value for rate

Thus each run gives directly a value for rate at avg. conc., a series of runs gives a set of rate-conc. Data.

2. Integral (plug flow) reactor

If the variations in the reaction rate within a reactor is so large then to account such variations in the method of analysis, then we have an integral Reactor.

Since the reaction rates are conc. dependent, such large variations in rate may be expected to occur when the composition of the reactant fluid changes significantly in passing through the reactor.

We may follow two procedures in searching for a rate equation.

Integral analysis

the reactor . We may follow two procedures in searching for a rate equation. Integral analysis

Differential analysis

the reactor . We may follow two procedures in searching for a rate equation. Integral analysis

3. Mixed Flow Reactor

A mixed flow reactor requires a uniform composition of fluid through out.

For a mixed flow reactor the performance Equation is given by:

For a mixed flow reactor the performance Equation is given by: Carberry basket-type experimental mixed flow
For a mixed flow reactor the performance Equation is given by: Carberry basket-type experimental mixed flow

Carberry basket-type experimental mixed flow reactor

Recycle reactor

Recycle reactor When the recycle is large enough mixed flow is approximated 4. Batch reactor In

When the recycle is large enough mixed flow is approximated

When the recycle is large enough mixed flow is approximated 4. Batch reactor In this system,

4. Batch reactor

In this system, we follow the changing composition with time & Interpret the results with batch reactor performance.

& Interpret the results with batch reactor performance. A recycle reactor without through Flow becomes a

A recycle reactor without through Flow becomes a batch reactor.

The Packed Bed Catalytic Reactors

Vent Flow Controller Pre-heater Reactor Gas Chromatograp h Integrator He O 2 CH 4 R.P.
Vent
Flow
Controller
Pre-heater
Reactor
Gas
Chromatograp
h
Integrator
He
O 2
CH 4
R.P.
He
T
T
T
Temperature
Controller
EXPERIMENT SETUP

CATALYST DEACTIVATION DIAGRAM

Pd Sites Al 2 O 3
Pd Sites
Al 2 O 3
SETUP CATALYST DEACTIVATION DIAGRAM Pd Sites Al 2 O 3 A Fresh Catalyst (high dispersion; high

A

Fresh Catalyst (high dispersion; high surface area)

Cintered Pd Al 2 O 3 B Old Catalyst Low dispersion (low activity)
Cintered Pd
Al 2 O 3
B
Old Catalyst
Low dispersion (low activity)

Pore cinteringPd Al 2 O 3 B Old Catalyst Low dispersion (low activity) γ -Al 2 O

Old Catalyst Low dispersion (low activity) Pore cintering γ -Al 2 O 3 C Old catalyst

γ-Al 2 O 3

Low dispersion (low activity) Pore cintering γ -Al 2 O 3 C Old catalyst Low surface

C

Old catalyst Low surface area (low activity)

The reactant gas can be made to contact solid catalyst in many ways, and each has its specific advantages and disadvantages.

Reactors cab be divided into two broad types.

1.

2.

Fixed Bed Reactor Fluidized Bed Reactor

Reactors cab be divided into two broad types. 1. 2. Fixed Bed Reactor Fluidized Bed Reactor

Fixed Bed Reactors

Reactors cab be divided into two broad types. 1. 2. Fixed Bed Reactor Fluidized Bed Reactor
Fluidized Bed Reactors Moving-Bed Reactor is an intermediate case which incorporates some of the advantages
Fluidized Bed Reactors Moving-Bed Reactor is an intermediate case which incorporates some of the advantages

Fluidized Bed Reactors

Moving-Bed Reactor is an intermediate case which incorporates some of the advantages and disadvantages of fixed-bed and fluidized-bed reactors

Merits and demerits of fixed bed and fluidized bed reactors

 

Characteristic

Fixed-Bed Reactor

Fluidized-Bed Reactor

Feature

1.

Gas Flow

Plug Flow (√)

Complex Flow & by passing (X) High Catalyst content (X)

Efficient contact (√)

Fixed bed favored (√)

2.

Temperature

Large Fixed beds (X) (low cond.) Exothermic Rxn. (X) (Hot Spot)

Good Control of Temp. Explosive nature of Rxn. can also performed

control

3.

Particle Size (small)

Plugging & High-Pressure drop (X)

Effective use of catalyst Pore and diffusion rxn. high

4.

Catalyst

Regeneration is difficult(X)

Liquid-like fluidized state Can be pumped easily

Regeneration

The two main difficulties in catalytic reactor design…

1. How to overcome non-isothermal behavior in packed beds. 2. How to overcome non-ideal flow of gas in fluidized beds.

non-isothermal behavior in packed beds. 2. How to overcome non-ideal flow of gas in fluidized beds.

Moving-Bed Reactor

The temperature field in a packed bed reactor for an exothermic reaction creates a radial

The temperature field in a packed bed reactor for an exothermic reaction creates a radial movement of heat and matter

The stage adiabatic packed bed reactor presents different situation. (Since no heat transfer in the zone of reaction. The temperature and conversions are related in much simple way.

Staged Adiabatic Packed Bed Reactors

Staged Adiabatic Packed Bed Reactors With proper interchange of heat and proper gas flow, staged adiabatic

With proper interchange of heat and proper gas flow, staged adiabatic packed bed reactors became versatile system

Staged Packed Beds (Plug flow) with intercooling

Staged Mixed Flow Reactors

Cold Shot Cooling

became versatile system Staged Packed Beds (Plug flow) with intercooling Staged Mixed Flow Reactors Cold Shot

Staged Packed Beds (Plug flow) with intercooling

Staged Packed Beds (Plug flow) with intercooling Sketch showing how staged packed beds can closely approach

Sketch showing how staged packed beds can closely approach the optimal temperature

Optimization of operations reduces to minimize the total amount of catalyst needed to achieve a given conversion.

Reversible Exothermic Reactions

Reversible Exothermic Reactions Three variables to optimize the amount of catalyst 1. Incoming Temp. (T a

Three variables to optimize the amount of catalyst

1. Incoming Temp. (T a )

2. Amount of catalyst used in 1 st stage ( b along with the adiabatic)

3. Amount of intercooling (c along the bc line)

of catalyst used in 1 s t stage ( b along with the adiabatic) 3. Amount
How to find exact (T a ) 1.Guess (Ta) 2. Move along the adiabatic line

How to find exact (T a )

1.Guess (Ta)

2. Move along the adiabatic line until the following condition is satisfied.

adiabatic line until the following condition is satisfied. This gives point b (amount of catalyst needed

This gives point b (amount of catalyst needed and outlet temperature from that stage

3. Cool to point c which has same rate as b:

Rxn rate leaving the reactor = Rxn rate entering next reactor (or stage)

4. Moving along the adiabatic from point c to d until point 2 is satisfied (d).

5. If point d is the desired final conversion then our Guess is correct.

Staged Mixed Flow Reactors

Staged Mixed Flow Reactors Staged Packed bed with recycle Choose the distribution of the catalyst So

Staged Packed bed with recycle

Staged Mixed Flow Reactors Staged Packed bed with recycle Choose the distribution of the catalyst So

Choose the distribution of the catalyst So as to maximize the KLMN area which Then Minimizes the shaded area

recycle Choose the distribution of the catalyst So as to maximize the KLMN area which Then
recycle Choose the distribution of the catalyst So as to maximize the KLMN area which Then