PDF

CH6701 Chemical Reaction Engineering - II 2019-2020
Unit I – CATALYSTS
Course Content
 Nature of catalysis
 Surface area and pore-volume distribution
 Catalyst preparation
Catalysts
 A substance that alters the reaction rate of a particular chemical reaction.
 Chemically unchanged at the end of the reaction
Two classes:
 Positive catalyst: increase the rate
 Negative catalyst (inhibitor): decrease the rate
Active sites
• Reactions are not catalyzed over the entire surface but only at certain active sites or centers
that result from unsaturated atoms in the surface.
• An active site is a point on the surface that can form strong chemical bonds with an
adsorbed atom or molecule.
Action of a catalyst
• It is important to remember that the use of catalyst DOES NOT vary ∆G &Keq values of
the reaction concerned, it merely change the PACE of the process.
• Whether a reaction can proceed or not and to what extent a reaction can proceed is solely
determined by the reaction thermodynamics, which is governed by the values of∆G &Keq,
NOT by the presence of catalysts.
• In another word, the reaction thermodynamics provide the driving force for a rxn; the
presence of catalysts changes the way how driving force acts on that process.
Representation of catalyst
St. Joseph’s College of Engineering 1 Chemical Engineering

Catalyst Preparation Methods

 Precipitation
 Gel formation
 Simple mixing of components
 Impregnation
Precipitation method
Gel formation method

Simple mixing of components
Impregnation method

Surface area of catalyst

 The area provided for the adsorption per gram of adsorbent is called as the surface
area (m2/g).
 Catalytic substance and support
 The catalyst substance is dispersed on the surface of the support or carrier.
 Silica gel and Alumina are widely used as supports
 Surface area plays an important role in this type of
catalyst
Determination of surface area

 The standard method for measuring catalyst areas is based on the physical adsorption
of a gas on the solid surface.
 Usually the amount of nitrogen adsorbed at equilibrium at the normal boiling point (-
195.8 oC) is measured over a range of nitrogen pressures below 1 atm.
 Under these conditions several layers of molecules may be adsorbed on top of each
other on surface.
 The amount adsorbed when one molecular layer is attained must be identified in order
to determine the area.
All-Glass Apparatus
 The apparatus operates at a low pressure which can be varied from near zero up to about 1
atm. The operating temperature is in the range of the normal boiling point.
 The data obtained are gas volumes at a series of pressures in the adsorption. The observed
volumes are normally corrected to cubic centimeters at 0 oC and 1 atm (standard
temperature and pressure) and plotted against the pressure in millimeters, or as the ratio of
the pressure to the vapor pressure at the operating temperature.
 Typical results from Brunauer and Emmett’s work are shown in figure for the adsorption
of several gases on a 0.606 g sample of silica gel.
 To simplify the classical experimental procedure a flow method has been developed in
which a mixture of helium (or other non-adsorbed gas) and the gas to be adsorbed is passed
continuously over the sample of solid.
 The operating total pressure is constant, and the partial pressure of adsorbable gas is varied
by changing the composition of the mixture.
 The procedure is to pass a mixture of known composition over the sample until equilibrium
is reached, that is, until the solid has adsorbed an amount of adsorbable component
corresponding to equilibrium at its partial pressure in the mixture.
 Then the gas is desorbed is measured with a thermal-conductivity cell or other detector.
This gives one point on an isotherm, such as shown in figure. Then the process is repeated
at successively different compositions of the mixture until the whole isotherm is obtained.
 The curves in figure are similar to the extent that at low pressures they rise more or less
steeply and then flatten out for a linear section at intermediate pressures.

 After a careful analysis of much data it was concluded that the lower part of the linear
region corresponded to complete monomolecular adsorption.
 If this point could be located with precision, the volume of one monomolecular layer of
gas, vm, could then be read from the curve and the surface area evaluated. The Brunauer –
Emmett – Teller method locates this point from an equation obtained by extending the
Langmuir isotherm to apply to multilayer adsorption
 Brunauer, Emmett and Teller adapted this equation for multilayer adsorption and arrived
at the result
 Where po is the saturation or vapor pressure and c is a constant for theparticular

temperature and gas-solid system. According toequation (2),
a plot of should give a straight line.

 Of additional significance is the fact that such straight lines can be accurately extrapolated
to (p/po = 0).The intercept I obtained from this extrapolation, along with the slope s of the
straight line, gives two equations from which v m can be obtained
 Solving these equations for the volume of adsorbed gas corresponding to a

monomolecular layer gives
 The volume vm can be readily converted to the number of molecules adsorbed. However,
to determine the surface area it is necessary to select a value for the area covered by one
adsorbed molecule. If this is α, total surface area is given by,
 Where No is Avogadro’s number, 6.02 x 1023 molecules / mol

 V is volume per mole of gas at conditions of vm, since vm is recorded at standard
temperature and pressure, V = 22,400 cm3 / g mol.
 Emmett and Brunauer proposed that is projected area of a molecule on the surface when
the molecules are arranged in close two- dimensional packing. This value is slightly larger
than that obtained by assuming that the adsorbed molecules are spherical and their
projected area on the surface is circular. The proposed equation is

 Where M is molecular weight and 𝜌is the density of the adsorbedmolecules.
Void volume and Solid density
Helium-Mercury method
 The volume of helium is displaced by a sample of catalyst is measured; then the helium is
removed, and the volume of mercury that is displaced is measured.
 Since mercury will not fill the pores of most catalysts at atmospheric pressure, the
difference in volumes gives the pore volume of the catalyst sample.
 The volume of helium displaced is a measure of the volume occupied by the solid
material.
 From this and the weight of the sample, the density of the solid phase,ρs , can be obtained.
Then the void fraction, or porosity, of the particle, may be calculated from the equation
where, mp = mass of the particle, Vg= void volume per gram of particles.
 If the sample of particles is weighed, the mass divided by the mercury volume gives the
density 𝜌pof the porous particles. Note that the porosity is also obtainable from this density
by the expression
 From the helium – mercury measurements the pore volume, the solid density, and the
porosity of the catalyst particle can be determined.
Problems
In an experiment to determine the pore volume and catalyst- particle porosity the following data
were obtained on a sample of activated silica (granular, 4 to 12 mesh size):
Mass of catalyst sample placed in chamber = 101.5 g

Volume of helium displaced by sample = 45.1 cm3
Volume of mercury displaced by sample = 82.7 cm3

Pore volume distribution

1. Mercury-Penetration Method
2. Nitrogen-Desorption Method
3. Combination of Mercury-Penetration & Nitrogen Desorption Method
Mercury penetration method

 The mercury-penetration method depends on the fact that mercury has a significant
surface tension and does not wet most catalytic surfaces. This means that the pressure
required to force mercury into the pores depends on the pore radius.
 The pressure varies inversely with a; 100 lb/in.2. (approximately) is required to fill pores
for which a = 10, 000oA, and 10, 000 lb/in.2 is needed for a = 100 oA.
 Simple techniques and equipment are satisfactory for evaluating the pore-volume
distribution down to 100 to200 oA, but special high-pressure apparatus is necessary to go
below a = 100 oA, where much of the surface resides.
 By equating the force due to surface tension (which tends to keep mercury out of a pore)
to the applied force, Ritter and Drake obtained
 Where θ is the contact angle between the mercury andpore wall (figure).
 Then the working equation for evaluating the radius corresponding to a given pressure is
Nitrogen-desorption method
 As the low temperature nitrogen-desorption experiment is continued to high pressures
multilayer adsorption occurs, and ultimately the adsorbed film is thick enough to bridge
the pore. Then further uptake of nitrogen will result in capillary condensation.
 Since the vapor pressure decreases as the capillary size decreases, such condensation will
occur first in the smaller pores. Condensation will be complete, as, (p/po= 0) when the
entire void region is filled with condensed nitrogen.
 Now, if the pressure is reduced by a small increment, a small amount of nitrogen will
evaporate from the meniscus formed at the ends of the largest pores.

 Pores which are emptied of condensate in this way will be those in which the vapor pressure
of nitrogen is greater than the chosen pressure.
 The Kelvin equation gives the relationship between vapor pressure and radius of the
concave surface of the meniscus of the liquid.
 Since some of the nitrogen is adsorbed on the surface, and therefore not present because of
capillary condensation, the Kelvin relationship must be corrected for the thickness of the
adsorbed layers.
 With this correction, the pore radius is related to the saturation pressure ratio (vapor
pressure ’p’ in the pore divided by the normal vapor pressure po) by
Where, V1= molal volume of the condensed liquid, 𝜎= surface tension., θ = contact angle
between surface and condensate
 Since nitrogen completely wets the surface covered with adsorbed nitrogen, θ= 0 and cos
θ = 1 . The thickness δ depends on p/po . The exact relationship has been the subject of
considerable study, but Wheeler’s form
 For nitrogen at – 195.8 oC (normal boiling point), for a-δ in angstroms, becomes
 For a chosen value of p/po , the above equation give the pore radius above which all pores
will be empty of capillary condensate.
 Hence, if the amount of desorption is measured for various p/po, the pore volume
corresponding to various radii can be evaluated.
 Differentiation of the curve for cumulative pore volume vs. radius gives the distribution of
volume.
Combination of Mercury-Penetration and Nitrogen- desorption method

 By combining mercury-penetration and nitrogen-desorption measurements,pore-
volumeinformation canbeobtained
 Over the complete range of radii in a pelleted catalystcontaining both macro- and
micropores.
 Figure shows the cumulative pore volume for two alumina pellets, each prepared by
compressing porous particles of boehmite (Al2O3.H2O). The only difference in the two is
the pelleting pressure.
 Increasing this pressure causes drastic reductions in the space between particles
(macropore volume) but does not greatly change the void volume within the particles or
surface area. The derivative of the volume curves in figure (1) gives the pore volume
distribution, and these results are shown in figure (2).

