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Chemical Reactors

ICE 306 – Process Equipments
Department of Chemical Engineering Faculty of Industrial Technology Parahyangan Catholic University April 2011

Homogenous Heterogeneous Chemical Biochemical Reversible Irreversible

Constant Density Variable density

Classification of Reactions

Elementary Non-elementary

Isothermal Nonisothermal Single Multiple

Exothermic Endothermic Catalytic Noncatalytic

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Type of Reactors

Single Phase Batch Semi Batch Plug Flow CSTR

Multi Phase Fixed Bed Moving Bed Fluidized Bed Trickle Bed Rotary,Bubble

Special Reactor Membrane Reactor Reactive Distillation electrochemical, bioreactor,etc..

Batch Reactors
Batch reactors : Reactants charged into a vessel at beginning of the operation, products are discharged at end of the operation operation. . are the and the

The chemical reactions take place over time time. . The vessel is usually agitated to provide good contacting between the reactants and to create uniform conditions conditions. .
Uzi Mann_Principles_of_Chemical_Reactor_Analysis_and_Design__New_Tools_for_Industrial_Chemical_Reactor_Operations

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Batch Reactors
The use of batch reactors in commercial processes is usually most suitable for small volume production, particularly for situations in which switching from one process or product to another is required, as in the manufacture of pharmaceuticals. pharmaceuticals. Typically, in such processes, the value of the products is relatively large compared with the cost of production production. . It may be used for large volume production (with multiple units in parallel) such as the production of “vinyl” (polyvinyl chloride or PVC) involving suspension polymerization, and of emulsion emulsion-polymerized latex latex. .
Missen- Introduction to Chemical Reaction Engineering & Kinetics

Batch Reactors
The advantages : • Simple in construction, • Small instrumentation and cost, • Flexibility of operation. The disadvantages : • Inherent downtime (filling,heating, discharging and cleaning) between batches • High maintenance cost. • Unsteady State operations Difficult to control heat transfer and product quality.
Kayode Coker- Modeling of Chemical Kinetics and Reactor Design

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Batch Reactors

Semi Batch Reactors
Semibatch reactor : A tank in which one reactant is charged initially and another reactant is added continuously during the operation operation. . The reactor has no outlet stream.

Uzi Mann_Principles_of_Chemical_Reactor_Analysis_and_Design__New_Tools_for_Industrial_Chemical_Reactor_Operations

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Semi Batch Reactors
This mode of operation is applied for for: : - improving improving the selectivity of the desirable product by maintain maintaining ing one reactant (the injected reactant) at low concentration. concentration . - controlling the heat generated during reactions reactions. . It is usually used for gas gas-liquid reaction of the type A(g) + B(l) products, Reactant A is dispersed (bubbled) continuously through a batch of reactant B; Example is an aerobic fermentation in which air (or 0,) is supplied continuously to a liquid substrate (e.g., a batch of culture, as in penicillin production).
Missen- Introduction to Chemical Reaction Engineering & Kinetics

Semi Batch Reactors

Kayode Coker- Modeling of Chemical Kinetics and Reactor Design

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Continuous Reactors
Continuous reactor : A vessel into which reactants are fed continuously and products are withdrawn continuously from it. Chemical reactions take place over space (the reactor volume), and the residence time of the reacting fluid in the reactor provides the required reaction time.

(a) tubular, (b) Continuous stirred tank reactors (c) CSTR in series

Uzi Mann_Principles_of_Chemical_Reactor_Analysis_and_Design__New_Tools_for_Industrial_Chemical_Reactor_Operations

Continuous Stirred Tank Reactor (CSTR)
As in the case of a batch reactor for commercial operation, a CSTR is normally used for a liquid liquidphase reaction. In the laboratory, it may also be used for a gasgasphase reaction for experimental measurements, particularly for a solidsolid-catalyzed reaction reaction. . The operation is normally one of steadysteady-state, except for startup, shutdown and operational disturbances or upsets, in which cases unsteadyunsteadystate operation has to be taken into account.
Missen- Introduction to Chemical Reaction Engineering & Kinetics

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Continuous Stirred Tank Reactor (CSTR)
The advantages : - Steady State operations: It is easy to maintain good temperature control with a CSTR. - It can be readily adapted for automatic control in general, allowing fast response to changes in operating conditions (e.g., feed rate and concentration); The disadvantages : - The conversion of reactant per volume of reactor is the smallest of the flow reactors CSTR in Series -This is not desirable for safety reasons if the reactants or products are particularly hazardous.
Missen- Introduction to Chemical Reaction Engineering & Kinetics

Heat transfer of CSTR

Chemical Process Design and Integration - R. Smith 2nd. Ed

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Plug Flow Tubular Reactor
A plugplug-flow reactor (PFR) may be used for both liquid liquid-phase and gasgas -phase reactions reactions. . The reactor itself may consist of an empty tube or vessel, or it may contain packing bed of particles particles. .
Missen- Introduction to Chemical Reaction Engineering & Kinetics

