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REACTORS AND

CATALYSTS

Reactors

Where a reaction takes place Ideal reactors:

Batch reactor

Continuous reactors

CSTR

PFR & PBR

Industrial reactors:

Liquid phase reactions

Gas phase reactions

Liquid phase reactions

CSTR, semi-batch/ batch reactor, slurry reactor

Semi-batch reactor:

Good temperature control by regulating feed rate

Capability of minimizing unwanted side reactions (through maintaining low

concentration of one of the reactants)

Two-phase reactions like gas is bubbled through liquid

CSTR:

Intense agitation

Good temperature distribution because it is well agitated

Conversion of reactant per volume is very small; requires large volume reactors (disadvantage)

Cascade of CSTRs provide high conversion

Most of homogeneous liquid phase flow reactors are CSTRs

Eg. Manufacture of Nitrobenzene from Benzene requires a cascade of CSTRs

CSTR

CSTR

CSTR

Gas phase reactions Tubular reactors (PFR, PBR)

Tubular reactors

Easy to maintain (no moving parts)

High conversion per reactor volume (in PFR) / per catalysts weight (in PBR)

Difficult to control temperature within the reactor, hot spots for exothermic reaction

Most of homogeneous Gas phase flow reactors are PFRs

Fixed bed reactor (PBR) packed with solid catalysts

Common catalytic reactors

Fluidized bed reactors

Heterogeneous reactions

Analogous to the CSTR (well mixed, so good temperature

distribution)

Handle large amounts of feed and solids

Good temperature control

Temperature is uniformly throughout (no hot spots)

Ease of catalyst replacement or catalyst regeneration (by sending catalyst to nearby regenerating equipment)

Circulating fluidized bed reactor for FTS

Circulating fluidized bed reactor for FTS

Fixed bed reactors

Plug flow for gases

Hot spots in exothermic reactions (can ruin the catalysts)

Eg: Hydrodemethylation of toluene to produce benzne

Plugging if small catalyst particles are used which create pressure drop

small catalyst particles are used which create pressure drop • Staged adiabatic packed bed reactor (proper

Staged adiabatic packed bed reactor (proper interchange of heat and proper gas flow

Staged packed bed with intercooling

Fixed bed reactor for FTS

Fixed bed reactor for FTS

Slurry reactor

Multiphase reactor (reaction between gas and liquid takes place on a solid catalyst)

Catalyst is suspended in the liquid and gas is bubbled through the liquid

Ideal situations: liquid phase is well mixed, catalysts are uniformly distributed, gas phase is in plug flow

Liquid phase may be a reactant (hydrogenation of methyl linoleate) or inert (FTS)

Liquid phase act as a sink for exothermic reaction

Good temperature control

Heat recovery is possible

Constant overall catalytic activity maintained easily by addition of small amount of

catalyst

Useful for catalysts that can't be pelletized

Large heat capacity of reactor acts as a safety feature against explosions Disadvantages

Reactor may plug up

Uncertainties in design process

Finding suitable liquids may be difficult

Higher ratio of liquid to catalyst than in other reactors

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/Slurry/Slurry.html

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/Slurry/Slurry.html

Trickle bed reactor

Multiphase reactor

Gas and liquid flow co-currently on a packed bed of catalyst particles

Trickle bed reactor • Multiphase reactor • Gas and liquid flow co-currently on a packed bed

Catalysis

Catalysis is the change in rate of a chemical reaction due to

the participation of a substance called a catalyst.

A catalyst is not consumed by the reaction itself

A catalyst may participate in multiple chemical transformations

Catalysts that speed the reaction are called positive catalysts

and that slow a reaction is called negative catalysts

Though the catalysts speed up a reaction, it never determines the equilibrium or endpoint of a reaction. This is governed by thermodynamics alone

According to transition theory, the catalysts reduces the potential energy barrier over which the reactants must pass

to form products

 Action of solid catalysts: the reactant molecules are changed, energized or affected to form

Action of solid catalysts: the reactant molecules are changed, energized or affected to form intermediates in the

regions close to the catalyst surface

Typical catalysts materials

The chemical nature of catalysts is as diverse as catalysis itself

Proton acids are probably the most widely used catalysts, especially for the many reactions involving water, including hydrolysis and its reverse

Multifunctional solids often are catalytically active, e.g.zeolite,

alumina, higher-order oxides, graphitic carbon, nanoparticles,

Transition metals are often used to catalyze redox reactions (oxidation, hydrogenation). Examples are Ni, Co, V.

Many catalytic processes, especially those used in organic synthesis,

requires noble metals such as Pt, Pd, Rh, Ru, Au

Typical petrochemical catalysts

Supported noble metals: Pt, Pd, Rh, Ru, Re, Pt-Re

Supported transition metals: Ni, Co, Fe, Cu, Mo

Catalyst supports: Al 2 O 3 , SiO 2 , TiO 2 , Activated Carbon, zeolites,

Raney type metal catalyst: Ni, Cu-Ni

Oxide catalysts:Cr 2 O 3 , Fe 2 O 3 , Al 2 O 3 -Cr 2 O 3 , Fe 2 O 3 - K 2 CO 3 -Cr 2 O 3 , Ca 3 Ni(PO 4 ) 3 ,Bi 2 O 3 MoO 3

Sulfides catalysts: MoS 2 /Al 2 O 3 , WS 2 /Al 2 O 3 , NiS/Al 2 O 3 , CoS/Al 2 O 3

Micro- and mesoporous materials

Catalyst classification

Metal catalyst on supported systems

Molecular sieve catalyst

Preparation of metals on support

For the effective utilization of the metal

The principal catalyst-preparation technique involves two stages.