Examples of catalytic reactions

 Catalytic cracking
 Catalytic reforming
 Aromatization
 Isomerization
 Hydrogenation of vegetable oils
 Enzymatic reactions in food processing
 Conversion of SO2 to SO3 with the presence of V2O5
 NH3 synthesis
Characteristics of catalytic reactions

 Catalyst remains unchanged at the end of the reaction
 Very small quantity required
 Decreases the activation energy
 Develops a new mechanism
 Does not alter the chemical equilibrium
 Ea, for catalyst << Ea, for non-catalyzed reaction
 Catalyst plays a specific role in chemical reactions
Steps in catalytic reactions:

1. Diffusion of reactant “A” from bulk fluid phase to the external surface of the catalyst
through the fluid film – External or surface diffusion step.
2. Diffusion of the reactant from the pore mouth into the catalyst pores – Pore diffusion
step.
3. Adsorption of reactant “A” onto the catalyst surface (External and pore surfaces).
4. Chemical reaction of the adsorbed reactant on the surface of the catalyst to form product
(Surface reaction)
5. Desorption of products from the surface to the fluid phase near the surfaces.
6. Diffusion of the desorbed products from the interior of the catalyst to the pore mouth at
the external surface i.e. to the external surface (Reverse pore diffusion).
7. Diffusion of the products from the external surface into the bulk fluid phase through the
fluid film surrounding the catalyst (Reverse-external diffusion)

Solid Catalyzed Reactions

 A substance that enhances the rate of a chemical reaction and is recovered at the end of the
reaction without change in its mass and chemical composition is called a catalyst.
 A catalyst which has a large area resulting from pores is called as a porous catalyst.
Characteristics of solid catalyst:

 Activity – it is a measure of the accelerating effect that a catalyst has on the rate of a given
reaction.
 Specificity (selectivity) – A property of a catalyst to speed up the main reaction (produce
desired product) in the presence of several side reactions.
Promoters and Inhibitors

 Components of a catalyst include: carrier, promoters and inhibitors
 Silica gel and Alumina are widely used as supports
 Promoter is defined as a substance addedduring preparation of a catalyst which
improves activity or selectivityor stabilizes the catalytic agent so as to prolong its life
 Will be present in small quantity. Some promoters are used to increase the number of
active sites hence making the catalyst more active
Examples
 Chlorides are used in hydrogenation and Isomerization catalysts
 Sulfiding improves hydro-desulfurization
Catalyst Deactivation
 Activity of a catalyst decreases with time
 Catalysts for cracking and some other hydrocarbon reactions lose much of their activity in
seconds due to poisons.
 Poisons are defined as substances either in the reactant stream or produced by the reaction,
which lowers the activity of a catalyst
 Continuous regeneration of cracking catalysts is necessary because of the deposition of one
of the products carbon on the surface

 The slow decrease in activity is due to chemisorption of reactants, products or impurities

in the liquid stream
 Rapid deactivation is caused by physical deposition of a substance that blocks the active
sites of a catalyst
 Rapid deactivation is also called as fouling
 Deactivation can also be caused by a change in the structure of the catalyst due to prolong
exposure to elevated temperature in the reacting atmosphere.
Eg: sintering
Types of Poisons
Based on the way poisons operate they are classified as:
1. Deposited poisons
2. Chemisorbed poisons
3. Selectivity poisons
4. Stability poisons
5. Diffusion poisons
Deposited Poisons
 Carbon deposition on catalyst is an example of this category
 The carbon covers the active sites of the catalyst and may plug the pore entrances
 This type is partially reversible and regeneration can beachieved by burning CO to CO2with
air or steam
Chemisorbed Poisons
 Compounds of Sulphur and other materials are chemisorbed on Ni, Cu, and Pt catalysts
 The decline in activity stops when an equilibrium is reached b/w the poison in the reactant stream
and that on the catalytic surface
 If the strength of the bond is weak the activity of the catalyst can be regained otherwise it is a
permanent poisoning
Selectivity Poisons
 Some materials in the reactants get adsorbed on the surface and catalyze undesirable reactions thus
lowering the selectivity
Example
 very small quantities of Ni, vanadium, iron etc. in petroleum stocks act as poisons in this way.
When such stocks are cracked the metals deposit on the catalyst and act as dehydrogenation
catalysis. This results in increased yields of hydrogen and coke and lower yields of gasoline
Stability Poisons
 When water vapour is present in SO2 - air mixture supplied to a Pt- alumina catalyst, a decrease in
oxidation activity occurs
 This type of poisoning is due to the effect of water on the structure of the alumina carrier.
 Temperature has pronounced effect on stability of poisoning.
 Sintering and localized melting may occur as the temperature is increased and thus changes the
catalyst structure

Diffusion Poison
Example
carbon deposition on cracking catalyst
 Blocking the pore mouths prevents the reactants from diffusing into the inner surface
 Entrained solids in the reactants or fluids which can react with the catalyst to form a solid residue,
can cause this type of poisoning
Accelerators
Accelerators materials that are added to the reactant stream to improve the performance of a
catalyst are called as accelerators.
Example
Steam added to the butene feed of a dehydrogenation reactor appeared to reduce the amount of
coke formed and increase the yield of butadiene. The catalyst used is iron
---------------------------------------------------------------------------------------------------------------------
Unit II - HETEROGENEOUS REACTORS
Course Content
 Rate equations for heterogeneous reactions
St. Joseph’s College ofEngineering
Adsorption isotherms 12 Chemical Engineering
 Rates of adsorption and desorption
Heterogeneous Reactions
The reactants, products and catalysts are in the different phases
Types
1. Catalytic type heterogeneous reactions
2. Non-Catalytic type heterogeneous reactions
Catalytic type heterogeneous reactions

Gas-Solid Reactions
Examples:
 Ammonia synthesis
 Oxidation of SO2to SO3usingV2O5Catalyst (manufacture of H2SO4)
 Catalytic cracking of crude oil
Gas-Liquid-Solid Reactions
Examples:
 Catalytic hydrogenation of acetone to propanol
 Catalytic oxidation of ethanol using O2 to acetic acid
Non-Catalytic heterogeneous reactions

 Gas-Liquid/Solid reactions
Ex: Combustion of coal, roasting of sulphide ores, etc.,
 Gas-Liquid reactions
Ex: (i) Purification of gas mixtures (Absorption) (ii)Ammonia+ aq. HNO3 -> Ammonium
nitrate (Absorption) (iii) Chlorination of liquid hydrocarbons
 Liquid-Liquid reactions
Ex: (i). soap preparation (acids + alkalies) (ii). Nitration of organic compounds
 Liquid-Solid reactions
Ex: calcium carbide+H2O -> Acetelyene
Rate equations for heterogeneous reactions

 No. of chemical steps (Series or Parallel steps)
 If the reaction consists of parallel steps
 At steady state condition, the reaction consists of series steps

Rate controlling step or rate limiting step

Consider the reaction type
Condition:
1. First order reaction w.r.to gaseous reactant A
2. No ash is formed on the solid surface
Steps involved:
3. Gas (A) is transported from the bulk of gas to the solid surface (B)
4. Surface reactions b/w A and B
5. Product R is transported from the solid surface to the bulk gas
Burning of carbon
 The rate of mass transfer of A through gas film by diffusion per unit surface to surface of
B
 The rate of reaction based on unit surface area of B
 These steps are in series. So at steady state, Flux of A to the surface = Surface reaction

k g (CAg - CAs ) = k"CAs

k gCAg = (k" + k g )CAs
Substitute CAs,
The overall rate of reaction
 For steps in series r1 = r2 = roverall
 This is the expression for overall rate in terms of bulk reactant concentrations
 The overall rate of a heterogeneous process is determined by the slowest step and hence it
is called as the rate controlling step.
 If kg>>k” then the overall rate reduces to
-rA” = k” CAg
 Which implies the chemical reaction is the rate limiting step (diffusion is rapid and
reaction is slow)
 If k”>>kg,then the overall rate reduces to
-rA” = kg CAg
 Mass transfer is the rate limiting step and rapid surface reaction
 If the reaction is taking place in the region of intermediate b/w chemically controlled
region and mass transfer controlled region, then the overall rate equation is
Contacting patterns for Two-phase systems

Adsorption isotherms
Adsorption (surfacephenomena)
 Physical adsorption (Physisorption, weak van der waals force)

 surface area and pore-size distribution in porous catalysts can be calculated
 Chemical adsorption (Chemisorption, covalent bond)
(i) Activated chemisorption (slowprocess)
The rate of adsorption varies with the temperature accordingto a finite Ea in the
Arrheniusequation
(ii) Non-activated chemisorption (rapidprocess)
Chemisorption occurs very rapidly, suggesting an Ea nearzero.
Difference b/w Physisorption and Chemisorption
Parameter Physisorption Chemisorption

Adsorbent All solids Some solids
Adsorbate All gases below critical temperature Some chemically reactive gases
Temperature range Low temperature High temperature
Heat of adsorption Low High
Rate , Ea Very rapid, low Ea Non activated, low Ea Activated, high Ea
Coverage Multilayer Monolayer
Reversibility High reversible Often irreversible
Determination of surface area and Determination ofactive-center areaand
Importance
pore size elucidation ofsurface reactivekinetics
The various adsorption isotherms are;

 Langmuir isotherm {Cg/C = (I/Cm) Cg + [1/(Kc. Cm)]}
 Freundlich isotherm {ln(C) = (1/n) ln(P) + ln(K. Cm)}

 Temkin isotherm {C = (k1Cm) ln(P) + (k1Cm)ln(k2)}
Langmuir isotherms
Assumptions
 Monolayer coverage on the surface of adsorbent
 No interactions between the adsorbate atoms or molecules
 Coverage-independent binding energy
 Thermodynamic equilibrium of adsorption and desorption rate being equal.
Derivations of the Langmuir Adsorption Equation

