Reactor Types and Their Industrial Applications
SEAN MORAN, Expertise Limited, United Kingdom
KLAUS-DIETER HENKEL, Buna AG, Schkopau, Germany
1. Introduction . . . . . . . . . . . . . . . . .
2. Basic Types of Reactors . . . . . . . . .
3. Survey of Commercially Important
Reactor Types . . . . . . . . . . . . . . . .
3.1. Reactors for Gas-Phase Reactions .
3.2. Reactors for Liquid-Phase Reactions
3.3. Reactors for Gas–Liquid Reactions.
3.4. Reactors for Solid-Catalyzed
Reactions . . . . . . . . . . . . . . . . . . .
3.4.1. Reactors for Heterogeneous Gas
Catalysis . . . . . . . . . . . . . . . . . . . .
3.4.2. Reactors for Liquid-Phase and Gas-
Liquid Reactions over Solid Catalysts
3.5. Reactors for Noncatalytic Reactions
Involving Solids . . . . . . . . . . . . . . .
3.5.1. Reactors for Noncatalytic Gas–Solid
Reactions . . . . . . . . . . . . . . . . . . . .
1. Introduction
The reactor in which chemical reactions take
place occupies a central position in the concep-
tion of a process plant, though it may not always
be physically central in the plant layout.
Upstream of the reactor are the process steps
which prepare the reactor feedstock for reaction,
involving physical treatment of the material
streams, as well as their conveyance, heat trans-
fer, mixing and purification operations. Down-
stream of the reactor there is usually at least one
separation process, recovering the product of the
reaction.
Frequently, there is a recycle of unreacted
feed chemicals from the separation stage to the
reactor inlet, for economical and environmental
reasons.
The reactor provides the time necessary for the
reaction to occur by retaining reactants for a
sufficient period. It also contains any catalysts
required for the reaction to take place, though not
all reactors use catalysts to facilitate reactions.
 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.b04_087.pub2
1 3.5.2. Reactors for Noncatalytic Liquid–
2 Solid Reactions. . . . . . . . . . . . . . . . 32
3.5.3. Reactors for Noncatalytic Solid-Phase
4 Reactions . . . . . . . . . . . . . . . . . . . . 32
4 3.6. Electrothermal Reactors. . . . . . . . . 32
4 3.7. Reactors for Electrochemical
7 Processes. . . . . . . . . . . . . . . . . . . . 35
3.8. Reactors for Biochemical Processes 43
7 3.9. Reactors for Photochemical and
Radiochemical Processes . . . . . . . . 43
16 3.9.1. Photochemical Reactors . . . . . . . . . . 54
3.9.2. Radiochemical Reactors . . . . . . . . . . 54
26 List of Abbreviations . . . . . . . . . . . 54
References. . . . . . . . . . . . . . . . . . . 54
28
29
Whether catalysts are used or not, the condi-
tions required to overcome the activation thresh-
old of each partial reaction are also supplied in
the reactor, and the proper temperature and
concentration are maintained.
The most important reaction-related factors
for the design of a reactor are
1. The activation principle selected, together
with the states of matter of the reactants
and the resulting number and types of phases
involved.
2. The concentration and temperature depen-
dence of the chemical reactions.
3. The heat of the reactions taking place.
The most important activation principles for
a reaction mixture include
1. Activation by addition of heat
2. Catalytic activation
3. Activation by decomposition of an initiator
2 Reactor Types and Their Industrial Applications
4. Electrochemical activation
5. Biological activation (actually a subset of 2.)
Less important options for activation are
electromagnetic energy such as visible or ultra-
violet light, or ionizing radiation.
With regard to phase relationships in the
reaction space, various combinations are possi-
ble. The reactants and reaction products can be
present (or be produced) in various phases.
Furthermore, inert diluents or heat-transfer
media can be present in different phases.
Finally, the catalyst, which is generally in the
solid or liquid phase, often has to be taken into
consideration.
The (negative or positive) heat of the reactions
taking place in a reactor influences the extent and
nature of provisions for heat transfer. Exother-
mic or endothermic reactions frequently require
the supply or removal of large quantities of heat.
Thermally neutral reactions involve considerably
less technical sophistication.
The concentration and temperature depen-
dences of a chemical reaction are described by
the reaction kinetics. In practice, most reaction
systems are complex and include parallel,
sequential, and equilibrium reactions.
To obtain the optimal yield of desired prod-
uct under these conditions, the temperature and
pressure must be maintained within certain
ranges. The temperature must also be controlled
along the reaction path, and a defined residence-
time distribution in the reactor must be
achieved.
If, in addition, mass or energy are to be
transferred from one phase to another, appro-
priate transport conditions have to be main-
tained. When catalysts are used, catalyst loss
due to aging and poisoning must be considered
by the designer. These factors impose complex
requirements that must be kept in mind when
designing a reactor.
Against the requirements established by the
chemistry, the designer must balance costs of
fabrication, consumption of materials, and oper-
ational reliability. In practice, many options
are often available for engineering a chemical
process and, in all such cases, design decisions
must depend on an assessment of the overall
process as well as commercial constraints on
the plant.
2. Basic Types of Reactors
(→ Model Reactors and Their Design
Equations)
A variety of reactor designs are used in industry,
but all of them can be assigned to certain basic
types or combinations of these. The basic theo-
retical models are as follows (see → Principles
of Chemical Reaction Engineering):
1. Batch stirred-tank reactor
2. Continuous stirred-tank reactor
3. Tubular reactor
These theoretical types of reactor are also
referred to as “ideal” reactors, which form the
basis of mathematical models differing in flow
and thermal conditions (→ Computational Fluid
Dynamics).
With respect to flow conditions, the ideal
stirred-tank batch reactor is characterized by
complete mixing on microscopic and macro-
scopic scales. In the ideal tubular reactor, plug
flow is assumed, i.e., no mixing occurs in the
direction of flow (axial mixing), but perfect mix-
ing takes place in the radial direction. Thus, as in
the batch stirred-tank reactor, all particles expe-
rience a well-defined residence time.
In contrast, the continuous stirred-tank
reactor has a very broad residence-time distri-
bution (→ Principles of Chemical Reaction
Engineering). The ideal mathematical analysis
is based on the assumption of a reaction system
that is homogeneous as regards the phase, such
that transport resistance between phases does
not occur.
The thermally ideal operating states are the
perfectly isothermal and adiabatic states, i.e.,
either very intensive heat exchange with the
surroundings or no exchange at all is assumed.
However, in practice, there are no ideal
reactors. Real stirred-tank reactors have less
than perfect mixing, and real plug flow reactors
have some axial mixing. In practical operation,
the ideal states are achieved only approximately.
Examples of typical non-idealities include:
1. The formation of real flow patterns, such as
dead zones, short-circuit flows, and channeling
2. Transport processes in the individual phases,
such as axial back mixing
 Reactor Types and Their Industrial Applications
3. The formation of concentration and temper-
ature profiles as a result of transport resist-
ances in and between phases
4. Segregation processes
5. Incomplete mixing of reactants
The essential advantages and disadvantages
of the three basic reactor types are discussed in
the following sections.
Batch Stirred Tank (→ Stirred Tank
Reactors)
Principal Applications:
1. Liquid-phase reactions
2. Liquid-solid reactions
Advantages:
1. Quick production changeover possible, mak-
ing them suitable for substances produced on
a small scale
2. Flexibility: Multiple uses possible from a
single plant
3. Certain process steps upstream or down-
stream of the reaction can also be performed
in the reactor
4. Well-defined residence time
5. Hygiene: Equipment is now available at
bench and small-scale production level which
incorporates single-use disposable contact
surfaces, e.g., plastic bags
Disadvantages:
1. Relatively high operating costs due to long
downtimes and high manpower requirements
2. Relatively high capital costs due to low
equipment utilization
3. Quality differences between charges because
reaction conditions are only partly reproducible
4. Limited temperature control capabilities,
especially with highly endothermic or exo-
thermic reactions
Continuous Stirred Tank (→ Model Reactors
and Their Design Equations, Chapter 3.
Continuous Stirred-Tank Reactors)
Principal Applications:
1. Liquid-phase reactions
3
2. Gas–liquid reactions
3. Gas–liquid reactions over suspended
catalysts
Advantages:
1. Low operating costs, especially at high
throughputs
2. Low capital costs. Reactors are smaller due
to high utilization
3. Consistent product quality due to reproduc-
ible process conditions
4. Wide range of throughput
Disadvantages:
1. Final conversions lower than in other basic
reactor types because of complete mixing
(i.e., unreacted starting materials can get into
the product stream)
2. Inflexible. Changeover to other products
generally complex and time-consuming
because of reaction-specific design
Tubular Reactor (→ Tubular Plug Flow
Reactors)
Principal Applications:
1. Homogeneous gas-phase reactions
2. Liquid-phase reactions
3. Gas- and liquid-phase reactions over solid
catalysts (→ Catalytic Fixed-Bed Reactors)
4. Gas–liquid reactions
Advantages:
1. Favorable conditions for temperature control
by heat supply or removal
2. No moving mechanical parts, hence espe-
cially suitable for high-pressure service
Disadvantages:
1. Very high degree of specialization, often with
complicated design and high investment costs
2. Relatively large pressure drops, giving high
running costs
Reactors are often interconnected to make up
for the drawbacks of a single reactor, especially
to adapt reaction conditions during scale-up to
4 Reactor Types and Their Industrial Applications
full capacity, as well as to optimize conversion
and yield. Partial reactors can be combined in a
single apparatus or connected in a system of
reactors; these partial reactors may differ in
shape and size.
Types of interconnections are series, parallel,
and recycle.
Series Connection:
1. Multibed reactors
2. Tower reactors, reaction columns
3. Cascades of stirred tanks (→ Stirred Tank
Reactors)
4. Multiple-hearth reactors (→ Metallurgical
Furnaces)
5. Different reactor types connected in series
(e.g., stirred tank and tubular reactor)
Parallel Connection: Multitubular reactors
Recycle Connection: Loop reactors (→ Loop
Reactors).
Complicated reactor designs result, espe-
cially when different reactor types are combined
in a single apparatus. At the same time, such a
combination offers maximum adaptability to the
requirements of a given reaction process.
The designer of a completely novel process
must examine every case individually to ensure
that the results justify the very high development
and investment costs for such special reactors.
The vast majority of designs are not, how-
ever, completely novel, so this is not the way in
which most design proceeds. Process designers
select from the range of well-developed and
characterized reactor types or, for more novel
processes, they would procure reactor types
developed by specialists.
Many processes are dependent on the effi-
ciency of reaction vessels for overall process
efficiency, and engineers are risk averse. They
incorporate no more novelty than is absolutely
necessary.
The following survey of real reactors includes
these special types of reactor designs only when
their utility extends beyond a single case.
3. Survey of Commercially
Important Reactor Types
The phase relationships in the reaction space are
crucial in the design of reactors for catalytic,
thermal, and polymerization processes and
accordingly form the top-level classification fea-
ture for such reactors. Since many different com-
binations of phases within a reactor are possible,
the survey is based only on the state of the
reactants at the inlet to the reactor or
the beginning of the reaction and the phase of
the reaction site (catalyst phase, liquid phase with
dissolved reactant). Reaction products that form
additional phases and inert substances of all types
(except for solvents, as just noted) are ignored.
Reactors used in electrothermal, electro-
chemical, biochemical, photochemical, and
radiochemical processes are treated separately.
Reactor types for which no industrial applica-
tion is currently known are not listed.
3.1. Reactors for Gas-Phase Reactions
Homogeneous gas-phase reactions utilized in
industry are generally characterized by large
positive or negative enthalpies of reaction and
high reaction temperatures. To minimize
undesirable reactions and the byproducts they
produce, residence times must usually be very
short. A high reaction temperature can be main-
tained in some cases using heat provided by
burning part of the feed.
Tables 1 and 2 describe the various types of
reactors used for gas phase reactions as well as
their practical applications.
3.2. Reactors for Liquid-Phase
Reactions
In general, liquid-phase reactions are exother-
mic. In the case of multiphase systems, intensive
mass and heat transfer must be provided for; this
is possible only in reactors with intense mixing,
such as stirred tanks. Along with a number of
other reaction types, nearly all industrially
important polymerization reactions take place
in the liquid phase.
The essential feature of polymerization
reactions is that, in contrast to other liquid-phase
reactions, the viscosity increases rapidly during
the course of reaction and causes difficulties in
heat and mass transport. In industry, this prob-
lem is countered by (1) the use of special stirring
and kneading devices; (2) running the process in
several stages; (3) raising the temperature as the
 Reactor Types and Their Industrial Applications 5