Plug Flow Tubular Reactor
The tubular plug flow reactor is relatively easy to maintain with no moving parts, and it usually produces the highest conversion per reactor volume of any of the flow reactors reactors. . One mechanical advantage is when high pressure is required. Under highhigh-pressure conditions ,a small smalldiameter cylinder requires a thinner wall than a large largediameter cylinder. The principal disadvantage of the tubular reactor is the difficulty in controlling the temperature within the reactor.
Kayode Coker- Modeling of Chemical Kinetics and Reactor Design Chemical Process Design and Integration - R. Smith 2nd. Ed

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Multiphase Reactors
LiquidLiquid-Liquid and GasGas-Liquid: Spray column, bubble column,membrane reactor,emulsion reactor LiquidLiquid-Gas and Solid Liquid : Slurry,fixed bed,moving bed,fluidized bed,rotary kiln reactor Three phase : Trickle bed, Membrane reactor
Chemical Process Design and Integration - R. Smith 2nd. Ed

Fixed Bed Reactor
A vessel filled with catalytic pellets and the reacting fluid passing through the void space between them. Relatively large pellets (e.g., larger than 1 cm) are used to avoid excessive pressure drop and higher operating cost. In general, heat transfer to/from large large-scale packedpacked-bed reactors is a challenge.
Uzi Mann_Principles_of_Chemical_Reactor_Analysis_and_Design__New_Tools_for_Industrial_Chemical_Reactor_Operations

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Characteristics of Fixed Bed Reactors
(1) The catalyst are held in place and do not move, (2) Reaction occurs only within the catalyst particles, (3) Reaction in bulk fluid is approximately zero.

Uzi Mann_Principles_of_Chemical_Reactor_Analysis_and_Design__New_Tools_for_Industrial_Chemical_Reactor_Operations

Fixed Bed Reactors

Catalytic

Non-Catalytic

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The Importance and Scale of Fixed Bed Catalytic Processes
The discovery of solid catalysts and their application to chemical processes in the early years of this century has led to the breakthrough of chemical industry. industry . Since these days, this industry has diversified and grown in a spectacular way, through the development of new or established processes, mostly based on the use of solid catalysts catalysts. . Today fixed bed reactors are mainly large capacity units units. .
Packed-bed reactor. (Schematic and photograph courtesy of Sasol/Sastech PT Limited.)

Heat transfer of fixed bed catalytic reactor

‘Hot spots’: undesired reactions and catalyst degradation. • Catalyst dilution (inert solid). • Multi-tubular. Not recommended when frequent catalyst regeneration is required
Chemical Process Design and Integration - R. Smith 2nd. Ed

Alternatives:

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Heat transfer of fixed bed catalytic reactor

Walas- Chemical Process Equipments

Heat transfer of fixed bed catalytic reactor
The main reactions for production of methanol from Syn Gas are: CO + H2 CO2 + H2  CH3OH CO + H2O

The temperature profiles between two configurations are different : For tubular reactor, the profile is seen to be relatively smooth. By contrast with the tubular reactor, the coldshot reactor experiences significant temperature fluctuations. Such fluctuations can, under some circumstances, cause accidental catalyst overheating and shorten catalyst life.
Chemical Process Design and Integration - R. Smith 2nd. Ed

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Some Applications of FBR

Technological Innovations in FBR
The introduction of better materials of construction where the use of centrifugal cast 25% CrCr-20% Ni steel tubes has enabled increasing the operating temperature and consequently the throughput. Better design of reactor internals (e.g., in phthalic anhydride synthesis), improving the rate and uniformity of heat removal by molten salts. More adequate shop techniques and increased shipping clearance, permitting the construction of multitubular reactors of large diameters containing up to 20,000 tubes.

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Technological Innovations in FBR
Modification of auxiliary equipment (e.g., the introduction of centrifugal compressors) boosted the capacity of wellwell-established processes like ammonia and methanol synthesis. Modification of flow pattern (e.g.. the use of radial flow reactors in catalytic reforming and ammonia synthesis) to reduce the pressure drop and thus enhance the recycle compressor capacity. The use of small catalyst particles in regions where heat transfer matters and larger particles in other zones to limit the pressure drop, as in primary steam reformers. The design of improved control schemes.