Langmuir proposed that dynamic equilibrium exists between adsorbed gaseous molecules and the
free gaseous molecules. Using the equilibrium equation, equilibrium constant can be calculated.
Where Ka represents equilibrium constant for forward reaction and Kd represents equilibrium
constant for backward direction.
According to Kinetic theory,
Rate of forward reaction = Ka [A] [B]
Rate of backward reaction = Kd [AB]
At equilibrium, Rate of forward reaction is equal to Rate of backward reaction
Ka [A] [B] = Kd [AB]
𝑲𝒂 [𝑨𝑩]
=
𝑲𝒅 [𝑨][𝑩]
𝑲𝒂 [𝑨𝑩]
𝑲= =
𝑲𝒅 [𝑨][𝑩]
The above equation represents the equilibrium constant for distribution of adsorbate between the
surface and the gas phase.
Derivation
 Langmuir Equation which depicts a relationship between the number of active sites of the
surface undergoing adsorption (i.e. extent of adsorption) and pressure.
 To derive Langmuir Equation and new parameter ‘ θ ’ is introduced. Let θ the number of
sites of the surface which are covered with gaseous molecules. Therefore, the fraction of
surface which are unoccupied by gaseous molecules will be (1 – θ).
 Now, Rate of forward direction depends upon two factors: Number of sited available on
the surface of adsorbent, (1 – θ) and Pressure, P. Therefore rate of forward reaction is
directly proportional to both mentioned factors.
Rate of forward reaction = P (1 – θ)
Rate of adsorption α P (1 – θ)
Rate of adsorption = Ka P (1 – θ)
 Similarly, Rate of backward reaction or Rate of Desorption depends upon number of sites
occupied by the gaseous molecules on the surface of adsorbent.

Rate of Desorption α θ
Rate of Desorption = Kdθ
 At equilibrium, rate of adsorption is equal to rate of desorption.
Ka P (1 – θ) = Kd θ
 We can solve the above equation to write it in terms of θ.
KaP – KaP θ = Kd θ
KaP = KaP θ + Kd θ
KaP = (Kd + KaP) θ
𝑲𝒂 𝑷
𝛉=
𝑲𝒅 + 𝑲𝒂 𝑷
 Divide numerator and denominator on RHS by Kd, we get
𝑲𝒂
𝑷
𝑲𝒅
𝜽= 𝑲𝒅 𝑲𝒂
+ 𝑷
𝑲𝒅 𝑲𝒅
Now put,
𝑲𝒂
𝑲=
𝑲𝒅
in above equation we get
𝑲𝑷
𝜽=
𝟏 + 𝑲𝑷
This is known as Langmuir Adsorption Equation.
Alternate form of Langmuir Adsorption Equation
On substituting
̅
𝑪
𝜽=
̅̅̅̅
𝑪𝒎
KP = KcCg
 Langmuir isotherm {Cg/C = (I/Cm) Cg + [1/(Kc. Cm)]}
 It is in the form y = mx +c
 Therefore y = Cg/𝐶̅ , x = Cg, m = 1/𝐶̅ m, C = 1/(Kc. 𝐶̅ m)
 On plotting graph between Cg vs Cg/𝑪 ̅ the slope and intercept can be found.
Limitations of Langmuir Adsorption Equation

 The adsorbed gas has to behave ideally in the vapor phase. This condition can be fulfilled
at low pressure conditions only. Thus Langmuir Equation is valid under low pressure only.
 Langmuir Equation assumes that adsorption is monolayer. But, monolayer formation is
possible only under low pressure condition. Under high pressure condition the assumption
breaks down as gas molecules attract more and more molecules towards each other. BET
theory proposed by Brunauer, Emmett and Teller explained more realistic multilayer
adsorption process.

 Another assumption was that all the sites on the solid surface are equal in size and shape
and have equal affinity for adsorbate molecules i.e. the surface of solid if homogeneous.
But we all know that in real solid surfaces are heterogeneous.
 Langmuir Equation assumed that molecules do not interact with each other. This is
impossible as weak force of attraction exists even between molecules of same type.
 The adsorbed molecules has to be localized i.e. decrease in randomness is zero (ΔS = 0).
This is not possible because on adsorption liquefaction of gases taking place, which results
into decrease in randomness but the value is not zero.
 From above facts we can conclude that, Langmuir equation is valid under low pressure
conditions.
Freundlich Adsorption Equation
We consider Langmuir Equation

𝑲𝑷
𝜽=
𝟏 + 𝑲𝑷
At low pressure value of KP<<1. Therefore
𝜽 = 𝑲𝑷 or 𝜽 𝜶 𝑷
The above equation shows linear variation between extent of adsorption of gas and pressure.
At high pressure value of KP>>1
𝑲𝑷
𝜽= =𝟏
𝑲𝑷
The extent of adsorption, θ is independent of pressure at high pressure conditions. The reaction at
this stage becomes zero order
Combining the results of equation
𝜽 = 𝑲𝑷𝟏/𝒏
On substitution of
̅
𝑪
𝜽=
̅̅̅̅
𝑪𝒎
 Freundlich isotherm {ln(𝐶 ) = (1/n) ln(P) + ln(K. Cm)}
̅
 It is in the form y = mx +c
 Therefore y = ln(𝐶̅ ) , x = ln(P) , m = 1/n, C = ln(K. Cm)
 On plotting graph between ln(𝐶̅ ) vs ln(P) the slope and intercept can be found
Types of adsorption isotherms

Rate controlling steps – Fluid-Solid Catalytic reactions
 Consider the reaction mechanism for solid catalyzed reactions
Surface Reaction Controlling

The concentrations 𝐶̅ A , 𝐶̅ B , 𝐶̅ C will be those corresponding to equilibrium for the
adsorption and Desorption steps.
̅ A eq = K ACA 𝑪
𝑪 ̅ u (1)
𝑪̅ B eq = K BCB 𝑪
̅u (2)
̅ ̅
𝑪C eq = K CCC 𝑪u (3)
The surface rate equation is
Substitute the above values into the surface rate equation,

The concentration of vacant sites can be expressed in terms of the total concentration of
̅m
sites 𝑪
̅m = 𝑪
𝑪 ̅u + 𝑪
̅A + 𝑪̅B + 𝑪̅ C (6)
Since 𝐶̅ A ( or 𝐶̅ B and 𝐶̅ C ) corresponds to the equilibrium value for adsorption, eqn (1), (2)
& (3) can be combined with eqn (6) to yield,
 Eqn (5)and(7) can be combined to give a relatively simpleexpression for the rate in terms
of fluid – phase concentrations,
 If the equilibrium constant for the overall reaction is denoted byK,
 Substitute
then,
 Substitute the eqn (11) into eqn (8)
Adsorption or Desorption Controlling

 Consider the reaction typeA + B ↔ C
 Simplify the aboveequation,
 Substituting this value of 𝐶̅ Ain the following rate controllingequations,
 Then the equation becomes

 The final rate equation for adsorption of A controlling the processis
 If, instead of adsorption, the rate of desorption of product Ccontrols the wholereaction,
Problems
1. Consider a solid catalyzed reaction A  R + S. Assuming Langmuir-Hinshelwood model,
derive the kinetic Rate equation. Assume Surface reaction to be rate controlling.
Ans: The reaction mechanism is
A + X  A.X (Adsorption)
A.X + X  R.X + S.X (Surface reaction)
R.X  R + X
S.X  S + X (Desorption)
Given, Surface reaction is rate limiting.
 The concentration of reaction components at equilibrium are
CA = K A CA C v CR = KR CR Cv and CS = KS CS Cv ------ 1
 For the surface reaction, we get r|sur = [ksur CA Cv – ksur| CR CS]

Substituting equation 1 into the above, we get
r|sur =ks (Cv2) [KA CA – (KR KS/Ksur) CR CS] ------ 2
 By equilibrium concepts for surface reaction, we know

K = (Ksur KA)/(KR KS) or (KR KS/Ksur)= KA,/K ------ 3
 We know, Cm = CA + C R + CS + Cv
Substituting equation 1 into the above and simplifying, we get
Cv = Cm /[(KA CA) + (KR CR) + (KS CS) + 1] ------ 4
 Finally Substituting equations 3 and 4 into equation 2, we get
r|sur =ks KA (Cm2) [CA – (1/K) CR CS]/[(KA CA) + (KR CR) + (KS CS) + 1]2
2. Tertiary butyl alcohol (TBA) is produced by the liquid phase hydration (W) of isobutene
(I) over an amberlyst-15 catalyst. The liquid is normally a multi-phase mixture of
Isobutene, water and the solid catalyst. The reaction can be represented as I + W  TBA.
If all the species set adsorbed on to the catalyst surface and if the adsorption of Isobutene
is rate limiting, derive the Rate equation for the reaction.
Ans: Let A – Isobutene (I), B – Water (W) and R – Tertiary Butyl Alcohol (TBA).
Thus the given reaction becomes A+BR
A + X  A.X (Adsorption)

B + X  B.X
A.X + B.X  R.X + X (Surface reaction)
R.X  R + X (Desorption)
Given, Adsorption of ‘A’ is rate limiting.
 The concentration of reaction components (leaving ‘A’) at equilibrium are

CB = KB CB Cv and CR = KR CR Cv ------ 1
 From the surface reaction, we get KS = [CR Cv]/[CA CB]
Or CA = [CR Cv]/[KS CB]

Using equation 1 and the overall equilibrium constant {K = [KA KB KS]/KR} into
the above, we get CA = (KA/K) (CR Cv/CB) ------ 2
 We know, Cm = CA + C B + CC + Cv
Substituting equations 1 and 2 into the above and simplifying, we get
Cv = Cm /[(KA/K)(CR/CB) + (KB CB) + (KR CR) + 1] ------ 3
 We know, the rate of adsorption of ‘A’ is

rA|= kA [ CA Cv – (1/KA) CA]
Substituting equation 2 into the above, we get
rA| = kA Cv [CA – (1/K) (CR/CB)]
Finally, Sub. equation 3 into the above, we get
rA| = (kA Cm) [CA – (1/K) (CR/CB)] / [(KA/K)(CR/CB) + (KB CB) + (KR CR) + 1]
__________________________________________________________________________
Unit III – GAS-SOLID CATALYTIC REACTORS
Course Content
 Diffusion within catalyst particle
 Effective thermal conductivity
 Mass and heat transfer within catalyst pellets
Solid Catalyzed Reactions