Table 1. Reactors for exothermic gas-phase reactions

Reactor type Diagram Features Examples of applications

Burner  for high reaction rates  combustion of H2S to SO2 (Claus vessel)
a1  very high reaction  carbon black production (furnace, gas,
temperatures thermal carbon black processes)
 explosion limits must be  chlorine–hydrogen reaction
a2 
taken into consideration chlorination of methane
 nitration of propane

c b

c
Tubular reactor  well-defined residence time (tubes up  chlorination
c to 1000 m long)  of methane
 intermediate injection  of propene to allyl chloride
a
possible  of butadiene to dichlorobutane
 pressure drops  chlorolysis of chlorinated
 good temperature control hydrocarbons
capability

c
Reactor with recycle  suitable for low reaction rates  chlorination of methane
c  good mixing cooling inside or outside
reactor

d
a

b
Fluidized-bed  nearly isothermal conditions because  chlorination
reactor
b heat transport is very efficient  of methane
  of 1,2-dichloroethane to
b+e intensive mixing
tri- and perchloroethylene
 chlorolysis of chlorinated
e hydrocarbons
c
c

a
Figure legend: a) Gaseous reaction mixture; a1, a2) Gaseous feed components; b) Gaseous product; c) Coolant; d) Partial stream of product;
e) Catalyst
6 Reactor Types and Their Industrial Applications

Table 2. Reactors for endothermic gas-phase reactions

Reactor type Diagram Features Examples of applications

Burner  very high reaction temperatures  Sachsse–Bartholomé process for acetylene

a attainable by partial combustion production
b of reactants  high-pressure gasification for synthesis
 short residence times gas production (Texaco, Shell)
a

Reformer  high reaction temperatures  steam cracking of naphtha and other

g attainable mainly by radiation hydrocarbons to ethylene
d  well-defined residence times  vinyl chloride production by cleavage of
b
dichloroethane
m 
i pyrolysis
c  of acetic acid to ketene
 of 2-methyl-2-pentene to isoprene
(in presence of HBr)
 of chlorodifluoromethane to
tetrafluoroethylene

Fluidized-bed reactor  heat supplied along with solids  Lurgi Sandcracker

e
d

b+f e

a+f

Moving-bed reactor  heat supplied along with solids  Langer– Mond process for production of
g  continuous removal of solid ultrapure nickel
products
c+h k
f
d
j
b
h

Reactor with fixed bed of  fixed bed ensures heat storage  Kureha process for acetylene and ethylene
inerts
d and intensive mixing production
 production of CS2 from CH4 and sulfur
vapor

c b
 Reactor Types and Their Industrial Applications
Table 2. (Continued )
Reactor type Diagram
Regenerative furnaces
d 
g no dilution by heat-transfer
k l j l
b
c
a
Figure legend: a) Oxygen or air; b) Hydrocarbon; c) Fuel gas; d) Product; e) Heat-transfer medium; f) Steam; g) Flue gas; h) Air; i) Quench;
j) Reaction section; k) Regeneration section; l) Catalyst; m) Convection zone
conversion increases; and (4) carrying out
polymerization in thin films.
For the sake of completeness, some impor-
tant nonliquid phase polymerization reactions
are included in this section, even though they do
not fall under liquid-phase reactions according
to the classification principle stated above.
These are, in particular, “gas-phase polymeriza-
tion” reactions, some of which take place over
solid complex catalysts of the Ziegler–Natta
type (high-density polyethylene, linear low-
density polyethylene, and polypropylene).
Table 3 summarizes the types of reactors
used in industry for liquid-phase reactions and
Table 4 some special reactor designs for polym-
erization reactions.
3.3. Reactors for Gas–Liquid Reactions
Gas–liquid reactions are the basis of many
industrially important processes, such as oxida-
tion, alkylation, chlorination, and scrubbing.
The prerequisite for an efficient reaction is rapid
mass transport between gas and liquid phases.
Important criteria for assessment include
1. The interfacial area
2. The mass or volume ratio of gas to liquid
3. The energy required to mix the phases
4. The concentrations of reactants
Other important factors are temperature con-
trol, heat transfer, and residence time (especially
that of the liquid phase).
7
Features Examples of applications
 battery operation  gas generation from heavy crudes
medium
Reactor design is dictated largely by the way
in which the liquid/gas interface is generated.
The following methods are used:
1. Reactors with a continuous liquid-phase and
fixed gas distribution devices such as bubble
columns (→ Bubble Columns), packed and
tray reactors (→ Reaction Columns)
2. Reactors with mechanical gas dispersion
such as sparged and/or stirred tanks
3. Reactors with continuous gas phase and
liquid dispersing devices e.g., spray reactors
and liquid-ring pumps
4. Thin-film reactors (→ Thin-Film Reactors)
Table 5 illustrates reactor types for gas-liquid
reactions as well as their commercially impor-
tant applications.
3.4. Reactors for Solid-Catalyzed
Reactions
Heterogeneous catalytic processes play a major
role in traditional chemical engineering,
because many key products and intermediates
can be manufactured in this way (→ Heteroge-
neous Catalysis and Solid Catalysts, 3. Indus-
trial Applications). Fluid or dissolved reactants
react in the presence of a solid catalyst, the
mechanism as a whole consisting of the reaction
proper and a series of upstream and downstream
transport steps.
8 Reactor Types and Their Industrial Applications

Table 3. Reactors for liquid-phase reactions (one or more phases present)

Reactor type Diagram Features Examples of applications

Tubular reactor  well-defined residence time  polymerization reactions

d  good temperature control  bulk polymerization to LDPE
capabilities  polycondensation to PA 66 (2nd
a stage)
 hydrolysis reactions
 of ethylene oxide and propylene
oxide to glycols
 of chlorobenzene to phenol and
chlorotoluene to cresol
 of allyl chloride

b  production of
 ethyl acetate from acetaldehyde
 isopropanolamine
 dehydrochlorination of 1,1,2-
d
trichloroethane to vinylidene
chloride
Reformer  high reaction temperature  visbreaking
b  well-defined residence time  delayed coking

n pyrolytic dehydrochlorination of
tetrachloroethane to
a p trichloroethylene
 high-pressure gasification of
q
heavy crudes
o

Multitubular reactor See Table 4  large heat-transfer area  bulk polymerization to PS, HIPS,
 multistage design with stirring and SAN
elements between stages is
possible
Sulzer mixer –  mixing elements consist of tubes  bulk polymerization to PS and
reactor (plug-flow
b carrying heat-transfer medium polyacrylates
configuration)  large heat-transfer area  temperature-controlled starch
 suitable for processes in which conversion
c/d
viscosity increases
 intensive radial mixing with little
axial backmixing
 very narrow residence-time
distribution

c/d

a
 Reactor Types and Their Industrial Applications 9

Table 3. (Continued )

Reactor type Diagram Features Examples of applications

Reactor with external  good mixing and heat-removal  cleavage of cumene hydro-
recirculation
a conditions peroxide to phenol and
 no moving parts acetone (2nd stage
 suitable for low reaction rates of Hock process)
 heat exchanger can be placed  Beckmann rearrangement of
outside reactor cyclohexanone oxime to
d caprolactam
 production of hydroxylamine
sulfate (Raschig process)
 production of phosphoric acid
d
(wet process)
 saponification of allyl
i chloride
 bulk polymerization to PS, HIPS,
SAN, and PMMA
b

Reactor with internal  very intensive mixing  production of melamine from

recirculation molten urea (high-pressure
b process)
 production of aromatic nitro
compounds
 production of adipic acid from
cyclohexanol and nitric acid
 bulk polymerization to PS, HIPS,
and SAN

Loop reactor See Table 4  for slurry polymerization  polymerization reactions

 suspension is circulated at
high velocity to prevent
buildup
Powder-bed reactor See Table 4  liquid monomers supported on
already polymerized granules
 for high conversion
 evaporating and condensing
monomer acts as heat-transfer
agent (boiling, cooling)
 vertical and horizontal
designs
 slurry polymerization to PP
 production of HDPE and LLDPE
 polymerization reactions
 polymerization to HDPE
and PP
 block copolymerization
to PE–PP