Multibed adiabatic reactors with endothermic reactions

Multibed adiabatic reactors for Catalytic Reforming

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Multibed adiabatic reactors with exothermic reactions

Multi-bed adiabatic reactor for ammonia synthesis

Multitubular adiabatic reactors with exothermic reactions

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Multitubular adiabatic reactors with endothermic reactions

Radial Flow Reactors

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Fixed Bed Non Catalytic Reactor
Fixed Fixed-bed noncatalytic reactors can be used to for GasGas-Solid or Liquid Liquid-Solid reaction For GasGas-Solid example, hydrogen sulfide can be removed from fuel gases by reaction with ferric oxide: Fe2O3 + 3 H2S Fe2S3 + 3 H2O 2 Fe2S3 + 3 O2 2Fe2O3 + 6 S

Chemical Process Design and Integration - R. Smith 2nd. Ed

Fixed Bed Non Catalytic Reactor
For Gas Gas-Liquid example, hydrogen sulfide and carbon dioxide can be removed from natural gas by reaction with monoethanolamine in an absorber : For H2S : HOCH2CH2NH2+ H2S  HOCH2CH2NH3HS For CO2 : HOCH2CH2NH2+ CO2 

HOCH2CH2NH3HCO3

Chemical Process Design and Integration - R. Smith 2nd. Ed

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Moving Bed Reactors
Moving Moving-bed reactor : A vessel where solid particles (either reactant or catalyst) are continuously fed and withdrawn. The gas flow is maintained to allow the downward movement of the particles.

Moving Bed Reactors

Moving Bed Catalytic Cracker

Moving Bed Reactor for direct oxidation of N2

Walas- Chemical Process Equipments

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Fluidized Bed Reactors
Fluidized Fluidized-bed reactor : A vessel filled with fine particles (e.g., smaller than 500 mm) that are suspended by the upward flowing fluid. The fluidized bed provides good mixing of the particles and, consequently, a uniform temperature.

Fluidized Bed Reactors
Fluidized bed reactors have now also found use in exothermic processes requiring close temperature control. - the oxidation of naphthalene into phthalic anhydride - the ammoxidation of propylene into acrylonitrile - the oxychlorination of ethylene into ethylene dichloride → The high turbulence created in the fluidfluid-solid mixture leads to much higher heat transfer coefficients than those which can be obtained in fixed beds.

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Fluidizing Phenomena

Fluidizing Phenomena

ut

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Fast Fluized Bed Reactors
In a fastfast-fluidized bed, the fluidization velocity is very high, resulting in significant entrainment of solid particles particles. . Therefore, continuous addition of fresh solid particles may be required for some operations operations. . Applications of fast fast-fluidized beds are in fluidizedfluidized-bed combustion and FischerFischer-Tropsch synthesis of hydrocarbons from CO and H2
Fast fluidized bed reactor

Pneumatic transport reactor
In this type, fluid velocities are considerably greater than the terminal velocities of the particles, so that virtually all of the particles are entrained entrained. . The vessel may be extremely tall, with no solid recirculation (e. (e.g., coal combustion) or it may provide for solid recirculation with external cyclones cyclones. . The process stream is extremely dilute in solid particles because of the high volume of gas passing through the “bed “bed. .” pellets pellets. .

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Problems on Fixed Bed Reactors for Catalytic Cracking
Catalytic cracking deposits carbonaceous products on the catalyst → rapid deactivation of the catalyst. catalyst. To maintain production capacity, the coke had to be burned off This regeneration required switching the reactor out of production. In order to eliminate the cycling, attempts were made to circulate the catalyst and burn off the coke in a separate vessel, the regenerator.

Catalytic Cracking of Gasoil for the Production of Gasoline
The catalyst containing 1 or 2 wt% coke is regenerated with air around 580 ° C, reducing the coke to 0.4 to 0.8 wt%.

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Recent Version of Catalytic Cracker
Catalysts are so active that the cracking mainly took place in the riser. To avoid over-cracking of the gasoline a very rapid separation of the products and the catalyst is required and this is achieved by means of a cyclone.

Application of Fluidized Bed Reactors
Petroleum applications
Gasolines, Aviation Fuel ,Diesel Feedstocks ,Jet Fuel Feedstocks ,Propane Butane, Propylene,Butylene ; Isobutane ,Cracked Naptha ,Gasoline from Methanol, Fuel Oils from Polyethylene

Petrochemical applications
Acetone Recovery ,Aniline, Aniline from Nitrobenzene ,Ethanol from Butadiene ,Polyethylene, Hydrogen from Steam Coal Gasification, Styrenes from Hydrocarbons, Cracking of Methylcyclohexane, Maleic Anhydride Maleic Anhydride from Benzene and Butylenes Vinyl Chloride , Vulcanization of Rubber

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Advantages and Disadvantages
The advantages of the fluidized bed are:
• Savings in operating expenses due to heat recovery in the reaction regeneration steps. • Rapid mixing of reactants-solids and high heat transfer rates. • Easy to control both the heat transfer and the fluid flow system.