 A substance that enhances the rate of a chemical reaction and is recovered at the end of the
reaction without change in its mass and chemical composition is called a catalyst.
 A catalyst which has a large area resulting from pores is called as a porous catalyst.
Characteristics of solid catalyst:
 Activity – it is a measure of the accelerating effect that a catalyst has on the rate of a given
reaction.
 Specificity (selectivity) – A property of a catalyst to speed up the main reaction (produce
desired product) in the presence of several side reactions.
Steps in catalytic reactions
Mechanism of solid catalyzed reactions

1. Diffusion of reactant “A” from bulk fluid phase to the external surface of the catalyst
through the fluid film – External or surface diffusion step.
2. Diffusion of the reactant from the pore mouth into the catalyst pores – Pore diffusion step.
3. Adsorption of reactant “A” onto the catalyst surface (External and pore surfaces).
4. Chemical reaction of the adsorbed reactant on the surface of the catalyst to form product
(Surface reaction)
5. Desorption of products from the surface to the fluid phase near the surfaces.
6. Diffusion of the desorbed products from the interior of the catalyst to the pore mouth at the
external surface i.e. to the external surface (Reverse pore diffusion).

7. Diffusion of the products from the external surface into the bulk fluid phase through the
fluid film surrounding the catalyst (Reverse-external diffusion)
The rate of the reaction for the porous catalyst particle depends upon
1. Surface kinetics
2. Pore (diffusion) resistances – reduced by reducing the catalyst particle size, which thus
shortens the diffusion path
3. Particle temperature gradient – caused by evolution or absorption of large amount of heat
during reaction
4. Film temperature gradient – temperature difference b/w the outer surface of the catalyst
particle and the bulk gas stream
5. Film (diffusion) resistance – concentration gradient across the gas film surrounding the
catalyst particle
Diffusion
The process which causes the net movement of molecules from higher concentration to one
of lower concentration without the help of any external force at a fixed temperature and
pressure is called diffusion.
 Diffusion occurs as a result of thermal movement of molecules.

 During its movement, a molecule collides with other molecules and changes it speed and
direction.
 So the rate of diffusion movement depends on the number of collisions between the
molecules
Types of diffusion
 Atomic diffusion, in solids.

 Eddy diffusion, in coarse-grained description of turbulent flow
 Effusion of a gas through small holes.
 Electronic diffusion, resulting in an electric current called the diffusion current
 Facilitated diffusion, present in some organisms.
 Gaseous diffusion, used for isotope separation
 Heat equation, diffusion of thermal energy
 Ito diffusion, mathematisation of Brownian motion, continuous stochastic process
 Knudsen diffusion of gas in long pores with frequent wall collisions
 Momentum diffusion, ex. the diffusion of the hydrodynamic velocity field
 Osmosis is the diffusion of water through a cell membrane.
 Reverse diffusion, against the concentration gradient, in phase separation
 Rotational diffusion, random reorientations of molecules
 Surface diffusion, diffusion of particles on a surface

Bulk Diffusion Knudsen Diffusion
Effective Diffusivity (De)
Accounts for the fact:
 Not all the area normal to the direction of the flux is available for the molecules to diffuse.
 The paths are tortuous.
 The pores are of varying cross-sectional areas.
𝐀𝐜𝐭𝐮𝐚𝐥 𝐝𝐢𝐬𝐭𝐚𝐧𝐜𝐞 𝐚 𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐞 𝐭𝐫𝐚𝐯𝐞𝐥𝐬 𝐛𝐞𝐭𝐰𝐞𝐞𝐧 𝐭𝐰𝐨 𝐩𝐨𝐢𝐧𝐭𝐬

𝝉̅ = tortuosity =
𝐒𝐡𝐨𝐫𝐭𝐞𝐬𝐭 𝐝𝐢𝐬𝐭𝐚𝐧𝐜𝐞 𝐛𝐞𝐭𝐰𝐞𝐞𝐧 𝐭𝐡𝐨𝐬𝐞 𝐭𝐰𝐨 𝐩𝐨𝐢𝐧𝐭𝐬

𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐯𝐨𝐢𝐝 𝐬𝐩𝐚𝐜𝐞

Φp =
𝐓𝐨𝐭𝐚𝐥 𝐕𝐨𝐥𝐮𝐦𝐞 (𝐯𝐨𝐢𝐝𝐬 & 𝑠𝑜𝑙𝑖𝑑𝑠)
σc = Constriction factor
Difference b/w Bulk diffusion and Knudsen diffusion
Bulk diffusion (or) Ordinary Knudsen diffusion

diffusion
Pores are considerably large Pore size of a solid catalyst is small
Gas is relatively densed Gas density is low
Bulk diffusivity is the function of Knudsen diffusivity is depends on the
molecular velocity and the mean free molecular velocity “v” and pore radius
path; i.e. the function of temperature “a”
and pressure
Gaseous diffusion in single cylindrical pore

The equation for the rate of diffusion (in a binary gaseous mixture of A and B) in terms of bulk
diffusivity and Knudsen diffusivity.
Where y A = mole fraction of A

x = coordinate in the direction of diffusion
D is combined diffusivity given by
For the reaction A → B, reaction and diffusion in a pore would require equimolal counter diffusion
i.e. NB = -NA Then eqn (3) becomes a = 0 and the effective diffusivity is
When pore radius is large ((DK )A → ∞)

The eqn (2) becomes
Substitute eqn (5) in (1)
If equimolal counter diffusion, NB = -N A
(i). When pore radius is very small ( DAB → ∞) (8)

The eqn (2) becomes D = (DK )A (9)
Substitute eqn (9) in (1)
This eqn is the usual one exp ressing Knudsen diffusion in a long capillary
Evans et al have shown NB / N A constant ratio to be (at constant p)

Calculation of diffusivities
Chapman - Enskog formula for bulk diffusivity at moderate temperatures and pressures (for binary
gas mixture A and B)
DAB = bulk diffusivity, cm2 / s

T = Temperature, K
M Aand MB = Molecular weights of A and B
pt = Total pressure of the gas mixture, atm
𝜎AB , ∈AB = constants in the Lennard - Jones potential energy function for the molecular pair AB;
𝜎AB is in o A
𝛺 AB = Collision integral, which would be unity if the molecules were rigid spheres and is a
function of k BT / ∈AB for real gases k B = Boltzmann's constant
Lennard - Jones equation (For nonpolar gases) unlike molecular pair AB can be estimated from
the constants for like pairs AA and BB
Where k B = Boltzmann's constant Tc = critical temperature

Vb = volume per mole at normal boiling point
For evaluating Knudsen diffusivity Average molecular velocity
For a circular pore of radius 'a'

Diffusion in porous catalysts

1. Steady flow type constant-pressure apparatus for measuring diffusion rates in porous
catalysts
2. Dynamic methods (pulse input)
3. To compare the observed and predicted global rates by combining the rate equation for
Chemical steps and intraparticle mass-transport resistance
4. Physical properties of the catalyst (surface area and pore volume per gram, density of the
solid phase and the void volume distribution according to particle size)
(i). The parallel-pore model (ii). The Random-pore model
Steady flow type- Constant pressure apparatus for measuring diffusion rates in porous
catalysts
Diffusion in porous catalysts

Steady flow type constant-pressure apparatus for measuring diffusion rates in porous catalysts
• Diffusion rates of H2 and N2 gases were studied.
The effective diffusivity is defined in terms of diffusion rates (per unit of cross sec tional area)
by the equation
Where (NA )e = diffusion flux in a porous catalyst

De = effective diffusivity (constant)
Then eqn (1) can be integrated to give
Where ∆r = length of the pellet

Dynamic methods
Dynamic methods
 A pulse input of diffusing component A can be inserted into a stream of helium flowing
through the upper chamber.
 Pure helium also flows through the lower chamber.
 Some of the pulse of A diffuses through the pellet and is measured as a response pulse at
the detector in the lower stream.
 For high flow rates of a no adsorbing component, the effective diffusivity is given by
 Where 𝜇 1 = first moment (retention time) of the diffusing component in the pellet
 𝜇 1 is obtained from the measured response pulse CA (t) by the eqn
 Where CA (t) = concentration (function of time, t) in the pulse response

 ∈p = porosity of pellet
 ∆r = length of pellet
The parallel-pore model

 Wheeler proposed a model based on the following physical properties of the catalyst
(i). surface area and pore volume per gram,
(ii).density of the solid phase and
(iii).the void volume distribution according to particle size
 Monodisperse pore-size distribution in a catalyst pellet.