Stirred tank, batch or  limited heat-transport capability  pharmaceutical production

semicontinuous
a  mechanical stirring means  bulk polymerization to PS,
 suitable for slow reactions PMMA,
 HIPS, ABS (1st stage of
c c each process)
 polycondensation to PA 66
 solution polymerization to
g PVAC, PAN, PE, PP, EPM,
EPDM, SB, SB–S,
EO–PO
 polycondensation to UF, MF,
PF resins
 precipitation polymerization to
b PVC, PAN, PE, PP, EPM,
EPDM∗

(continued )
10 Reactor Types and Their Industrial Applications

Table 3. (Continued )

Reactor type Diagram Features Examples of applications

Stirred tank, as above  suitable for fast reactions with
continuous large negative or positive heat of
reaction approximately complete
mixing conversion generally not
complete mechanical stirring
means
 suspension polymerization
to PVC, EPS,
PMMA, PVAC∗, and
ion-exchange resins
based on PS, HIPS,
ABS (2nd stage)
 production of aromatic nitro
compounds
 sulfonation of benzene
 esterification of PA and alcohol
to diphthalates
 bulk and solution polymerization
to PS, PMMA, HIPS, and ABS
(1st stage in each case);
copolymers with nonazeotropic
monomer ratios
 precipitation polymerization
to PAN, IIR, PE, PP
 emulsion polymerization to PVC
and SAN
 esterification
 of acrylic acid with alcohol
 of acetic acid with ethanol
 dehydration
 of 1,4-butanediol to
tetrahydrofuran
 of ethanol to diethyl ether
 saponification
 of benzyl chloride
 of fatty acids
 dehydrochlorination
 of 3,4-dichloro-1-
butene to chloroprene
 of 1,1,2-trichloroethane
to vinylidene chloride
 cyclization of glycols to
1,4-dioxane
 nitration of aliphatic
hydrocarbons
 alkylation of isobutane with n-
butenes
 production of melamine
from molten urea
(Montecatini)
 oxidation
 of cyclohexanone/ol
with HNO3 to adipic acid
 of mono- to dicarboxylic acids
 of allyl alcohol with H2O2 to
glycerol
 Reactor Types and Their Industrial Applications 11

Table 3. (Continued )

Reactor type Diagram Features Examples of applications

Cascade of stirred  suitable for slow reactions  polymerization reactions

tanks
a adaptable to needed reaction  transesterification of
conditions stage by stage DMT∗ to DGT∗
residence-time distribution  polycondensation to
c c
close to that of tubular reactor PET and PBT solution
 polymerization to BR, IR, UP,
UF, MF, PF resins
c c  solution or precipitation
polymerization to PE, PP, EPM,
EPDM
 emulsion polymerization to
c c SBR, CR, NBR
 production of hydroxylamine
sulfate (Raschig process)
 production of cyclohexanone
b oxime from cyclohexanol
and hydroxylammonium sulfate
 nitration of aromatic
hydrocarbons
 decomposition of ammonium
carbamate to urea
 production of plasticizers from
phthalic anhydride and alcohol
 production of MDA in
conjunction with downstream
tubular reactor
 production of methacrylamide
from acetocyanohydrin
 production of MDI from MDA∗
and TDI from TDA
Reaction column  reaction and separation in a single  aldol condensation
c apparatus of n-butanal to
f
a  equilibrium can be modified by 2-ethylhexenal
l removing one or more compo-  saponification
c nents from reaction space  of chloropropanol
with milk of lime
 of fatty acids
h  esterification
 of acetic acid with butanol
k e
 of phthalic anhydride
m
with alcohols
 decomposition
 of amalgam
d  of ammonium carbamate
i to urea and water

b d

(continued )
12 Reactor Types and Their Industrial Applications

Table 3. (Continued )

Reactor type Diagram Features Examples of applications

Multichamber tank  virtually identical to cascade of  polymerization to LDPE (ICI)

stirred tanks  alkylation of isoparaffins with
 requires little space olefins (Kellogg)
a  chamber-by-chamber feed
injection possible

Fluidized-bed reactor  very good heat- and mass-  polymerization to HDPE,

transport conditions LLDPE, PP
b  fluid coking of heavy residual
oils (Exxon)
 melamine production
j from molten urea

a
Spray reactor  direct heating in hot stream of gas  thermal H2SO4 cleavage
a  production of MgO
from MgCl2 (spray
calcination)

b
Falling-film reactor  gentle temperature control due to  sulfation of fatty alcohols
a1 large heat-transfer area  diazotization of aromatic amines
 diazo coupling
a2
c c

b
Figure legend: a) Liquid reaction mixture; a1, a2) Liquid feed components; b) Liquid product; c) Coolant; d) Heating agent; e) Water; f) Organic
phase and water; g) Baffle; h) Organic phase; i) Partial stream of product; j) Catalyst; k) Reaction mixture from preceding reaction stage; l) Water
from preceding stage; m) Packing; n) Off-gas; o) Fuel gas for burners; p) Quench; q) Convection zone; r) Mixing element consisting of tubes
carrying heat-transfer medium; s) Mixing elements rotated 90°
 Reactor Types and Their Industrial Applications 13

Table 4. Special reactor designs for polymerization reactions

Reactor type Diagram Features Examples of applications

Multitubular reactor  large heat-transfer area  bulk polymerization to

a  multistage design with PS, HIPS, and SAN
stirring elements between
stages is possible

c
c

b
Multistage multitubular  high complexity  various polymers
reactor with interstage a  high cost
stirring

b
Reactor with external  heat exchangers in external loop  alkylation of
recycle (multitubular or
d  mixing elements can be  ortho-toluidine with
a b
screw-conveyor type) included ethylene
 suitable for continuous and  phenol with isobutene
batch processes  air oxidation of liquid
c
c hydrocarbons

c
c
f

e
d
a
(continued )
14 Reactor Types and Their Industrial Applications

Table 4. (Continued )

Reactor type Diagram Features Examples of applications

Reactor with external  various polymers

recycle (annular)
c b a c

c c

d e
c c
a
c c
Reactor with internal  various polymers
recirculation

a
Sulzer loop reactor  plug flow gives high conversion  production of
rates  polystyrene
g  high surface area per unit  styrenic copolymers
volume  poly(methyl
methacrylate)
g g h  polyethylene
 silicone polymers
 polypropylene
d  polyamide
e  terpene resins
 polyoxymethylene
b
a  biodegradable polymers
e
Loop reactor  for slurry polymerization  slurry polymerization
 suspension is circulated at to PP
high velocity to prevent  production of HDPE and
buildup LLDPE
a1

a2

b
 Reactor Types and Their Industrial Applications 15

Table 4. (Continued )

Reactor type Diagram Features Examples of applications

Tower reactor  for continuous processes  bulk and solution polym-

b  section-by-section erization of PS, HIPS,
temperature control ABS, SAN, PA 6
c possible
 little backmixing at high
viscosity
c  also in cascade or with
c
upstream stirred tank
c
c

c
c
c
c

Ring-and-disk reactor  narrow residence-time distribution  final stage in production of

PET and PBT

Extruder  for highly viscous media  polymerization reactions

a  production of POM from
trioxane
 final stage in production
of PA 66

Powder-bed reactor  liquid monomers supported on  polymerization reactions

already polymerized granules  polymerization to HDPE
b
 for high conversion and PP
 evaporating and condensing  block copolymerization
monomer acts as heat-transfer to PE–PP
o agent (boiling, cooling)
 vertical and horizontal
designs

(continued )
16 Reactor Types and Their Industrial Applications

Table 4. (Continued )

Reactor type Diagram Features Examples of applications

Mixing head  special design for bringing several  production of PUR

j liquid reactants together
i

a1 a2

b
Belt reactor with mixing  especially for highly viscous media  polymerization to PAN,
head i l PAC, PVC, PVAC
a1 a2

m b

Spinning jet with  uses lower temperatures than other  production of acrylic and
coagulating bath b fiber spinning techniques other fibers

n
n

Figure legend: a) Polymerization mixture; a1, a2) Feed components; b) Polymerization product; c) Coolant; d) Static mixer; e) Pump; f) Screw-
conveyor design for viscous media; g) Sulzer mixer–reactor; h) Sulzer mixer–reactors in plug-flow configuration; i) Air; j) Plunger; k) Nozzle;
l) Mixing head; m) Belt reactor; n) Spinning bath; o) Packed bed of polymer granules

3.4.1. Reactors for Heterogeneous Gas Fixed-bed reactors can be classified by their
Catalysis type of temperature control:

Reactors with a fixed catalyst bed are distin-
guished from those with moving catalyst.
Fixed-Bed Reactors (→ Catalytic Fixed-Bed
Reactors). The characteristic design features of
a reactor with fixed catalyst are the pressure
drop of the gas flowing through the catalyst bed
and the avoidance of unstable operation points,
especially with strongly exothermic reactions,
when flow through the catalyst bed becomes
nonuniform. Fixed-bed reactors must be shut
down after a certain time of operation to regen-
erate or replace the catalyst.
1. Reactors with no special temperature control
features (adiabatic operation)
2. Reactor systems with stagewise temperature
control (chiefly for equilibrium reactions)
3. Reactors with continuous heat exchange
along the flow path (polytropic operation)
Fixed-bed reactors without equipment for
temperature control are marked by a particu-
larly simple construction and low flow resist-
ance, which makes them suitable for high gas
throughputs. A summary of these reactors
appears in Table 6.
 Reactor Types and Their Industrial Applications 17