The disadvantages are: • Inefficient contacting due to solids movement and the bypassing
of solids by bubbles. • Possible channeling, slugging, and attrition of catalyst. • Possible agglomeration and sintering of fine particles in the dilute phase under certain conditions (e.g., high temperature).

Slugging

Slugging occurs when the bubble size equals the tube diameter. Slugging can be avoided by reducing the height/diameter ratio.

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Channeling
Channeling occurs when the fluid has preferential paths through the reactor and may be avoided by a better distributor and by increasing the height-to-diameter ratio. A rule of thumb says that the pressure drop over the distributor should be at least one tenth of the pressure drop over the bed.

Bubble Column Reactors
Bubbling column reactor : A vessel filled with a liquid reactant and a gas reactant, fed from the bottom, moves upward in the form of bubbles. bubbles. The liquid reactant is fed from the top and withdrawn from the bottom bottom. . The gaseous reactant is absorbed in the liquid reactant, and the reaction takes place in the liquid phase. phase.

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Bubble Column Reactors
An important example of bubble column reactors is in partial oxidation of pp-xylene to make terephthalic acid, a monomer for polyester (PET), p-xylene + +02 02 terephthalic acid In partial oxidation such as these the reaction occurs homogeneously (in the liquid phase, and the desired product remains in the liquid phase, where it is separated from the other organic) organic).

Bubble Column Reactors

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Bubble Column Reactors

Spray Column Reactor
In this reactor, the liquid is sprayed from the top and force the gas to rise. In combustion of liquid oils such as heavy diesel fuels, the fuel is sprayed through nozzles into air.

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Rotary Kiln Reactors
Rotary reactors or rotary kilns are the reactors facilitating the chemical reaction between the gas and/or and/or solid phases usually at high temperatures. temperatures. In a rotary reactor, transformation of solids takes place within a rotating layer of solids while gas flows along the surface of the solids layer layer. .

Rotary Kiln Reactors

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Three Phase Reactors

Trickle Bed Reactors
In th this is reactor, the liquid and gas flow co co-currently over the fixed bed of catalyst particles particles. . An external pump sometimes is used instead of the builtbuilt-in impeller shown. Such units were developed for the liquefaction of coal oal. .

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Application of Trickle Bed Reactors

Slurry Reactor
It is a multiphase flow reactor where the the reactant gas is bubbled through a solution containing solid catalyst particles particles. . Temperature control is quite simple simple. . Catalyst activity can be maintained by small addition of catalyst

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Application of Slurry Reactors

Membrane Reactors

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Membrane Reactors

A membrane reactor is really just a plug-flow reactor that contains an additional cylinder of some porous/membrane material within it. Membrane reactors combine reaction with separation to increase conversion. Membrane reactors are commonly used in dehydrogenation ,hydrogenation or partial oxydation reactions.
Fogler , Elements of Chemical Reaction Engineering

Membrane Reactors

Sanchez Marcano, Catalytic Membranes and Membrane Reactors

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Membrane Reactors

Sanchez Marcano, Catalytic Membranes and Membrane Reactors

Membrane Reactors

(a)
CH4

(b)

(a) Partial Oxydation of Methane (b) Dehydrogenation of Ethane

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Reactive Distillation

Reactive Distillation
Reactive distillation is used with reversible, liquid phase reactions. For many revesible reactions the equilibrium point lies far to the left and little product is formed : However, if one or more of the products are removed more of the product will be formed because of Le Chatlier's Principle :

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Reactive Distillation
Benefits of reactive distillation include:
Increased speed and improved efficiency Lower costs – reduced equipment use, energy use and handling Less waste and fewer byproducts Improved product quality – chemicals are exposed to heat only once, reducing opportunity for degradation

Reactive Distillation
Reactive distillation can be used with a wide variety of chemistries,including the following following: :
Acetylation; Aldol condensation; Alkylation Amination;Dehydration;Esterification Etherification;Hydrolysis;Isomerization Oligomerization;Transesterification

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Fuel Cell
A fuel cell → an electrochemical reactor that converts hydrogen and oxygen to produce electricity, with water and heat as its by byproduct. product.

Fuel Cell

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Proton Exchange MembraneMembrane-FC

Fuel Cell Applications

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References
1. Chemical Process Equipments – Stanley M Walas 2. Allbright’s Chemical Engineering Hand Book 3. Perry’s Chemical Engineering Hand Book 4. Chemical Reactor Design and Analysis – Froment & Bischoff 5. Elements of Chemical Reaction Engineering - Scott Fogler H 6. Chemical Reaction Engineering - Octave Levenspiel 7. Introduction to Chemical Reaction Engineering & Kinetics, Ronald W. Missen Missen, , Charles A. Mims, Bradley A. Saville 8. The Engineering of Chemical Reactions – Lanny D. Schmidt 9. Chemical Reactor Design, Optimization and Scaleup – E. Bruce Nauman

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