̅ can be written as
The mean pore radius 𝒂
Where Vg = Total pore volume in a pellet Sg = Total pore surface area in a pellet
 By using Vg, Sg and ρs, Wheeler replaced the complex porous pellet with an assembly
(having a porosity εp) of cylindrical pores of radius ã.
 To predict De from this model the only other property necessary is the length x L of the
diffusion path.
 If we assume that, on the average, the pore makes an angle of 45o with the coordinate ‘r’
in the resultant direction of diffusion, xL = √2r.
 Owing to pore interconnections and non-cylindrical shape, this value of xL is not
satisfactory.
 Hence it is customary to define xL in terms of an adjustable parameter, the tortuosity
factor,
XL = δ r
Combine the above equation with the following molal flux of A eqn,
The diffusion flux in the porous pellet can be written as,
∈𝑫
Effective diffusivity, De =
𝜹
The Random-pore model

 Pellets containing a bidisperse pore system.
 The pellet consists of an assembly of small particles.
 When the particles themselves contain pores (micropores), there exists both a macro and
a micro void-volume distribution.
 The voids are not imagined as capillaries, but more as an assembly of short void regions
surrounding and between individual particles.
 The nature of the interconnection of macro and micro void regions is the essence of the
model.
 Transport in the pellet is assumed to occur by a combination of diffusion through the
macro regions (of void fraction εM), the micro regions (of void fraction εµ) and a series
contribution involving both regions.
 It is supposed that both micro and macro regions can be represented as straight, short
cylindrical pores of average radii ãM and ãµ.
 The magnitude of the individual contributions is dependent on their effective cross-
sectional areas.
 The effective diffusivity can be calculated as,

 No tortuosity factor is involved in this model. The actual path length is equal to the
distance coordinate in the direction of diffusion.
 The random-pore model can also be applied to monodisperse systems.
 For a pellet containing only macropores εµ =0, Eq.(1) becomes
 Ex: For silica gel εM =0, the Eq. (1) becomes
Effective thermal conductivity

 The effective thermal conductivities of catalyst pellets are surprisingly low.
 Significant intrapellet temperature exists, and the global rate may be influenced by
thermal effects.
 The effective thermal conductivity is the energy transferred per unit of total area of pellet
(perpendicular to the direction of heat transfer).
 The defining equation may be written as
 Small values of ke is due to numerous void spaces (hinder the transport of energy)
 Thermal resistance in porous materials (path through the solid phase)
 The effective thermal conductivity of pellets of microporous particles of silver was only
2 to 4 times that of alumina pellets, at the same macropore void fraction, pressure and
temperature.
 In contrast, the thermal conductivity of solid silver is about 200 times as large as that of
solid alumina.
 ke is the strong function of the void fraction, increasing as εp decreases.
 Thermal conductivity of bulk solid should have little influence on ke.
 The effective thermal conductivity is a function of volume fraction of the void phase
and the thermal conductivities of the bulk fluid and solid phases, kf and ks.
 The relationship is

Mass transfer with reaction

The effectiveness factor η as follows:
The local rate (per unit mass of catalyst) may be expressed as

r = f (C, T) (2)
Eqn (1) may rewritten as
rp = η rs
rp = η f (Cs , Ts ) (3)
For isothermal conditions, the eqn (3) can be written as
rp = η f (Cs ) (4)
Effectiveness factors for spherical particle

 Irreversible reaction A→B is first order
 For an isothermal conditions r = f (CA) = k1 CA
 The rate of the reaction for the whole catalyst pellet can be written as
rp = η k1 f (CA )s (1)
The mass balance over the spherical - shell volume of thickness ∆r
Where 𝝆p = density of the pellet

Apply lim it ∆r → 0 and assume effective diffusivity is independent of the concentration of

reactant, this difference eqn becomes
At the center of the pellet symmetry requires
and at the outer surface C = Cs at r = rs (5)
Linear differential eqn (3) with boundary conditions (4) and (5) may be solved by conventional
methods to yield
Where 𝜑s is a dimensionless group (Thiele - type modulus for a spherical pellet)
The rate of reaction for the whole pellet
Then eqn (1) become as
Differentiating eqn(6), evaluating the derivative r = rs , substituting this int o eqn (8) gives
Then the desired rate for the whole pellet

Pore diffusion resistance combined with surface kinetics

Single cylindrical pore, first order reaction
A → Product, first order reaction At steady state material balance for reactant A for this
elementary section gives
output - input + disappearance by reaction = 0 (1)
Reactant A entering by diffusion,
Reactant A leaving by diffusion

Disappearance of reactant A on surface by reaction
Substitute in equation (1)
eqn (2) ¸ (-𝜋r 2 D∆x)
Here the rate is based on unit surface area of the wall of the catalyst pore k" (m / s)
-rA )V = (-r' )W = (-r'' )S (4)
in terms of rate constant
kV = k' W = k ''S (5)
Cylindrical catalyst pore
In terms of volumetric units substitute eqn (6) in eqn (3)
The general solution of eqn (8)
Boundary conditions
(i). At the pore entrance
CA = CAS at x = 0 (10)
(ii). there is no flux or movement of material through the interior end of the pore

Apply B.C (i) in eqn (9)

CAS = M1 + M 2 (12)\
From eqn (9)
Apply B.C (ii)
Similarly
Substitute M1 and M 2 into eqn (9)
Eqn (17) becomes
we have
Substitute in eqn (18)


Effectiveness factor for a first order reversible reaction A↔B at isothermal conditions, for
a spherical catalyst pellet
The rate eqn for a reversible first order reaction is
r = k R (C - Ceq ) (1)
where Ceq = equilibrium concentration of reactant
k1 = forward rate constant K = equilibrium constant

The mass balance of reactant on a spherical shell is
Taking limit ∆r →0 and replacing C with variable

C' = C - Ceq
Boundary conditions are
The solution for the eqn
Mass and Heat transfer with reaction

 When the heat of reaction is large, intrapellet temperature gradients may have a larger
effect on the rate per pellet than concentration gradients.
 When heat of reaction is low, the center ad surface temperatures may differ appreciably,
because catalyst pellets have low thermal conductivities.
 The combined effect of mass and heat transfer on rp can still represented by the general
definition of the effectiveness factor.
 The nonisothermal η may be calculated in the same way as the isothermal η, except that
an energy balance must be combined with the mass balance.

Nonisothermal Effectiveness Factors

Consider irreversible first - order reaction A → B
Q the effect of temperature on De is neglected
The differential energy balance over the spherical shell of thickness ∆r is
Taking limit ∆r → 0
Assume : k e is independent of temperature
(2)
Boundary conditions :
The mass balance over the spherical - shell volume of thickness ∆r
Apply limit ∆r → 0 and assume effective diffusivity is independent of the concentration of

reactant, this difference eqn becomes
At the center of the pellet symmetry requires
and at the outer surface
Where
The solution of eqn (1 - 4) and eqn (5 - 8) gives the concentration and temperature profiles
within the pellet.
An analytical relation between the concentration of reactant and temperature at any point in the
pellet
Or
Solve this eqn and applying the boundary conditions eqn (3, 4) and eqn (7, 8)
This eqn is originally derived by Damkoehler. This eqn is valid for any form of rate expression

The maximum temperature rise in a pellet would occur when the reactant has been consumed by
the time it diffuses to the center Eqn (11) becomes for C = 0
The effectiveness factor h is expressed as a function of three dimensional parameters

1. The Thiele - type modulus
2. The Arrhenius number
3. A heat of reaction parameter
Carberry has shown that for (𝜑s )s > 2.5, the η - vs - (𝜑s )s relationship could be characterized by
the single parameter β𝛾, rather than by 𝛾 and β separately.
For example, for first - order irreversible reaction found that
Where
Weisz and Hicks have extended the analyis to the problem of combined mass and energy
transport.

For a first - order irreversible reaction the criterion may be expressed as
when β = 0, it approaches isothermal condition

If 𝜑 ≤ 1, the nonisothermal effectiveness factor will be near unity, so that intrapellet gradients
can be neglected.
Packed Bed Reactor (PBR)

 Primarily employed in the manufacture of Industrial chemicals
 Most widely used reactors for immobilized enzymes and immobilized microbial cells
Advantages:
 High conversion per unit mass of catalyst
 Low operating cost
 Stabilization of operating conditions
Disadvantages:
 Poor temperature control
 Undesired thermal gradients may exist
 Channeling may occur
 Unit may be difficult to service and clean
Fluidized Bed Reactor (FBR)

 Primarily employed in petroleum refineries in the cracking of crude oil.
 In this type of reactor, a fluid (gas or liquid) is passed through a granular solid material
(usually a catalyst possibly shaped as tiny spheres) at high enough velocities to suspend
the solid and cause it to behave as though it were a fluid
Advantages:
 Good mixing
 Good uniformity of temperature
 Catalyst can be continuously regenerated with the use of an auxiliary loop
Disadvantages:
 Bed-fluid mechanics not well known
 Severe agitation can result in catalyst destruction and dust formation
 Uncertain scale-up
 Entrainment loss
Problems
1. A first order heterogeneous irreversible reaction A  R is taking place within a spherical
catalyst pellet which is plated throughout the pellet. The reactant concentration midway
between the external surface and the center of the pellet is equal to 1/10 of the concentration
at the external surface. The concentration of the reactant at the external surface is 0.001
gmol/lit. The pellet diameter is 2 x 10-3 cm and the diffusion coefficient is 0.1 cm2/s.
(i) What is the concentration of the reactant at a distance of 3 x 10-4 cm from the external pellet
surface?
(ii) To what diameter should the pellet be reduced, if the effectiveness factor is to be 0.8?