Table 5. Reactors for gas – liquid reactions

Reactor Diagram Features Examples of

type applications

Tubular  large transfer areas can be  production of

reactor c provided adiponitrile from
with  temperature can be adipic acid
injector controlled by and ammonia
b indirect transfer  production of
 well-defined nitroaniline by
residence time amidation of
 little back chloronitrobenzene
mixing  oxidation of
a
a ethylene to
acetaldehyde
(2nd stage)
Bubble  can be equipped with  oxidation of
column
d internal draft tube or ethylene to
external recirculation acetaldehyde
a  simple design  toluene to
•• •
•• •• •••••
 practically isothermal benzoic acid
•• • • • • c conditions can be cyclohexane to
• ••• • • • •
• ••••••••• •
achieved by cyclohexanone/ol
evaporation of  acetaldehyde to
b a liquid component acetic acid and
 limited temperature and acetic anhydride
pressure ranges  cumene to
 suitable for cumene
continuous and hydroperoxide
semicontinuous operation  para-xylene to
 high backmixing dimethyl
in liquid phase terephthalate
(1st stage) butane
to acetic acid
 butene to ketones
 propane to acetone
 copper chlorides to
copper oxychlorides
 alkylation of benzene
with ethylene
and propene
 epoxidation of
propene with
organic
hydroperoxides
(Halcon)
 hydroformylation
of propene (oxo
synthesis)
 chlorination of
benzene to
chlorobenzene
 decarboxylation of
benzoic acid to
phenol
 ethylene to 1,2-
dichloroethane
 alkalis to
hypochlorites
 1,2-dichloro-
ethane or vinyl
chloride
to 1,1,2-
trichloroethane
(continued )
18 Reactor Types and Their Industrial Applications

Table 5. (Continued )

Reactor Diagram Features Examples of

type applications
 production of
acrylic acid or
acrylates from
acetylene,
CO2, water
or alcohol
 production of
vinyl ether
from acetylene
and alcohol
 carboxylation of
methanol to acetic
acid
 production of
methylpyridine
from ethylene
and ammonia
 hydrolysis of
trichloroethylene to
monochloroacetic
acid
 hydration of
acetylene
to acetaldehyde
 production of
propionic acid
from ethylene, CO2
and water (Reppe
process)
Liquid-ring  combines  production of
pump
a+b c+d compression, absorption acetic anhydride
and reaction from acetic acid
and ketene

Sparged  continuous and  oxidation of

d 
stirred b a semi-continuous operation para-xylene to
tank possible terephthalic acid
 stirrer shaft must be sealed (Amoco process)
 much backmixing in both  ethylene to

• • • phases acetaldehyde
• •• • • •  external liquid  propene to

• • • •• • recirculation can be acetic acid

•
• • •• • • added  benzoic acid to
• phenol
•  cyclohexane to
cyclohexanone/ol
 toluene to
benzaldehyde
c  butane to methyl
ethyl ketone
 cyclohexanol to
adipic acid
 acetaldehyde to
acetic anhydride
 Reactor Types and Their Industrial Applications 19

Table 5. (Continued )

Reactor Diagram Features Examples of

type applications
 alkylation of ben-
zene with ethylene
 chlorination of
aromatics
 hydrogenation
of natural fats
to fatty acids
or their esters
 acetylation of
carboxylic acids to
vinyl ethers
 production of pure
SO2 from liquid
sulfur and SO3
Cascade of  narrower residence time  epoxidation of
a d
stirred b distribution than single propene with
tanks tank organic
hydroperoxides
(Halcon)
f • 
• •• • • • • hydrolysis of fats
• •
• •• • • • • •
f
• •• • • • ••• •• • • •
• •• • •
to fatty acids and
•
• • • •• • f f f f

glycerol
production of
phthalic acid
(Progil)
c

Reaction  tray or packed column  oxidation of ethyl-

column
d design benzene, cumene,
 combination of isobutane
reaction and to their hydroper-
separation permits oxides (1st stage of
a control of Halcon process)
e equilibrium  absorption of
 cocurrent or  nitrogen oxides
countercurrent operation in nitric acid
e production
 ammonia and
b
CO2 in soda
production
 gases in scrubbers
 chlorination of
c  ethylene to 1,2-
dichloroethane
 acetylene to
tetrachloroethane
 trichloroethylene
to perchloro-
ethylene
 hydrochlorination
of ethylene to
chloroethane
 precipitation of
NaHCO3 in soda
production
 high temperature
debromination of
salt brines
 production of
(continued )
20 Reactor Types and Their Industrial Applications

Table 5. (Continued )

Reactor Diagram Features Examples of

type applications
 alkyl and dialkyl
sulfates
 phthalimide from
phthalic anhydride
 ammonium nitrate
from NO3 and
NH3
 sulfonic acids
(benzene-, chloro
sulfonic acids)
 chloropropanols
from propene,
chlorine and water
Spray  suitable for high gas  gas treatment and
reactor
a throughputs and high gas off-gas scrubbing
(jet side solids transport  production of
scrubber) b resistance acetic anhydride
 very large from acetic acid
interfacial areas and ketene
 production of
H3PO4 (Knapsack
process)
 acid refining of
lubricants
c  hydrolysis of
dichloro-
methylsilane
 production of
potassium
hyperoxide
by contacting of
liquid potassium
with air
Falling film  gentle temperature control  sulfonation of
reactor d due to large heat transfer dodecylbenzene,
area fatty alcohols
a and olefins

b c

Rotary kiln  for reaction of molten sol-  oxidation of

a ids with gases  sodium to sodium
peroxide (two-
d stage process)
 molten sulfur to

b SO2

c g

Figure legend: a) Liquid feed component; b) Gaseous feed component; c) Liquid product; d) Off-gas; e) Packing; f) Heating agent or coolant;
g) Drive unit; h) Catalyst; i) Reaction mixer with mixing nozzle; j) Pump; k) Heat exchanger; l) Gas separator; m) Sulzer mixer–reactor; n) Static
mixer

Table 6. Fixed-bed catalytic reactors for gas-phase reactions with no special provisions for temperature control
Reactor type Diagram
Simple fixed-bed reactor
(axial flow) path
upstream of primary
reformer propionic acid
Fixed-bed reactor with
combustion zone
Radial-flow reactor
(→ Radial-Flow
Packed-Bed Reactors)
Shallow-bed reactor
j 
i
Reactor Types and Their Industrial Applications 21
Features Examples of applications
a  very simple design not  reforming (platforming,
suitable for reactions Rheniforming, etc.)
with large positive or  hydrotreating
negative heat of  CO converting
reaction and high  amination of methanol
temperature sensitivity to methylamines
c  desulfurization and methanation
in synthesis-gas hydrogenation
of nitrobenzene to aniline
(Allied, Bayer)
 production of vinyl propionates
b from acetylene and isomerization
of n-alkanes
 dehydrogenation of
ethylbenzene to styrene
 disproportionation of toluene
to benzene and xylene
e  direct heating by  methane cleavage in secondary
d combustion of part of reformer
l hydrocarbon feed
m
c
b
a  much lower pressure  ammonia synthesis (Topsoe,
drop than axial-flow Kellogg)
reactor  dehydrogenation of ethylbenzene
 multistage to styrene (Dow)
configuration  reforming
possible
 enhanced backmixing
c due to small thickness
of bed
 uniformity of flow
requires exact sizing of
distributing and
b collecting ducts
a  used for high reaction  oxidation of ammonia to NOx
rates and unstable  oxidative dehydrogenation of
products methanol to formaldehyde
 very short residence  production of hydrocyanic acid from
time ammonia, methane, and air
c  catalyst can also be in (Andrussow process)
gauze form
suitable for
k autothermal operation
b
(continued )
22 Reactor Types and Their Industrial Applications
Table 6. (Continued )
Reactor type Diagram
Regenerative furnace
e 
d supplied by catalyst
h regeneration
c g
b
f
Figure legend: a) Gaseous reaction mixture; b) Gaseous product; c) Catalyst; d) Air; e) Hydrocarbon; f) Flue gas; g) Reaction section;
h) Regeneration section; i) Condensate; j) Steam; k) Steam generator; l) Burner; m) Inert guard bed
Reactor systems with stagewise temperature
control are used primarily for equilibrium
reactions. Such a reactor consists of simple
adiabatic reactor elements connected in series
and can take the form of several separate units or
a system housed in a common reactor shell.
Temperature control is accomplished by heat
transfer between reactor stages or by the injec-
tion of temperature-controlled gas or vapor
streams at points along the flow path. Table 7
presents reactor systems of this type along with
their commercially important applications.
If the reaction process imposes special
requirements on temperature control, heat-
transfer surfaces must be located throughout
the reactor volume. The best-known design
for such a reactor is the multitubular reactor,
which is frequently used in the chemical indus-
try. The drawbacks relative to other fixed-bed
reactors include the much more complicated
design and the limitation on throughput due
to the smaller cross-sectional area available
for flow.
Temperature control is achieved by the use of
gaseous and liquid heat-transfer media. One
highly effective approach is the use of boiling
liquids (e.g., pressurized water and evapora-
tively cooled reactors). A special case is the
autothermal process regime, in which the
reaction mixture itself is used as a temperature
control medium before it flows through the
catalyst bed. Fixed-bed reactors with continuous
heat exchange are described in Table 8, along
with applications.
Features Examples of applications
 suitable when catalyst  dehydrogenation of butane to
ages rapidly and can be butadiene (Houdry process)
regenerated by burning SO2 reduction with methane
off (Andrussow process)
 reaction heat can be
c  battery operation
Moving-Bed and Fluidized-Bed Reactors
(→ Fluidized-Bed Reactors). In moving-bed
reactors, transport of the catalyst is influenced
by gravity and the drag force exerted by the
flowing reaction fluid on the catalyst particles.
The flow regime in the reactor can vary widely,
depending on the ratio of these forces. The follow-
ing features must be taken into consideration when
designing and specifying reactors of this type:
1. The possibility of continuous catalyst
regeneration
2. Increased mechanical loads on the catalyst
and reactor materials
3. The favorable conditions for heat and mass
transport resulting from rapid movement of
solids and small catalyst grain size
Table 9 lists moving bed reactor types and
significant applications.
3.4.2. Reactors for Liquid-Phase and Gas–
Liquid Reactions over Solid Catalysts
Fixed-bed reactors such as trickle-flow reactors
(→ Three-Phase Trickle-Bed Reactors) and
packed bubble columns (→ Bubble Columns)
are used for liquid-phase reactions, as well as gas-
liquid reactions over solid catalysts. The presence
of a liquid phase, however, leads to much greater
drag and friction forces on the catalyst.
If the reaction involves both gas and liquid
phases, maintenance of uniform flow conditions
through the catalyst bed and intensive mixing of
the phases can be difficult.

