Unit II – GAS-SOLID NON-CATALYTIC REACTORS

 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

1. Solid particles contain large amount of inert material which remain as a non-flaking ash or
2. 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

Kinetic models

The closest representation of reality which can be treated without too many mathematical complexities

 The progressive-conversion model

 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 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 in to 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

 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.

The above eqn. is the unreacted core shrinks with time

For complete conversion

Fractional Conversion determination

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 eqn.(5) represents the conditions of a reacting particle at any time
The above eqn. relates the radius of unreacted core with time when the diffusion through
ash layer controls the overall reaction rate.

For complete conversion

The above eqn. gives an idea regarding the progress of reaction in terms of the time
required for complete conversion.

Fractional conversion determination

Chemical reaction controls
 For complete conversion

Fractional conversion determination

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 reaction, finally disappearing.

The following 3 steps during this reaction

 Diffusion of reactant A from the main body of gas through the gas film to the solid surface
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 ain
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

Chemical reaction controls

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

This relationship is referred to as the Froessling correlation

Stokes Regime Small particles

For complete conversion

Fractional conversion determination

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)

Diffusion through gas film controls

Chemical reaction controls

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 vary along the length 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.

Semi batch 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

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 treated in unit time.
 Since the density of solid may change during reaction, F is defined as the volumetric feed rate of
solid in the general case.
 Where density change of the solid is negligible, F can represent the mass feed rate of solid as well

 Let F(R,) be the quantity of material of size about Ri fed to the reactor.
 If R, 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.
 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 its
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

Chemical reaction controls

Diffusion through Ash layer controls