Ans: (i) We know, the concentration profile for the diffusion through porous spherical catalyst
is
CA/CAs = (rs/r) [sinh(m r)/sinh(m rs)]
 Substituting the given CAs = 1x10-3 mol/lit, CA = (1/10) CAs = 1x10-4 mol/lit, rs =
ds/2 = 1x10-3 cm and at r = rs/2 (mid-way) = 5x10-4 cm into the above , we get (by
trial and error method) m ≈ 6000
 Now substituting rs - r = 3x10 cm or r = 7x10-4 cm, determined ‘m’ and the other
-4
given data’s into the above equation, we get CA ≈ 2.364x10-4 mol/lit
(ii) We know, for spherical catalyst,

ηs = [3/(m rs)] {[1/tanh(m rs)] – [1/(m rs)]}
 For the given rs = ds/2 = 1x10-3 cm and m ≈ 6000, the above equation yields
 ηs ≈ 0.417
 Also, we know ηs α (1/rs) or ηs1/ηs2 = rs2/rs1
 Substituting the given ηs = 0.8 along with the determined values into the above,
we get
o rs2 ≈ 0.0005 cm
Says that the pellet is approximately reduced to half of its original value.
2. A first order catalytic reaction A  R is carried out in a packed bed reactor. The molal
feed rate of the reactant is 12.5 kmol/hr. The following data is available;
W (kg cat) 0.625 1.87 3.125 4.375 6.25 7.5 8.75
XA 0.058 0.139 0.213 0.288 0.381 0.440 0.493
Calculate the weight of the catalyst for 40% conversion in a packed bed reactor, if the
molal feed
rate is increased to 125 kmol/hr.
 Ans : We know
That is, a plot of XA vs. W/FAo will give slope as –rAI.
 From the given data, FAo = 12.5 kmol/hr, we have

W/FAo (X) 0.05 0.15 0.25 0.35 0.5 0.6 0.7
XA (Y) 0.058 0.139 0.213 0.288 0.381 0.440 0.493
 From the plot between XA vs. W/FAo, at XA = 0.4, We get

W/FAo ≈ 0.53
 Now, for the given new FAo = 125 kmol/hr, we get

W = 0.53 * 125 ≈ 66.25 Kg

Unit IV – GAS-SOLID NON-CATALYTIC REACTORS
Course Content
 Models for explaining the kinetics
 Volume and surface models
 Controlling resistances and rate controlling steps
 Time for complete conversion for single and mixed sizes
 Fluidized and static reactors
Gas-Solid non-catalytic reactions
Two cases
1. The particle size remains unchanged during the reaction
2. The particle size changes with progress of reaction
The particle size remains unchanged during reaction

 Solid particles contain large amount of inert material which remain as a non-flaking ash
or
 A firm product material is formed by the reactions.
Example
(i). Roasting of sulphide ores in air to yield metal oxides
(ii). Similarly iron pyrites
(iii). The reduction of metal oxides to corresponding metals
(iv). The nitrogenation of calcium carbide

(v). Treatment of carbonaceous material
The particle size changes with progress of reaction
Examples
Kinetic models
The closest representation of reality which can be treated without too many mathematical
complexities
1. The progressive-conversion model (PCM)
2. The shrinking unreacted-core model (SCM)
The progressive conversion model (PCM)

 The reactant gas enters and reacts throughout the particle at all times, most likely at
different rates at different locations within the particle.
 The solid reactant is converted continuously and progressively throughout the particle.

Shrinking Core Model (SCM)

Assumption
 The reaction first begins at the outer surface of the solid particle and the deeper layers do
not take part in the reaction until all the outer layer has transformed into solid or gaseous
product.
 Gradually, the reaction zone then moves inward (into the solid), constantly reducing the
size of core of unreacted solid and leaving behind completely converted solid (solid
product) and inert material (inert constituent of the solid reactant).

SCM for spherical particles of unchanging size/fixed size

The following five steps occur in succession during the reaction
1. Diffusion of gaseous reactant A through the gas film surrounding the particle to the
surface of solid particle – External diffusion.
2. Penetration of A by diffusion through pores and cracks in the blanket (layer) of ash to the
surface of the unreacted core – pore or internal diffusion.
3. Reaction of gaseous reactant A with solid B at the surface of the unreacted core –
reaction surface.
4. Diffusion of any gaseous products back to the exterior surface of solid through the ash
(ash layer) – reverse internal diffusion.
5. Diffusion of gaseous products through the gas film back into the main body of gas –
reverse external diffusion.
Rate controlling step - SCM Unchanging size

1. Diffusion through gas film
2. Diffusion through the ash (converted solid and inert material) / ash layer
3. Chemical reaction
Diffusion through gas film controls

 No gaseous reactant A is present at the surface of particle. So the concentration driving
force, CAg - CAs = CAg and this is constant during the reaction
 The rate of reaction of A per unit surface = The molar flux of A from the main body of
gas to the surface of the particle.

From the stoichiometry of the reaction A(g) + bB(s) → products
Combining eqns (1) and (2)
The amount of B present in a particle is
where 𝜌B = molar density of B in solid (mol / m3 ) V = volume of a particle (m3 of solid)

The decrease in volume of radius of unreacted core as a result of disappearance of dNB moles of
solid reactant is given by
Substitute eqn (5) in eqn (3)
Re arranging eqn (6)

Integrate the eqn (7) between the limits
The above eqn is the unreacted core shrinks with time

For complete conversion
time for complete conversion of a particle be 𝜏 at complete conversion rc = 0
The eqn (8) reduced to
The above eqn represents the radius of unreacted core in terms of fractional time for complete
conversion
Fractional Conversion determination
The radius of unreacted core in terms of fractional conversion
1 - XB = fraction of B unreacted
The eqn (12) is represents the relationship of time with the radius of unreacted core and
fractional conversion of B

Diffusion through ash layer controls
The instantaneous rate of reaction of A at any time is given by the rate of diffusion of A to the
reaction surface,
Where
QA = flux of A through a spherical surface of any radius r in the ash layer
QAs = flux of A through the exterior surface of particle QAc = flux of A to the reaction surface
The flux of A through the ash layer may be represented by Fick's law
where De = effective diffusion coefficient of A in the ash layer

Combining eqn (1) and (2)
Separate the above eqn
Integrate the eqn (4) with the limits

The eqn (5) represents the conditions of a reacting particle at any time. We have
Eqn (5) becomes
We have
Eqn (7) becomes
Integrate the eqn (9)
Limits:
The solution of the above integral
The above eqn relates the radius of unreacted core with time when the diffusion through ash
layer controls the overall reaction rate

The time required for complete conversion of a particle (𝜏) is obtained by putting rc = 0
Eqn (11) can be reduced to

The above eqn gives an idea regarding the progress of reaction in terms of the time required for
complete conversion
Fractional conversion determination
Eqn (13) in terms of fractional conversion becomes
Chemical reaction controls
The rate at which moles of A are consumed in the reaction per unit surface is given by
From stoichiometry

where k" is the first order rate constant for the surface reaction
Amount of B present in a particle, NB = 𝜌B V
Eqn (3) becomes
Integrate eqn (5) with the limits

The above eqn gives the time 't' at which the core has a radius rc and the fractional conversion XB
for the particle in terms of 𝜏
Rate of reaction for shrinking spherical particles (Variable/Changing particle size)

 When no ash forms, as in the burning of pure carbon in the air, the reacting particle shrinks
during disappearing.
The following 3 steps during this reaction
 Diffusion of reactant A form the main body of gas through the gas film to the solid surface.
 Reaction on the surface b/w reactant A and solid.
 Diffusion of reaction products from the surface of the solid through the gas film back into
the main body of gas. Note that the ash layer is absent and does not contribute any
resistance.
Here the rate controlling step may be gas film diffusion or chemical reaction

 The expressions derived for single particles of unchanging size are directly applicable to
the shrinking spherical particles (changing size) when chemical reaction controls the
overall rate of reaction.
Diffusion through gas film controls
 The changing of particle size in turn changing the film resistance.

 Film resistance at the surface of a particle depends upon the following parameters.
1. Relative velocity b/w particle and fluid
2. Particle size

3. Fluid properties
 The correlation for mass transfer of component with mole fraction y in a fluid to free
falling solids is
Where Schmidt number,
Reynolds number,
During reaction a particle changes in size; hence k g also varies In general k g rises for an
increase in gas velocity and for small particles
Eqn (3) represents particle in the Stokes law regime
Let us derive conversion - time relationship for such particles
Stokes Regime - Small particles

At the time when a particle, originally of size Ro , has shrunk to size R, we may write
The rate of reaction in terms of size R of shrinking unreacted particle is given by
Substitute eqn(5) in eqn(6),
In the Stokes regime eqn(2) reduced to

Now eqn(7) becomes
Integrating eqn(9) with the limits
 The above eqn expresses the relationship of size with time for shrinking particles in
the Stokes regime.
 This eqn well represents small burning solid particles as well as small burning liquid
droplets

SCM for Cylindrical particles of Unchanging size/Fixed size (Radius R and Length L)
1. Diffusion through gas film controls
2. Chemical reaction controls
3. Diffusion through ash layer controls

The time required to achieve the same fractional conversion for particles of different but
fixed/constant/unchanging sizes is given by
Design of Fluid-Particle Reactors

Factors control the design of fluid-solid reactors
1. The reaction kinetics for single particles
2. The size distribution of solids being treated and
3. Flow patterns of solids and fluid in the reactor
Various contacting patterns in fluid-solid reactors

Contacting patterns
Solid and gas both in plug flow
 The compositions of solids and gas will vary along their flow paths.
 Reactor operations are isothermal.
Contacting patterns are
 Countercurrent flow (blast furnace and cement kilns)
 Co-current flow (rotary dryers-heat sensitive materials)
 Cross flow (moving belt feeders)
Solids in mixed flow
 In fluidized-bed reactors, the solids are in mixed flow.
 Reactors operate under isothermal conditions.
Semibatch operations
 Gas passes through a stationary bed of solids, charged and removed batch wise.
 Approximates plug flow, used for small scale operations
 Ex- ion-exchange column.
Batch operations
 Batch of solid and fluid
 Ex: acid attack of solid
 Composition of fluid is uniform throughout the reactor
 This is fairly correct in situations where fractional conversion of fluid-phase reactants is
not too high.

 Fluid back mixing is considerable.

 This assumption does not have much deviation from reality.
Objectives
 Design of reactors for non-catalytic fluid-solid reactions.
 Develop performance equations for various frequently met patterns assuming uniform gas
composition within reactor in every case.
Mixture of Particles of Different but Unchanging Sizes, Plug Flow of Solids, Uniform Gas
Composition
 Solid feed consisting of a mixture of different-size particles.