Table 7. Fixed-bed catalytic reactors for gas-phase reactions with stage-wise temperature control
Reactor type
Cascade of fixed-bed reactors
Multibed reactor with cold-gas
or steam injection
Multibed reactor with
interstage cooling
Multibed reactor with heat
supply
Figure legend: a) Gaseous reaction mixture; b) Gaseous product; c) Catalyst; d) Heating agent; e) Cold gas; f) Coolant
Reactor Types and Their Industrial Applications 23
Diagram Features Examples of applications
a  large pressure and temperature differ-  reforming of heavy gasoline
ences are possible  hydrocracking
 conversion of H2S and SO2
to elemental sulfur (Claus
c c c process)
 isomerization of five-to-
six-ring naphthenes
d d
b
d d
 used for exothermic equilibrium  ammonia synthesis
a 
reactions methanol synthesis
 injection of reaction mixture leads to  hydrocracking
lower conversion and thus increased  hydrogenation of benzene
number of stages  desulfurization of vacuum
c  injection of water lowers concentration gas oil
at constant conversion
 adaptation of bed depth to progress of
c reaction
e
b
a  used for exothermic equilibrium  ammonia synthesis (ÖSW,
reactions Fauser, Montecatini)
 internal or external heat exchangers  SO2 oxidation (with interstage
 no dilution effects adsorption)
c  adaptation of bed depth to progress of  hydrodealkylation of
reaction alkyl aromatics
f f
b
a  used for endothermic equilibrium  dehydrogenation of ethylben-
reactions zene to styrene (Dow)
 interstage heating or interstage injection
f of superheated steam
c
c f f
c
f
24 Reactor Types and Their Industrial Applications

Table 8. Fixed-bed catalytic reactors for gas-phase reactions with continuous temperature control

Reactor type Diagram Features Examples of applications

Multitubular reactor  temperature control with liquid  oxidation of

a gaseous or boiling heat transfer  ethylene to ethylene oxide
agent is shell side space  ortho-xylene or naphthalene
 relatively expensive design to phthalic anhydride
 high cost and long downtime  propene to acrolein or
c for catalyst replacement acrylic acid
 internals in shell-side space  acrolein to acrylic acid
to improve heat transfer  methanol to formaldehyde
 distribution devices needed for stream (formox process)
d of reaction gas in large reactors  naphthalene to 1,4-
 relatively large pressure drop napthoquinone
 autothermal processing  ethanol to acetaldehyde
c possible  alkylation of
 benzene with ethylene
or propene to ethylbenzene,
diethylbenzene or cumene
(Mobil, Badger
b
processes)
 ammonia synthesis
(TVA, NEC processes)
 hydrogenation of
 CO2 to methanol
 phenol to
cyclohexanone/ol
 natural fats to fatty acids
 dehydrogenation of
 ethylbenzene to styrene
 diethylbenzene to
divinylbenzene
 cyclohexanol to
cyclohexanone
 2-butanol to methyl ethyl
ketone
 ethanol to acetaldehyde
 hydration of propene to
isopropanol
 dehydration of
 phenylmethylcarbinol to
styrene
 acetic acid to acetic
anhydride
 ethanol to diethyl ether
 oxychlorination of ethylene
to ethylene dichloride
(Stauffer process)
 production of vinyl
acetate from acetic acid
and ethylene or acetylene
 production of methyl
tert-butyl ether from
methanol and isobutene
(1st stage)
 hydrochlorination of
 acetylene to vinyl
chloride
 ethanol or methanol to
chloroethane or
chloromethane

Table 8. (Continued )
Reactor type Diagram
Tubular reformer
j
a
b
Fixed-bed reactor
g
with heating or
cooling elements f pressure conditions
a 
d classical examples are Fischer-Tropsch
e
d
d b
f
Figure legend: a) Gaseous reaction mixture; b) Gaseous product; c) Heating agent or coolant; d) Catalyst; e) Cooling tubes; f) Circulating water;
g) Steam; h) Tube sheet; i) Fuel gas for burners; j) Off-gas
The crucial factor for the efficiency of cata-
lytic processes is the wetting of the catalyst by
the liquid. Since reactors of this type are usually
operated adiabatically, local overheating may be
a danger with exothermic reactions. Fixed-bed
reactors are well suited to high-pressure pro-
cesses by virtue of their simple design.
Suspension Reactors. A second important
group are suspension reactors, in which very
fine catalyst particles are distributed throughout
the volume of the liquid (e.g., stirred tanks (→
Stirred Tank Reactors) and bubble columns (→
Bubble Columns) with suspended catalyst).
Because transport resistances are reduced, these
reactors offer a close approach to isothermal
operating conditions and a favorable utilization
of the catalyst volume.
Reactor Types and Their Industrial Applications 25
Features Examples of applications
 direct heating of catalyst tubes  primary reformer
 for endothermic reactions and high reaction
temperatures
 advantageous when only the heating or  methanol synthesis (Linde
cooling system has to be designed to special isothermal reactor)
reactor and butadiene reactor of four stage
process
Sophisticated separation techniques may be
required to separate the finely divided catalyst
from the liquid in the outgoing stream from the
reactor. This arrangement, however, permits
continuous catalyst replacement. Equipment
for this purpose can be installed inside or out-
side the reactor. All suspension reactors have
the disadvantage of increased backmixing, espe-
cially of the liquid phase, which can affect
product purity.
The fluidized-bed reactor (→ Fluidized-Bed
Reactors) differs from the suspension reactor in
the use of coarser catalyst particles and the
formation of a well-defined agitated catalyst
bed below the liquid level.
Industrially important reactors for liquid-
phase and gas–liquid reactions over solid cata-
lysts are listed, together with their applications,
in Tables 10 and 11.
26 Reactor Types and Their Industrial Applications
Table 9. Moving-bed catalytic reactors for gas-phase reactions
Reactor type Diagram Features
Moving-bed reactor  gravity transport of catalyst
 reaction conditions largely
e similar to those in fixed-
h bed reactor
d
 advantageous when catalyst can
f be regenerated by burning
b off residues
a g
Fluidized-bed reactor  catalyst agitated by gravity
b and resistance force of
b+c gas flow
 almost isothermal
conditions can be achieved
c c in fluidized bed
 pressure drop independent
of gas throughput over
a wide range
 form of fluidized bed can be
varied as a function of
geometric and hydraulic
c 
conditions
 strong backmixing internals
to improve mass transport
a 
and heat transfer are common
 catalysts must have high
abrasion resistance
Examples of applications
 cracking (TCC, Houdry
flow process)
 dehydrogenation of
butane
 cracking (Kellogg, FFC,
Flexicracking)
 hydrocracking
 reforming
 ammoxidation
 of propene to acrylonitrile
(Sohio process)
 of ortho-xylene to
ortho-phthalodinitrile
 production of adiponitrile
from adipic acid and
ammonia
oxychlorination of ethylene
to 1,2-dichloroethane
(Goodrich)
production of melamine
from urea (BASF)
 hydrogenation
 of nitrobenzene to
aniline (BASF, Cyanamid)
 of ethylene
 oxidation
 of ortho-xylene or naphthalene
to phthalic anhyride
 of butane to MA∗
(Du Pont)
 of SO2 to SO3
 of ethylene to
ethylene oxide
 of NH3 to NO
 of HCl to chlorine
 dehydrogenation
 of isopropanol
 of n-butane to n-butene
 production of
chloromethylsilanes
from chloromethane
 production of vinyl chloride
(Cloe process)
 chlorination of methane
and ethylene
 production of butadiene
from ethanol
 isomerization of n-butane
 production of isoprene
 postchlorination of PVC
 combustion
 Reactor Types and Their Industrial Applications 27

Table 9. (Continued )

Reactor type Diagram Features Examples of applications

Entrained-flow reactor  uses very fine-grained  Fischer–Tropsch process

b b catalyst (Synthol process)
 whole quantity of catalyst
circulates continuously between
reaction section and tempering
or regeneration unit
c

h g
c c

Figure legend: a) Reaction mixture; b) Gaseous product; c) Catalyst; d) Air; e) Flue gas; f) Blocking steam; g) Reaction section; h) Regeneration
section

Table 10. Fixed-bed catalytic reactors for liquid-phase and gas–liquid reactions

Reactor type Diagram Features Examples of applications

Trickle-flow  can operate in cocurrent (illus-
reactor
f trated)
or countercurrent mode
 temperature control by inter-
a b
mediate
injection or recirculation
 danger of uneven liquid
e distribution and incomplete
wetting of catalyst
 narrow residence-time
distribution
d c
 desulfurization and refining of petroleum products
 hydrocracking
 production of butynediol from acetylene and
formaldehyde

direct hydration of propene to 2-propanol (Texaco)
 hydrogenation
 of organic intermediates (butynediol, adiponitrile,
ethylhexenal)
 of aldehydes, esters, and carboxylic acids to alcohols
 of natural fats to fatty acids
 of residues (low-temperature hydrogenation of tars)
 post-hydrogenation

Packed bubble  danger of flooding limit  amination of alcohols

column
d throughput  cobaltizer and decobaltizer in
f capacity oxo synthesis
 catalyst subject to greater  disproportionation of toluene
mechanical stress (retention to benzene and xylene
c necessary)
 high liquid proportion pro-
motes
heat removal
e  large amount of backmixing in
liquid phase

Figure legend: a) Liquid reactants; b) Gaseous reactants; c) Liquid product; d) Off-gas; e) Catalyst; f) Rupture disk

Table 11. Suspended-bed and fluidized-bed reactors for liquid-phase and gas–liquid reactions over solid catalysts
Reactor type
Bubble column with
suspended catalyst
Reactor with external
recirculation
Sparged stirred tank with
suspended catalyst
28
Diagram Features Examples of applications
e  simple design  hydrogenation
 small pressure drop  of CO (Fischer–Tropsch synthesis)
 danger of undesired  of tars and coals (bottom phase)
liquid-phase reactions  of benzene to cyclohexane
c+d
 inhomogeneous catalyst distribution  hydrodesulfurization
must be prevented
c  suitable if product drops out as solid
d
a+d a
b
See Table 3  heat-exchange and mixing devices in  hydrogenation of organic intermediates
external loop (nitrobenzenes, nitriles, nitronaphthalenes,
 for continuous and batch operation etc.)
 catalyst separation outside reactor
a+d  can also be operated in semicontin-  hydrogenation of organic intermediates
b e
uous and batch modes (nitro compounds, aromatics, butynediol)
 ensures intensive mixing of all  fat hydrogenation
phases  catalytic refining
Reactor Types and Their Industrial Applications
 increased cost for sealing and
maintaining stirrer drive
c+d c
Cascade of sparged stirred
tanks with suspended
catalyst
 higher final conversions than
a+d
a in single stirred tank
e e e
b  suitable for slow reaction rates
b b  adaptable to intermediate
injection and other
c interconnections
 hydrogenation of NO to hydroxylamine
 continuous hydrogenation of fats
 hydrolysis of fats to fatty acids and
glycerol production of toluenediamine
from dinitrotoluene

d
c+d
b

Fluidized-bed reactor  small pressure drop catalyst must  hydrocracking and desulfurization of
e have very high mechanical strength heavy petroleum fractions and still residues
(H-Oil process; three-phase fluidized bed)