First, rendering a metal-salt component into a finely divided form on a

support (dispersion) and secondly; conversion of the supported metal salt to a metallic or oxide state (thermal treatment)

Dispersion techniques may be impregnation, adsorption from solution,

co-precipation, or deposition

Thermal treatment may be calcination (inert atmosphere) or reduction (active atmosphere)

Impregnation is achieved by filling the pores of a support with a

solution of the metal salt from which the solvent is subsequently

evaporated. The catalyst is prepared either by spraying the support with a solution of the metal compound or by adding the support material to a solution of a suitable metal salt, such that the required weight of the

active component is incorporated into the support without the use of

excess of solution. This is then followed by drying and subsequent

decomposition of the salt at an elevated temperature. This technique has been widely used for the preparation of small amounts of catalyst for

basic studies.

Adsorption is defined as the selective removal of metal salts or metal

ion species from their solution by a process of either physisorption or chemical bonding with active sites on the support. Depending upon the

strength of adsorption of the adsorbing species, the concentration of the

active material through the catalyst particle may be varied and

controlled. This technique is widely used in the preparation of industrial catalysts as it permits a greater degree of control over the dispersion and distribution of the active species on the support.

Co- precipitation: The preparation of supported catalysts by the co-

precipitation of metal ions with the support ions usually produces an intimate mixing of catalysts and support. An example of this technique is the co-precipitation of metal ions with aluminium ions to produce a

precipitated alumina gel containing the metal hydroxide. This precipitate

when calcined produces a refractory support with active component dispersed throughout the bulk as well as at the surface.

Chemical Vapour Deposition (CVD): It is the vapour plating of the support with a volatile inorganic or organometallic compound. The process requires only a moderate vacuum and is currently one of the

methods under research in industry as a means of preparing catalysts

with a purely surface deposition.

Thermal treatment :

Calcination :

To get metal oxides as catalyst

In the presence of inert gases such as nitrogen, helium

Reduction :

To get metal as catalyst In the presence of reducing gases such as Hydrogen

Multifunctional solids/Porous

solids/Molecular sieve catalysts

Porous solids with pores of the size of molecular dimensions 0.3 to 2 nm

Eg: zeolites (crystalline), carbon (amorphous), glasses, oxides, aluminosilicates

Nowadays mesoporous materials (2 to 50 nm pore size) also use as

catalysts

Zeolite catalysts

Crystalline and uniform pore size

Most commercial molecular sieve catalyst

The high concentration of ionic hydrogen atoms (H + ) attached to oxygen atom framework is another key feature for zeolite catalyst

Different types of zeolites - named according to the framework eg: ZSM-5 medium pore size (0.45 to 0.6 nm dia) formed by ten ring, zeolite X, Y large pores (~ 0.8 nm) by 12 ring

• ZSM-5 catalysts ZSM-5 has some unique features for its catalyst activity towards cracking and

ZSM-5 catalysts

ZSM-5 has some unique features for its catalyst activity towards cracking and aromatization

Pore structure

Well defined three dimensional intersecting channel system, medium pore size, and high diffusivity for hydrocarbons

Acidity

strong acid sites, the easiness for their availability (acid sites lie on the

intercrystalline surface), high silica-alumina ratio (Si/Al 10 to 100)

surface), high silica-alumina ratio (Si/Al – 10 to 100) Crystal structure of zeolite ZSM-5 (a) building

Crystal structure of zeolite ZSM-5 (a)

building unit, (b) chain, (c) sheets, (d) three

dimensional channel structure

Catalyst deactivation

Catalyst loose its activity due to:

Sintering or crystal growth of the active material

Fouling of the active surface with involatile reaction by-products

Poisoning of the active surface by feed impurities

Blockage of the support pore structure

Sintering (aging)

Structural modification

Loss of catalyst activity or loss of active surface area

Resulted from the prolonged exposure to high temperature

Eg. Reforming of heptane over Pt/Al 2 O 3 Catalyst deactivation due to sintering

exposure to high temperature • Eg. Reforming of heptane over Pt/Al 2 O 3 Catalyst deactivation

Fouling

Coke deposition on the surface of the catalyst

Common for reactions involving hydrocarbons

Coking can be reduced by running the reaction at elevated pressure and hydrogen rich streams

Usually regenerated by burning off the carbon

by running the reaction at elevated pressure and hydrogen rich streams • Usually regenerated by burning
by running the reaction at elevated pressure and hydrogen rich streams • Usually regenerated by burning

Poisoning

Poisoning molecules irreversibly chemisorbed to active sites, reducing the number of active sites available for reaction

Poisoning molecule may be reactant, product or any other impurity in

the feed

may be reactant, product or any other impurity in the feed • Blockage • Molecules having

Blockage

Molecules having size larger than the pore diameter block the entry of

smaller molecules into the pores

Larger molecules may be reactant or product

Eg: formation of PAH inside the pores of ZSM-5 during aromatization

reactions