 The size distribution of this feed can be represented by a discrete distribution.
 Size analysis obtained by screen analysis.
 Let F be the quantity of solid being treated in unit time
 Let F(Ri) be the quantity of material of size about Ri fed to the reactor.
 If Rm, is the largest particle size in the feed, we have for particles of unchanging size
 When in plug flow all solids stay in the reactor for the same length of time tp.
 The conversion XB(Ri) for any size of particle Ri can be found.
Important Note:

 As particles smaller R are completely converted they do not contribute to the fraction
unconverted and thus are not included in the summation equation.
 Where R is the radius of the largest particle which is completely converted in the reactor.
 Smaller particle requires a shorter time for complete conversion compared to the larger
size particles.
Mixed Flow of Particles of a Single Unchanging Size, Uniform Gas Composition
 Fluidized bed reactor with constant flow rates of both solids and gas into and out of the
reactor.
Assumption
 Uniform gas concentration and mixed flow of solids, this model represents a fluidized-
bed reactor in which there is no elutriation of fine particles.
 The conversion of reactant in a single particle depends on its length of stay in the bed,
and it’s appropriate controlling resistance.
 However, the length of stay is not the same for all the particles in the reactor; hence we
must calculate a mean conversion, XB of material.
 The solids leaving the reactor
 Where E is the exit age distribution of the solids in the reactor

 For mixed flow of solids with the mean residence time in the reactor

 For mixed flow of the single size of solid which is completely converted in time, we
obtain
Rate controlling steps

Film resistance controls
The time – conversion relationship is
Substitute in the following expression
The expansion form is

The time – conversion relationship for chemical reaction controls
Substitute in the following expression

The solution of the above equation is
The expansion form is
Diffusion through Ash layer controls

The mean fraction of unconverted B is given by
Mixed flow of a size mixture of particles of unchanging size and uniform gas composition
1. Diffusion through gas film controlling
2. Chemical reaction controlling

3. Diffusion through ash layer controlling

Fluidized with entrainment of solid fines/solid carry over in fluidised bed

1. Diffusion through gas film controlling
2. Chemical reaction controlling


3. Diffusion through ash layer controlling

Problems
1. Two small samples of solids are introduced into a constant environment oven and kept
there for one hour. Under these conditions, 4mm particles are 58% converted and 2mm
particles are 87.5% converted.
(i) Find the rate controlling mechanism for the conversion of solids.
(ii) Find the time needed for complete conversion of 1mm particles.
Ans: (i) Let D1 = 4mm or R1 = 2mm and D2 = 2mm or R2 = 1mm.
So, XB1 = 0.58 and XB2 = 0.875
 Assuming that chemical reaction controls the process, we know

t/Τ = [1 - (1 – XB)1/3]
Given, t = 1 hr.
 For 4mm particles, (1/Τ1)= [1 - (1 – 0.58)1/3] or Τ1 ≈ 4 hr
 For 2mm particles, (1/Τ2)= [1 - (1 – 0.875)1/3] or Τ2 = 2 hr
This implies that Τ α R. Therefore, Chemical reaction controls the process.
(ii) Since Τ α R, the time needed for complete conversion of 1mm particle is 1 hour.
2. A feed consisting of 30% of 50µm, 40% of 100µm, and 30% of 200µm particles is to be
fed continuously in a thin layer onto a moving grate cross-current to a flow of reactant gas.
For the planned operating conditions the time required for complete conversion is 5, 10,
and 20 minutes for the three sizes of particles. Find the conversion of solids for a mean
residence time of 8 minutes in the reactor.
Ans: Given, the solids are in plug flow (moving grate) with tp = 8 min.
 Considering the gas at uniform composition, we know
Rm
1 – X B = ∑[1 – XB(Ri)] F(Ri)/F
R(tp=Τ)
 From the given time for complete conversion, we observe that Τ α R. Therefore,
the chemical reaction controls the operation. Thus, we have
1 – XB(Ri) = {1 – [tp/T(Ri)]}3
 Given T(50) = 5 min, T(100) = 10 min, T(200) = 20 min and F(50)/F = 0.3,
F(100)/F = 0.4 and F(200)/F = 0.3
Substituting the given values into the above equations, we obtain

1 – X B = 0 + [1 – (8/10)]3 (0.4) + [1 – (8/20)]3 (0.3) = 0.068
0r X B = 0.932 (or) 93.2%
3. A fluidized bed reactor is operating at steady state with a solid feed of varying size
distribution as mentioned below;
50µm – 20%, 80µm – 20%, 100µm – 25%, 150µm – 15% and 200µm – 20%.
The fluidizing gas phase reactant has uniform composition. The time for complete
conversion is 4, 8, 12, 16 and 19 minutes respectively of the above mentioned particles.
The feed rate is 1.3 kg/min and the reactor contains 15 kg of solids. Assuming the solids
are hard and remain unchanged in size & weight and also that chemical reaction is rate
controlling, calculate the average fractional conversion of the solid particles.
Ans: We know, for mixture of particles under mixed flow (fluidized bed) and chemical
reaction
controls
 Given (50) = 4 min, (80) = 8 min, (100) = 12 min, (150) = 15 min, (200)
= 18 min and F(50)/F = 0.20, F(80)/F = 0.20, F(100)/F = 0.25, F(150)/F = 0.15
F(200)/F = 0.20; Also, W = 15 Kg and F = 1.3 Kg/min.
 Substituting the given data along with = W/F = 15/1.3 = 11.5385 min into the
above equation, we get
≈ 0.204 or ≈ 0.796
_____________________________________________________________________________

Unit V – GAS-LIQUID REACTIONS
Course Content
 Absorption combined with chemical reactions
 Mass transfer coefficients and kinetic constants
 Application of film, penetration and surface theories
 Hatta number and enhancement factor for first order reaction
 Tower reactor design
Classification
 Gas- Liquid reaction [G/L Reactions]
 Liquid- Liquid reaction [L/L Reactions]
Objectives
1) To produce a particular product
Eg: Production of chlorobenzene by reaction of gaseous chlorine with liquid benzene-
G/L Reactions Production of ammonium nitrate by action of ammonia on aqueous nitric
acid- G/L Reaction
2) To separate a constituent from a fluid
Eg: Nitric acid by absorption of nitric oxide in water- G/L Reactions

Mass Transfer Theories

 Two-film theory
 Penetration theory
 Surface renewal theory
 Film-surface renewal theory
Two-film theory (Whitman’s)
 Steady-state: concentrations at any position in the tower do not change with time.
 Interface between the gas phase and the liquid phase is a sharp boundary.
 Laminar film exists at the interface on both sides of the interface
 Equilibrium exists at the interface, thus there is negligible resistance to mass transfer
across the interface: (xi, yi) is the equilibrium concentration.
 No chemical reaction: rate of diffusion across the gas- phase film must equal the rate of
diffusion across the liquid-phase film.
The flux in the gas phase,
The flux in the liquid phase,
At steady state fluxes are equal

Mass transfer coefficient α diffusivity

Penetration theory
 Most of the industrial processes of mass transfer is unsteady state process.
 In such cases, the contact time between phases is too short to achieve a stationary state.
 This non stationary phenomenon is not generally taken into account by the film model.
 In the absorption of gases from bubbles or absorption by wetted-wall columns, the mass
transfer surface is formed instantaneously and transient diffusion of the material takes
place.
Assumptions: Penetration theory

1. Unsteady state mass transfer occurs to a liquid element so long it is in contact with the
bubbles or other phase.
2. Equilibrium exists at gas-liquid interface.
3. Each of liquid elements stays in contact with the gas for same period of time.
Penetration theory
 The time of exposure of a fluid to mass transfer is quite short as a result there may be an
opportunity for concentration gradient to develop and the transfer process becomes an
unsteady one.

CAo = concentrat ion of solute in the bulk (inside an eddy )

CAi = concentrat ion of solute at the int erface
Zb = Depth of eddy from the int erface
The unsteady state transfer can be given by
Flux at the interface,
In terms of liquid mass transfer coefficien t (K Lavg )
Surface renewal theory

 For the mass transfer in liquid phase, Danckwert (1951) modified the Higbie’s
penetration theory.
 He stated that a portion of the mass transfer surface is replaced with a new surface by the
motion of eddies near the surface and proposed the following assumptions:
 The liquid elements at the interface are being randomly swapped by fresh elements from
bulk.
 At any moment, each of the liquid elements at the surface has the same probability of
being substituted by fresh element.
 Unsteady state mass transfer takes place to an element during its stay at the interface.
where,
S = rate of production of fresh surface per unit total surface at the interface
Film - Surface renewal theory

Rate equation for Straight Mass Transfer (i.e. Physical Absorption of A)

In physical absorption of gaseous A in a liquid, we have two resistances in series
1, Gas- film resistance
2, Liquid- film resistance
Rate of transfer of A Form Gas to Liquid is given by the rate expressions

For Gas film,
For Liquid film,
Combining the two equations with Henry’s law PAi= HA.CAi to eliminate the unknown interface
conditions PAi and CAi

This is the overall rate expression
Henry's law is given by:
Eq.(5) becomes
We know that
Substitute in Eq. (7)
Rate Equation for Mass transfer and Reaction

Here we have 3 factors to consider: what happens in the 1, Gas film
2, Liquid film
3, Main body of the liquid
We have 8 special cases from infinitely fast to very slow reaction

General Rate expression for mass transfer with reaction is

When reaction occurs in the liquid film the absorption of A from gas is larger than straight mass
transfer. Thus for the same concentration at the two boundaries of the liquid film we have
Liquid film
for same CAi, CA, CBi and CB in two cases

E is a fn(Ei and MH) , E is always >= to 1
Ei - enhancement factor for an infinitely fast reaction
M2H - maximum possible conversion in the film compared to maximum possible diffusion
through the film
MH - Hatta modulus
E is plotted against MH with Ei as a parameter, for a second order reaction- numbers on the
curves are the values of Ei
Case A: Instantaneous reaction with low CB

 Element of liquid contains either A or B but not both
 Reaction occur at a plane between A containing and B containing liquid called Reaction
plane