Figure legend: a) Liquid feed components; b) Gaseous feed components; c) Liquid product; d) Catalyst; e) Off-gas; f) Heating agent or coolant; g) Heat exchanger; h) Pump; i) Reaction mixer with mixing nozzle
Reactor Types and Their Industrial Applications
29
30 Reactor Types and Their Industrial Applications
3.5. Reactors for Noncatalytic Reactions
Involving Solids
Various specialized reactors are available for
noncatalytic reactions involving solids. The dis-
cussion that follows deals only with the indus-
trially important types.
3.5.1. Reactors for Noncatalytic Gas–Solid
Reactions
In general, noncatalytic gas–solid reactions are
characterized by low overall reaction rates and
high process temperatures; in addition, the
structure and geometry of the solid can change
during the reaction.
Reactors for this service can essentially be
grouped into those for semi-continuous opera-
tion, that is, with no solids transport (vertical
shaft kilns and rotary drums), and those for
continuous operation, that is, with continuous
solids transport. The second type, in turn, can
be divided into
1. Reactors with gravity transport of solids
2. Reactors with mechanical transport of solids
3. Reactors with pneumatic transport of solids
These three groups differ widely with respect
to residence time, their conditions of mass and
heat transfer between gas and solid phases, and
heat-input capabilities.
The first group includes moving-bed
reactors. Since the gas has to flow through
the bed of solids, mass and heat transport
between the phases is relatively good. Temper-
ature control may be effected by simultaneously
carrying out exothermic and endothermic
reactions in the same reactor.
Reactors with mechanical transport of sol-
ids include rotary kilns and multiple-hearth
furnaces (→ Metallurgical Furnaces). Trans-
port of gas and solid phases through the reactor
largely occurs separately. Intensive heat and
mass transfer occurs only at the surface of the
bed of solids. The complete involvement of the
solid phase in the reaction process requires
continuous, intensive mixing of the solids.
Heat is often supplied directly by burners.
Multiple unit operations can be in operation
within a single piece of equipment (e.g., dry-
ing, heating, cooling, and various reaction
steps).
Reactors with pneumatic transport of solids
includes fluidized-bed and entrained-flow
reactors, dust roasters, and suspension fur-
naces. Solids transport by a gas stream is usually
possible only with small particle sizes and a very
narrow particle size distribution. Because of the
favorable conditions for heat and mass trans-
port, these reactors offer shorter residence times
and thus higher throughputs than other types.
Possible options for heating these reactors are
the incorporation of heat-transfer surfaces, sup-
plementary solid heat-transfer media, and direct
heating.
Industrially important reactor types for non-
catalytic gas–solid reactions are listed in
Table 12 along with examples of commercial
applications.
3.5.2. Reactors for Noncatalytic Liquid–Solid
Reactions
Reactors used for noncatalytic liquid–solid
reactions must be designed for the transport
and mixing of phases, sometimes at high solids
concentrations. Batch and semi-continuous
designs are therefore dominant.
Table 13 presents a survey of important
reactor types for noncatalytic liquid–solid
reactions and examples of practical
applications.
3.5.3. Reactors for Noncatalytic Solid-Phase
Reactions
Reactors used for noncatalytic solid-phase
reactions are similar to those used for noncata-
lytic gas–solid reactions. Long residence times
and high reaction temperatures are necessary,
especially for reactions between different solids,
because of the low transport rates therein. Heat
can be supplied by indirect or direct process
heating.
Inert gases are employed for heat transport
and agitation of the solids. Important applica-
tions are listed in Table 14.
 Reactor Types and Their Industrial Applications 31

Table 12. Reactors for noncatalytic gas–solid reactions

Reactor Diagram Features Examples of applications

type

Shaft  simple design  ore dressing

a  
reactor, long residence times attainable autothermal coal gasifica-
retort,  semicontinuous operation tion (Lurgi pressure
kiln gasification)
d  thermal production of
activated carbon
 chlorination of scrap iron
to FeCl3
 reduction of copper
compounds with H2 and
HCl to CuCl
 production of CS2 from
wood charcoal and sulfur
vapor

Moving bed  long residence times available  flue gas desulfurization

d  
reactor continuous operation coal carbonization
 heat supplied with gas stream and coking (Lurgi
purge-gas process)
 oil shale retorting

(continued )
32 Reactor Types and Their Industrial Applications

Table 12. (Continued )

Reactor Diagram Features Examples of applications

type

Multiple  for very long residence times  roasting and reduction of

a d 
hearth individual hearths can be ores
reactor heated directly  production of activated
 continuous operation carbon
 gas can flow countercurrently
or cocurrently
 small quantities of gas possible

Rotary kiln  relatively complicated design  roasting of ores

a  
for long residence times production of
 direct heating possible  calcium cyanamide from
 continuous operation nitrogen and calcium
 gas can flow countercurrently carbide
or cocurrently  nickel carbonyl
 activated carbon
d
b  ZnO from zinc

c  burning of sulfur to SO2

g

Fluidized-  burning of carbon for

bed d energy production
reactor  autothermal coal
gasification
 Winkler generator
 Ruhrgas process
 allothermal coal
a gasification with solid
heat transfer agents
 carbonization and coking
 fluidised bed process
 Lurgi-Ruhrgas sulfur
process
 roasting of ores
 chlorination of ores and
c lime
 production of
 activated carbon
 AlF3 from Al2O3 and HF
b (multistage)
 Reactor Types and Their Industrial Applications 33

Table 12. (Continued )

Reactor Diagram Features Examples of applications

type

Entrained  solids in dust form with very  carbonization and

c+d
flow narrow grain size distribution coking of coals
reactor  very short residence time (entrained solids
 suspended dust can be carbonization
f conveyed with or process)
without recycle  suspended smelting
 for high throughputs for beneficiation of
 internals for heat copper and nickel ores
recovery by steam (INCO process)
generation  coal gasification:
 Koppers Totzek
process
 Prenflo process
 Shell process

see Table see fluidized bed reactors  very fine particles with narrow  ore roasting
12 Dust grain size distribution must be
roasters used
 solids drop downwards
 velocity and residence
time are governed by
ratio of gravity and
resistance force

Figure legend: a) Solid feed components; b) Gaseous feed components; c) Solid product; d) Off-gas; e) Air; f) Cyclone; g) Drive unit

3.6. Electrothermal Reactors Plasma Reactions, Section 2.1.; → Metallurgi-

A variety of electrical heating schemes are
used in some important noncatalytic reactions
between gases and solids requiring very high
reaction temperatures and large quantities of
heat. In the simplest case, resistance heating
elements (rods, strips, etc.) are used for this
purpose. A much more efficient method,
however is direct electric heating. Options
here include arc, resistance, and induction
heating.
The very high temperatures produced by the
arc cause ionization in gases and thus activate
the reactants; this feature is utilized in plasma
processes for high-temperature pyrolysis (→
cal Furnaces, Section 5.5.).
Equipment used for solid reactions includes
arc and resistance-heated reduction furnaces
and the Acheson furnace (→ Metallurgical
Furnaces, Section 5.2. → Section 5.3.). The
Acheson furnace is a resistance-heated device
for pure solid–solid reactions; that is, in con-
trast to other processes, no melting of the solid
charge occurs. All electrothermal processes
are characterized by very high equipment
cost and high electric power consumption.
The most common prerequisite for their eco-
nomical operation is usually a low unit price
for energy.
34 Reactor Types and Their Industrial Applications

Table 13. Reactors for noncatalytic liquid–solid reactions

Reactor type Diagram Features Examples of applications

Stirred tank  batch or  production of alkali cellulose and

a+b semicontinuous nitrocellulose
operation  reduction of nitrobenzene
predominant with metals to aniline or
 solids content hydrazobenzene
limited by power of  bauxite digestion
stirring  production of salicylic acid
apparatus from dry sodium
phenolate (Kolbe–Schmitt process)
 hydrolysis of calcium cyanamide
to cyanamide
 production of BF3 from B2O3,
CaF2, and H2SO4
 production of alkylaluminums
from aluminum, olefin, and
hydrogen
 production of tetraethyllead

Cascade of  for low reaction  apatite digestion

a+b
stirred tanks rates and high final  cellulose digestion
conversions
 semicontinuous
operation with
solids fixed in
tank and liquid
recirculating

c
 Reactor Types and Their Industrial Applications 35

Table 13. (Continued )

Reactor type Diagram Features Examples of applications

Tank with  production of ammonium sulfate from

liquid
a ammonium carbonate and gypsum
recirculation

Rotary drum  for batch  production of cellulose acetate and cellulose

operation, high sol- ethers
ids content  production of AlF3 by
wet process

b a c

Fluidized-bed  semicontinuous  water treatment

reactor operation
 intensive liquid
c circulation

Steeping press  combination of  production of cellulose ether

reaction and
liquid separation
 batch operation
b

(continued )
36 Reactor Types and Their Industrial Applications

Table 13. (Continued )

Reactor type Diagram Features Examples of applications

Kneader  used for highly vis-  production of nitrocellulose, cellulose ether,

a+b cous media and cellulose acetate
 for batch  production of celluloid from
operation nitrocellulose
 production of superphosphate

Screw-  used for highly vis-  digestion of rutile or ilmenite with

b
conveyor cous media H2SO4
reactor  batch operation

Multiple-  continuous  production of acetylene from carbide (dry gas

hearth
a b operation generator)
reactor  long solids
residence time

Rotary kiln  direct heating for  digestion of fluorspar or phosphate with

b
high reaction H2SO4 reducing decomposition of H2SO4 in
temperatures presence of carbon

c e

Figure legend: a) Solid feed components; b) Gaseous feed components; c) Solid product; d) Off-gas; e) Air; f) Cyclone; g) Drive unit
 Reactor Types and Their Industrial Applications 37

Table 14. Reactors for noncatalytic solid-phase reactions

Reactor type Diagram Features Examples of applications

Shaft reactor see Table 11  metallurgical processes,

a
e.g.,
 powder boriding of
d iron-based materials
 direct reduction of
iron ores with carbon
(Kinglor–Metor
process)

Multiple-hearth see Table 11  calcination

a d
reactor

b
c

Rotary kiln see Table 11  cement production

a  burning of lime, dolomite,
gypsum, and
magnesite
 calcination
d  thermal decomposition of FeSO4
b and BaCO3
c  reduction of barite
g
with carbon to BaS
 reduction of ores with
carbon (e.g., to ZnO)

(continued )
38 Reactor Types and Their Industrial Applications
Table 14. (Continued )
Reactor type Diagram
Fluidized-bed
reactor d
Figure legend: a) Solid feed components; b) Gaseous feed components; c) Solid product; d) Off-gas; e) Air; f) Cyclone; g) Drive unit
This group of reactors and their applications
are summarized in Table 15.
3.7. Reactors for Electrochemical
Processes (→ Electrochemistry, 2.
Inorganic Electrochemical Processes;
→ Metallurgical Furnaces)
In electrochemical reactions, electrons are sup-
plied to a reactant in the electrolyte or removed
from it with the aid of an electric current. A
minimum voltage called the decomposition
voltage must be applied to the electrodes for
this purpose. In addition to the electrochemical
reactions occurring on the electrode surface,
transport processes and chemical reactions in
the electrolyte bath are important.
Electrochemical processes have the follow-
ing advantages:
1. High product purity (no secondary reactions)
2. Low reaction temperature (except for fused-
salt electrolysis)
3. Easy control of reaction rate through varia-
tion of electrode voltage
They have the following disadvantages:
1. High energy losses in the system
2. Large space requirements
3. High investment costs
Features Examples of applications
see Table 11  burning of lime (multistage)
For these reasons, electrochemical processes
are used only when no available thermal or
catalytic process can accomplish the same pur-
pose, which is especially true in the production
of chlorine, aluminum, and copper.
The design of the reaction system (i.e., cell
geometry and flow configuration), the electrode
arrangement and material, and control of phases
and concentrations are highly process specific.
Typical designs are illustrated in Table 16.
3.8. Reactors for Biochemical Processes
(→ Biochemical Engineering; →
Biotechnology, 1. General)
Some important biochemical processes, such as
those used in making antibiotics, beer, wine, soy
sauce, and baker’s yeast, have been known for
centuries (→ Biocatalysis, 1. General, Chapter 3.
History). Typical of these processes is their use of
enzymes as biocatalysts.
In modern industrial applications, the
enzymes can be present as cell constituents of
living microorganisms, or they can be in a purif-
ied form, either free or bound to inert supports (→
Biocatalysis, 2. Immobilized Biocatalysts).
The prerequisite for the use of live micro-
organisms is engineering the provision of
favorable living conditions. Such conditions
include the presence of adequate amounts of
specific nutrients as well as gases such as
 Reactor Types and Their Industrial Applications 39

Table 15. Electrothermal reactors

Reactor type Diagram Features Examples of applications

Plasma torch  very high temperature for  high-temperature pyrolysis for

plasma generation the production of ethylene and
 very short acetylene arc furnace (Hüls)
f
residence time  d.c. torch (Hüls)
 large product spectrum  a.c. plasma (Hoechst)
c

g
h

Fluohm reactor  resistance heating with graphite  production of HCN

d fluidized bed (Shawinigan process)

Reduction arc  very high reaction  production of

a 
furnace temperatures calcium carbide
 continuous raw material feed and  phosphorus
periodic product discharge or  corundum
batch process  decomposition of
g
BaCO3
 metallurgical processes
(e.g., production of
ferroalloys)

(continued )
40 Reactor Types and Their Industrial Applications

Table 15. (Continued )

Reactor type Diagram Features Examples of applications

Reduction  for low temperatures and lower  production of glass melts

a 
resistance specific electrical power than metallurgical processes
furnace the arc furnace (e.g., reduction of
metal oxides)
 chlorinating digestion of
g rare-earth ores
i

Acheson furnace  reaction takes place in the  production of

solid phase  graphite
a j
 batch process  silicon carbide
 very long residence times

g g

Reactor with  production of

k 
indirect electric cyanamide from carbide in a
a
heating furnace with heating
elements
 MgCl2 from MgO in a
blast furnace with
electric heating

b i

Figure legend: a) Solids; b) Molten product; c) Gaseous reaction mixture; d) Gaseous product; e) Catalyst; f) Carrier gas; g) Electrodes; h) Plasma;
i) Slag; j) Resistive charge; k) Off-gas

oxygen (in aerobic processes) and carbon diox-
ide (in cell culture). The design also needs to
allow for maintenance of the temperature,
pressure, and pH in certain ranges, and the
maintenance of aseptic (rather than sterile)
conditions. Where these considerations are
paramount, for example in the pharmaceutical
industry, single-use technologies are now
becoming increasingly popular.
The maintenance of a controlled state sup-
portive of metabolism is important for reactor
design. Aerobic processes require an adequate
and controlled supply of oxygen. In anaerobic
processes, the admission of gas from outside
must be prevented; gases and vapors resulting
from the reaction must also be removed from the
reactor whilst maintaining aseptic conditions.
Reactors for these processes can be classified
as follows:
1. Reactors with dissolved or suspended bio-
catalysts (submerged processes) for aerobic
or anaerobic conditions
2. Reactors with immobilized biocatalysts for
aerobic or anaerobic conditions
Reactors for use in submerged aerobic pro-
cesses have provisions for efficient aeration and
 Reactor Types and Their Industrial Applications 41

Table 16. Electrochemical Reactors

Reactor type Diagram Features Examples of

applications

Metal winning  high product purity (no sec-  production of

by fused salt
e ondary reactions)  aluminum
electrolysis b  low reaction temperature  magnesium
(except for fused-salt  sodium
electrolysis)
 easy control of reaction rate
p through variation of elec-
trode voltage
_ h h _

+ g

Electrolytic  high product purity (no sec-  refining of

metal refining ondary reactions)  copper
p
 low reaction temperature  nickel
+ – h + (except for fused-salt
electrolysis)
 easy control of reaction rate
through variation of elec-
g g trode voltage

q q
r

Electrolysis of  high product purity (no sec-  electrolysis of water

inorganic
f ondary reactions)  fluorine production
material  low reaction temperature by electrolysis of
d (except for fused-salt hydrogen fluoride
electrolysis)  production of sodium
 easy control of reaction rate chlorate by
through variation of elec- electrolysis of
h g trode voltage sodium chloride
– +  electrochemical oxi-
dation of sodium
chlorate to
perchlorate
 recovery of persulfu-
+– +– 0 +– ric acid
a  production of ozone

Electrolysis of  high product purity (no sec-  production of adipo-

organic
s ondary reactions) nitrile from
material  low reaction temperature acrylonitrile
(except for fused-salt  production of
electrolysis) dimethyl sebacate
 easy control of reaction rate  reduction of nitro-
through variation of elec- benzene to aniline
h g trode voltage  production of per-
– + fluorocaprylic acid
 production of
dihydrostreptomycin

(continued )
42 Reactor Types and Their Industrial Applications

Table 16. (Continued )

Reactor type Diagram Features Examples of

applications

Mercury  high product purity  chlorine production

amalgam
c l (no secondary reactions) by chlor-alkali
process  low reaction temperature electrolysis
+ g + + (except for fused-salt
electrolysis)
k  easy control of reaction rate
through variation of
electrode voltage
h f+d

m n

Diaphragm cell  high product purity (no sec-  chlorine production

process ondary reactions) by chlor-alkali
+  low reaction temperature electrolysis
c b (except for fused-salt
electrolysis)
 easy control of reaction rate
g
through variation of elec-
trode voltage

o h–

Membrane  high product purity  chlorine pro-

b d
process (no secondary duction by
+ – reactions) chlor-alkali
 low reaction temper- electrolysis
c a+c
a + 40% f ature (except for
fused-salt
electrolysis)
 easy control of
reaction rate through
variation of electrode
a
a + 20% c voltage
g i h

Figure legend: a) Water; b) Chlorine; c) Sodium chloride; d) Hydrogen; e) Sodium; f) Sodium hydroxide; g) Anode; h) Cathode; i) Membrane; j)
Product; k) Amalgam; l) Recycle brine + chlorine; m) Mercury; n) Graphite; o) Diaphragm; p) Electrolytic salt solution of metal to be refined; q)
Anode slime; r) Electrolyte removal; s) Organic feed solution; t) Oxygen

intensive liquid circulation. Aeration is accom- A summary of the most important reactor
plished with fixed or moving distributors, noz- types and their applications is given in
zles, submerged or rotating jets. Liquid Table 17. The use of membranes for solids
circulation is ensured by various stirring sys- removal and recycle can be used along with
tems or by forced or natural convection. many of these reactor types to produce
 Reactor Types and Their Industrial Applications 43

Table 17. Reactors for submerged aerobic processes

Reactor type Diagram Features Examples of applications

Sparged stirred tank  various stirring and circulation apparatus suitable for  production of
d b higher viscosities  antibiotics
 amino acids
 yeast
 aerobic wastewater
treatment

Reactors with forced

circulation
Bubble column  very broad residence-time distribution  production of yeast
d  good dispersion properties  aerobic wastewater
treatment
e

c
a

Jet reactor  free jet, jet nozzle, or central tube designs possible  aerobic wastewater
d  for low viscosities treatment
 high gas velocities, good mass
transfer

(continued )
44 Reactor Types and Their Industrial Applications

Table 17. (Continued )

Reactor type Diagram Features Examples of applications

Submerged-jet reactor  very broad residence-time distribution  processing of spent sul-

a  good mass transfer fite liquor
d
 danger of slime settling out  fermentation of waste
b
substrates