 Reactants A and B diffuse to the reaction plane for reaction to occur
 At steady state, flow rate of B towards the reaction plane will be b times the flow rate of
A.
 Rate of disappearance of A and B based on the unit interfacial surface are given by
kAg, kAl and kBl are mass transfer coefficients in gas and liquid phase
Equilibrium relationship between pA and CA at the interface is given by Henry’s law

pAi= HA CAi (2)
According to the two-film theory the liquid phase mass transfer coefficient for A and B are given
by
Now we will determine the unknown x, x0, CAi and pAi from the above equation to obtain
desired rate equation
From eqn (1) we have
÷ above equation with H A gives

using (6) to sub for x0 / x, (5) becomes,
Henry's law is
sub CAi from (8) into (7) yields

Special case: negligible gas phase resistance

If pure gaseous reactant A is used, then the gas phase resistance is negligible.
So, pA = pAi or kg → ∞
Eqn(11) reduces to
Case B: Instantaneous reaction with high CB

Concentration of B is high, more precisely if
then the reaction plane stays at Gas-liquid interface rather than liquid film. So there is a control
in the resistance of the gas phase and rate is not affected by any further increase in concentration
of B.
Rate is given by,

Case C: Fast reaction with low CB

 Here reaction takes place in a zone where both A and B are present
 Reaction is fast enough the reaction zone remains totally within the liquid film
 So, A does not enter the main body of the liquid to react there.
 As the reaction is fast the last resistance term in the general rate equation is neglected

Case D: Fast reaction with high CB
 When CB is so high, its considered to be constant throughout the liquid film

 Second order reaction rate simplifies to the more easily solved pseudo first order rate
expression
 Due to high CB and fast reaction the reaction zone spreads from the interface in the liquid
film but not cross the boundary
In this case enhancement factor is given by

Rearranging (22) gives
Case E and F: Intermediate rate with respect to Mass transfer

 Reaction is so slow that some of A diffuses through the liquid film into the main body of
the liquid
 Reactions occurs both within the film and in the main body of the liquid
 General rate equation with its three resistances
Case G: Slow reaction with respect to Mass Transfer

 All reaction in the main body of the liquid
 Liquid film still offering resistance to the transfer of A into the main body of the liquid
 So the gas film, liquid film and main body of the liquid act as resistances in series

Case H: Infinitely Slow reaction

 Mass transfer resistance is negligible
 Concentrations of A and B are uniform throughout the liquid
 Rate is determined by chemical kinetics alone

Rate of reaction based on unit volume of liquid is given by
Role of Hatta Number, MH

 Used to find out whether the reaction is fast or slow
 We focus on unit surface of Gas liquid interface
 We assume that gas phase resistance is negligible
 Film conversion parameter

• If MH>>1, all reaction occurs in the film and surface area is the controlling rate factor.
• If MH<<1, no reaction occurs in the film and bulk volume becomes the controlling rate
factor.
More precisely it has been found that
1. If MH>2, reactions occur in the film and we have cases A, B, C and D
2. If 0.02<MH<2, we have intermediate cases E, F and G
3. If MH<0.02, reactions occur in the main body of the liquid with no film resistance and we
have case H
 When MH is large – large interfacial area → Packed column, plate column and agitated
tank
 When MH is small - large volume of liquid → Bubble tank, bubble column, packed
bubble column and agitated tank
Use of solubility Data to determine the kinetic Regime

 Here we make use of solubility data expressed as Hendry’s law constant
 When reaction occurs in the film we can predict the relative importance of both film
resistances based on the numerical value of HA
 We consider the rate expression for straight mass transfer of A across the gas and liquid
film
 HA very small- gas is highly soluble in liquid
 gas film resistance is large and thus controls the rate.

 HA is large- Slightly soluble gases
 - liquid film resistance is large and thus controls the rate

 Gas film resistance controls for highly soluble gas- Eg: Ammonia in water; HA=0.02
(Pa.m3)/mol at 200C
 Liquid film resistance controls for slightly soluble gas- Eg: O2 in water;
HA=7400(Pa.m3)/mol at 200C
 Highly soluble gas is easy to absorb and has its main resistance in the gas phase.
Therefore, for such gases chemical reaction is not beneficial
 A sparingly soluble gas is difficult to absorb and has its main resistance in the liquid
phase.

 Therefore, for such gases chemical reaction that speeds up the rate is beneficial
Design of Gas-Liquid reactors

Tower and tank contactors for G/L reactions
Various ideal contacting patterns for G/L contactors

Straight Mass Transfer/ Physical Absorption
Countercurrent flow in a tower – Plug flow G + Plug flow L:

 To develop design equation, we have to combine the rate equation with the material
balance.
 For steady-state countercurrent operation we have for a differential element of volume dVr
‘A’ lost by gas (mol/s) = ‘A’ gained by liquid (mol/s)=-rA’’’’(dVr)
Rate at which the solute gas A is transferred from the gas phase to the liquid phase is given by
Gas film: Rate at which the solute A is transferred from the gas phase to the interface is
At steady state,
‘A’ lost from gas (mol/s)=‘A’ gained by liquid (mol/s)=-rA’’’’(dVr)

Usually, the mass transfer rate is given as flow of material per unit surface of interface
Integrating the above equation for the whole tower, we get
Now we express YA in terms of pA and XA in terms CA and obtain expression for Vr in terms of
the gas film and liquid film driving forces
putting the value of FgdYA from (12), We get
Rearranging, We get
Integration for the whole tower gives


Problems
1. The concentration of an undesirable impurity ‘A’ in air is to be reduced from 0.10% to
0.02% by absorption in pure water. Find the height of tower required for counter current
operations. Data: For consistency, units are given in moles, meters, and hours;
 For the packing used,
 kA(g) a = 32,000 mol/hr-m3-atm
 kA(l) a = 0.1 hr-1
 The solubility of A in water, HA = 125 x 10-6 atm-m3/mol
 Liquid mass flow rate, L = 7 X 1015 mol/hr-m2
 Gas flow rate, G = 1 X 1015 mol/hr-m2 at  = 1 atm
 Molar density of liquid, CT = 56,000 mol/m3
Ans:
 From the given data’s of individual mass transfer coefficient and the solubility of
water, we find the overall mass transfer coefficient as
1/(KAg a) = 1/ (kAg a) + (HA/ kAl a) = 128.125 x 10-5 m3-atm-hr/mol
 By material balance on the absorption tower and with given data, we get
CA = 8000 pA – 1.6
 Then, pA – pA* = pA – HA CA = pA – 125x10-6 (8000 pA – 1.6) = 2 x 10-4 atm.
 Thus, we know the height of tower required for counter current operations is
pA2
h = [G/π(KAg a)] ∫[dpA/(pA – pA*)]

pA1
0.001
= [(1x105) (128.125 x 10-5)/(1)] ∫[dpA/(2 x 10-4)

0.0002
Or h ≈ 512 m
-------------------------------------------------- ALL THE BEST ------------------------------------------

PDF

Uploaded by

Copyright:

Available Formats

PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

PDF

Uploaded by

Copyright:

Available Formats

CH6701 Chemical Reaction Engineering - II 2019-2020

St. Joseph’s College of Engineering 1 Chemical Engineering

Catalyst Preparation Methods

Gel formation method

St. Joseph’s College of Engineering 2 Chemical Engineering

Simple mixing of components

St. Joseph’s College of Engineering 3 Chemical Engineering

Surface area of catalyst

Determination of surface area

St. Joseph’s College of Engineering 4 Chemical Engineering

 Where po is the saturation or vapor pressure and c is a constant for theparticular

a plot of should give a straight line.

 Solving these equations for the volume of adsorbed gas corresponding to a

 Where No is Avogadro’s number, 6.02 x 1023 molecules / mol

St. Joseph’s College of Engineering 5 Chemical Engineering

 Where M is molecular weight and 𝜌is the density of the adsorbedmolecules.

Void volume and Solid density

Mass of catalyst sample placed in chamber = 101.5 g

St. Joseph’s College of Engineering 6 Chemical Engineering

Pore volume distribution

Mercury penetration method

St. Joseph’s College of Engineering 7 Chemical Engineering

Combination of Mercury-Penetration and Nitrogen- desorption method

St. Joseph’s College of Engineering 8 Chemical Engineering

Examples of catalytic reactions

Characteristics of catalytic reactions

Steps in catalytic reactions:

St. Joseph’s College of Engineering 9 Chemical Engineering

Solid Catalyzed Reactions

Characteristics of solid catalyst:

Promoters and Inhibitors

St. Joseph’s College of Engineering 10 Chemical Engineering

 The slow decrease in activity is due to chemisorption of reactants, products or impurities

St. Joseph’s College of Engineering 11 Chemical Engineering

Unit II - HETEROGENEOUS REACTORS

Catalytic type heterogeneous reactions

Non-Catalytic heterogeneous reactions

Rate equations for heterogeneous reactions

 At steady state condition, the reaction consists of series steps

St. Joseph’s College of Engineering 13 Chemical Engineering

Rate controlling step or rate limiting step

 The rate of reaction based on unit surface area of B

St. Joseph’s College of Engineering 14 Chemical Engineering

k g (CAg - CAs ) = k"CAs

The overall rate of reaction

 For steps in series r1 = r2 = roverall

Contacting patterns for Two-phase systems

St. Joseph’s College of Engineering 15 Chemical Engineering

 Physical adsorption (Physisorption, weak van der waals force)

Difference b/w Physisorption and Chemisorption

Parameter Physisorption Chemisorption

The various adsorption isotherms are;

St. Joseph’s College of Engineering 16 Chemical Engineering

 Temkin isotherm {C = (k1Cm) ln(P) + (k1Cm)ln(k2)}

Derivations of the Langmuir Adsorption Equation

St. Joseph’s College of Engineering 17 Chemical Engineering

Alternate form of Langmuir Adsorption Equation

Limitations of Langmuir Adsorption Equation

St. Joseph’s College of Engineering 18 Chemical Engineering