Reactors with natural

circulation
Bubble column  much backmixing, broad residence-time distribution  production of
e  for low viscosities  biomass
b   citric acid
•• • •• ••
simple construction
• • • •• •
• • •
• • • ••
•• • •
• •• •• •••

a c

Loop reactor  for low viscosities  aerobic wastewater

d  little dispersive action treatment

b
••
•• •
•• •••• ••
••
• • • •••
c • •• ••

Sieve-tray tower  good mass transfer due to fine bubble structures  aerobic wastewater
d b treatment

e
c

a
 Reactor Types and Their Industrial Applications
Table 17. (Continued )
Reactor type Diagram
Surface reactors
Trickle-bed reactor
d and negligible dispersive action
a
e
Reactor with rotating
internals
d b
Figure legend: a) Gas; b) Fermentation medium; c) Product; d) Off-gas; e) Recycle stream
membrane bioreactors [7] (→ Membrane
Reactors).
Reactors for anaerobic conditions do not
have aeration equipment, as oxygen is toxic
to many anaerobic microorganisms, though
they may have closed gas circulation systems.
Usually, sealed vessels with or without stirrers
are used (fermenters), though most of the con-
figurations used for aerobic bioreactors are also
used for anaerobic systems. Anaerobic mem-
brane reactors have become commercially
important [7]. Applications of these reactor
types include fermentation processes such as
lactic acid fermentation, alcohol production, and
mash fermentation, as well as anaerobic waste-
water treatment.
The immobilization of enzymes on suitable
supports enables the use of reactor designs
similar to those for heterogeneous catalytic
processes. If the enzymes are supported on
semipermeable membranes, separation and
reaction can be combined in membrane reactors
(→ Membrane Reactors, Chapter 4. Biocatalytic
Membrane Reactors).
45
Features Examples of applications
 low mass-transfer coefficients  production of
acetic acid
 aerobic wastewater
treatment
 use of paddles, cylinders, etc.  aerobic wastewater
suitable for viscous media treatment
Reactors with immobilized biocatalysts,
together with their applications, are listed in
Table 18.
3.9. Reactors for Photochemical and
Radiochemical Processes
Photochemical and radiochemical principles are
used to a very limited extent in industry because
the required conditions for practical economical
operation such as sufficiently high quantum
efficiency are seldom met.
3.9.1. Photochemical Reactors (→ Photo-
chemistry, Chap. 3.)
The rate of a photochemical reaction is deter-
mined by the concentration of reactants and by
the intensity, quantity, and wavelength of light
supplied. Light in the wavelength range that is
absorbed by the reaction mixture can be for-
mally treated as a reactant. As a consequence,
photochemical reactions exhibit a position
46 Reactor Types and Their Industrial Applications

Table 18. Reactors for biochemical processes over immobilized biocatalysts (for aerobic and anaerobic conditions)

Reactor type Diagram Features Examples of applications

Fixed-bed reactor  high conversions possible  production of

b  high catalyst density  amino acids
 danger of uneven flow through  fructose
systems and poor mass transfer  ethanol
 high mechanical stress on catalyst  wastewater treatment
 high pressure drop
c  mechanically simple design

Stirred tank with suspended catalyst  continuous or batch operation  production of fructose
d b  good conditions for external mass  wastewater treatment
transport
 only partial conversion achievable
 mechanical stress on catalyst grains
• •
• • • • •• • •
•• • • • •• due to shear forces
•• • •
• • • •• • ••
•• • • ••• • • •  possibility of continuous catalyst
•• • • • •••• • • ••
• •• •• • replacement
• • • • •
• • • •• • •
• • • •• ••
••
• ••• • • • • • ••• ••
•• •
•
•• ••••• ••••
•
• •• • • •• •••
•
a

Fluidized-bed reactor  good conditions for external mass transport  production of

d  possibility of continuous catalyst  ethanol
replacement  enzymes
 low catalyst concentration  wastewater treatment
 high flow velocities necessary
•• • •••
• •••• ••• ••
c

•• •
•• •• •• • •
• ••
••••• •• •••
•• • • • ••

b
 Reactor Types and Their Industrial Applications 47

Table 18. (Continued )

Reactor type Diagram Features Examples of applications

Membrane reactor  various membrane configurations possible  production of

e  catalyst separated from substrate  enzymes
 capacity limited by transport  pharmaceuticals
resistance of membranes  amino acids
 aging and fouling of membranes  wastewater treatment
g  large pressure drop

Figure legend: a) Biocatalyst; b) Fermentation medium; c) Product; d) Off-gas; e) Permeate; f) Membrane tube; g) Retentate

dependence of the reaction rate, even with List of Abbreviations

complete mixing, because the flux density of
light quanta decreases with increasing distance ABS acrylonitrile–butadiene–styrene
from the light source. The feasible thickness of copolymer
the reaction space, and thus the type and size of BR butadiene rubber
reactor that can be used, depends not only on the CR chloroprene rubber
power of the emitter, but also on the optical DGT diglycyl terephthalate
properties of the reactor material and the DMT dimethyl terephthalate
reaction medium. Intensive mixing must be EO–PPO ethylene oxide–pol(propylene
ensured, especially for thick beds. Light can oxide) block copolymer
be supplied from outside (through the reactor EPDM ethylene–propene–diene copolymer
wall) or by submerged light sources. When EPM ethylene–propene copolymer
high-power light sources are used, a large EPS expandable polystyrene
amount of heat is evolved and supplemental HDPE high-density polyethylene
cooling devices must be employed. HIPS high-impact polystyrene
A survey of reactor types and their industrial IIR isobutylene–isoprene rubber (butyl
applications appears in Table 19. rubber)
IR isoprene rubber (synthetic)
LDPE low-density polyethylene
3.9.2. Radiochemical Reactors (→ Radiation LLDPE linear low-density polyethylene
Chemistry) MA maleic anhydride
MDA 4,4’-diaminodiphenyl methane
Radiochemical reactions are induced by the MDI methylene diphenylene isocyanate
action of ionizing radiation. In addition to MF melamine–formaldehyde
high energy consumption, the extremely com- NBR butadiene–acrylonitrile copolymer
plex design of radiation sources and shielding (nitrile rubber)
works against the wider use of this reaction PA polyamide
principle. Table 20 covers some commercially PAC polyacrylate
important applications of radiochemistry. PAN polyacrylonitrile
48 Reactor Types and Their Industrial Applications

Table 19. Reactors for photochemical processes

Reactor Diagram Features Examples of applications

type

Tubular  for homogeneous gas- and  chlorination of benzene to

reactor
a liquid-phase hexachlorocyclohexane
reactions  sulfochlorination
 chlorination of
methane to dichloromethane
d

c
b

Bubble  requires favorable optical  sulfochlorination of paraffins

column
f conditions and low viscosity (cascade)
also used in cascades and with  side-chain chlorination of
c
central tube aromatics
 production of dodecanethiol
• from 1-dodecene and H2S
• •• •
• •• •
• • •• •
• • •
• ••• • ••• •
• • d
b g
a

Stirred  optically induced differences in reaction  oximation of cyclohexane

tank
f b rate equalized by intensive stirring with nitrosyl chloride
d  production of pro
vitamin D3
a e

Falling-  suitable for poor optical conditions  production of vitamin D2

film because film is very thin
d
reactor
b
e

h
e

Belt  especially for highly viscous media  polymerization to PAN, PAC,

reactor PVC, PVAC
b
d

i
c

Figure legend: a) Gaseous feed components; b) Liquid feed components; c) Product; d) Emitter; e) Coolant; f) Off-gas; g) External reflector; h)
Falling film; i) Belt
 Reactor Types and Their Industrial Applications 49

Table 20. Reactors for radiochemical processes

Reactor type Diagram Features Examples of applications

Radiochemical  high energy  production of ethyl bromide (Dow process) -

reactor
a consumption illustrated
 extremely complex  radiative cross-linking of poly(vinyl chloride)
b design and
polyethylene
 production of alkyltin compounds

••

••••
degradation of polymers
Pb
•• •
••
 various chlorinations

• Co60 •••
•• • •
••
c
•• •
•• • Pb •
• • ••
•
••• •• •• •• •• •••
•• •• • •••••• ••• •
•• • •

Figure legend: a) Gaseous reaction mixture; b) Liquid product; c) Shielding

PBT poly(butylene terephthalate) References

PE polyethylene
PE–PP polyethylene–polypropylene 1 Chemische Reaktoren-Ausrüstungen und ihre Berechnung
(1981) Verfahrenstechnische Berechnungsmethoden, part 5,
copolymer
VEB Deutscher Verlag für Grundstoffindustrie, Leipzig.
PET poly(ethylene terephthalate) 2 Gerrens, H. (1980) Über die Auswahl von Polymerisations-
PF phenol–formaldehyde reaktoren. Chem. Ing. Tech., 52, 477–488.
PIB polyisobutylene 3 Reichert, K.H. and Geiseler, W. (eds) (1989) Polymer Reaction
Engineering, VCH Verlagsgesellschaft, Weinheim, Germany.
PMMA poly(methyl methacrylate)
4 Deckwer, W.-D. (1988) Bioreaktoren. Chem. Ing. Tech., 60,
PPO poly(propylene oxide) 583–590.
POM polyoxymethylene 5 Schügerl, K. (1990) Characteristic Features of Bioreactors, in
PP polypropylene Bioreaction Engineering, vol. 2, John Wiley and Sons, New
York.
PS polystyrene
6 Heger, A. (1990) Technologie der Strahlenchemie von Poly-
PUR polyurethane meren, Carl Hanser Verlag, München.
PVAC poly(vinyl acetate) 7 Judd, S. (2011) The MBR Book, 2nd edn, Butterworth Heine-
PVAL poly(vinyl alcohol) mann, New York.
PVC poly(vinyl chloride)
SAN styrene–acrylonitrile copolymer
SBR styrene–butadiene rubber
Further Reading
SB styrene–butadiene block copolymer Froment, G.F., Bischoff, K.B., and Wilde, J. (2010) Chemical
SB–S styrene–butadiene–styrene block Reactor Analysis and Design, 3rd edn, Wiley, Hoboken.
Jakobsen, H.A. (2008) Chemical Reactor Modeling, Springer,
copolymer
Berlin.
TDA toluene diamine Luyben, W.L. (2007) Chemical Reactor Design and Control, Wiley,
TDI toluene diisocyanate Hoboken.
UF urea–formaldehyde Mann, U. (2009) Principles of Chemical Reactor Analysis and
Design, 2nd edn, Wiley, Hoboken.
UP unsaturated polyester
Mann, U. (2007) Reactor Technology, in Kirk Othmer Encyclopedia
of Chemical Technology, 5th edn, John Wiley & Sons, Hoboken.
Nauman, E.B. (2008) Chemical Reactor Design, Optimization, and
Scaleup, 2nd edn, Wiley, Hoboken.