Article No : b04_087

Reactor Types and Their Industrial Applications

KLAUS-DIETER HENKEL, Buna AG, Schkopau, Federal Republic of Germany

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 293 3.5.2. Reactors for Noncatalytic Liquid – Solid

2. Basic Types of Reactors . . . . . . . . . . . . . . 294 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 314
3. Survey of Real Reactors and their Uses. . . 295 3.5.3. Reactors for Noncatalytic
3.1. Reactors for Gas-Phase Reactions . . . . . . . 296 Solid-Phase Reactions . . . . . . . . . . . . . . . . . 314
3.2. Reactors for Liquid-Phase Reactions . . . . . 296 3.6. Electrothermal Reactors . . . . . . . . . . . . . . 314
3.3. Reactors for Gas – Liquid Reactions . . . . . 303 3.7. Reactors for Electrochemical Processes . . 317
3.4. Reactors for Solid-Catalyzed Reactions . . . 303 3.8. Reactors for Biochemical Processes . . . . . 320
3.4.1. Reactors for Heterogeneous Gas Catalysis . . 303 3.9. Reactors for Photochemical and
3.4.2. Reactors for Liquid-Phase and Gas – Liquid Radiochemical Processes . . . . . . . . . . . . . . 322
Reactions over Solid Catalysts . . . . . . . . . . . . 310 3.9.1. Photochemical Reactors . . . . . . . . . . . . . . . 324
3.5. Reactors for Noncatalytic Reactions 3.9.2. Radiochemical Reactors . . . . . . . . . . . . . . . 324
Involving Solids . . . . . . . . . . . . . . . . . . . . . 310 References . . . . . . . . . . . . . . . . . . . . . . . . . 326
3.5.1. Reactors for Noncatalytic
Gas – Solid Reactions . . . . . . . . . . . . . . . . . 311

1. Introduction The most important activation principles for a

reaction mixture include
The reactor in which the chemical reaction takes
place occupies a central position in the chemical 1. Activation by addition of heat
process. Grouped around the reactor are the 2. Catalytic activation
process steps involving physical treatment of the 3. Activation by decomposition of an initiator
material streams, such as conveyance, heat trans- 4. Electrochemical activation
fer, and separation and mixing operations. The 5. Biochemical activation
reactor provides the volume necessary for the
reaction and holds the amount of catalyst re- Less important options for activation are
quired for the reaction. The energy required to visible or ultraviolet light and radioactive
overcome the activation threshold of each partial radiation.
reaction is also supplied in the reactor, and the With regard to phase relationships in the
proper temperature and concentration are reaction space, a number of combinations are
maintained. possible. The reactants and reaction products can
The most important reaction-related factors be present, or be produced, in various states of
for the design of a reactor are aggregation. Furthermore, inert diluents or heat-
transfer media can be present in different phases.
1. The activation principle selected, together Finally, the catalyst, which is generally in the
with the states of aggregation of the reactants solid or liquid phase, often has to be taken into
and the resulting number and types of phases consideration.
involved The (negative or positive) heat of the reactions
2. The concentration and temperature depen- taking place in a reactor influences the extent and
dence of the chemical reactions nature of provisions for heat transfer. Exother-
3. The heat of the reactions taking place mic or endothermic reactions frequently require

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.b04_087
294 Reactor Types and Their Industrial Applications Vol. 31

supply or removal of large quantities of heat. flow is assumed, i. e., no mixing occurs in axial
Thermally neutral reactions involve consider- (flow) direction, but ideal mixing takes place in
ably less technical sophistication. the ra-dial direction. Thus, as in the batch stir-
The concentration and temperature depen- red-tank reactor, all particles experience a well-
dences of a chemical reaction are described by defined residence time. In contrast, the continu-
the reaction rate. In practice most reaction ous stirred-tank reactor has a very broad resi-
systems are complex and include parallel, se- dence-time distribution (! Principles of
quential, and equilibrium reactions. To obtain Chemical Reaction Engineering). The ideal
the highest possible yield of desired product analysis is based on the assumption of a reaction
under these conditions, the temperature and system that is homogeneous as regards the
pressure must be held within certain ranges, phase. Thus transport resistance between phases
the temperature must be controlled along the does not occur.
reaction path, and a definite residence-time The thermally ideal operating states are the
distribution in the reactor must be achieved. isothermal and adiabatic states, i. e., either very
If, in addition, substances or energy have to be intensive heat exchange with the surroundings or
transferred from one phase to another, appro- no exchange at all is assumed.
priate transport conditions have to be imple- In practical operation, the ideal states are
mented. When catalysts are used, catalyst loss achieved only approximately. Examples of typi-
due to aging and poisoning must be considered. cal nonidealities include
These factors impose a complex of require-
ments that must be kept in mind when design- 1. The formation of real flow patterns, such as
ing a reactor. dead zones, short-circuit flows, and channeling
Against the requirements established by the 2. Transport processes in the individual phases,
process, the designer must balance costs of such as axial backmixing
fabrication, consumption of materials, and 3. The formation of concentration and tempera-
operational reliability. In practice, many pos- ture profiles as a result of transport resistances
sibilities are often available for realizing a in and between phases
chemical process, and in such cases the deci- 4. Segregation processes
sion must depend on an assessment of the 5. Incomplete mixing of reactants
overall process as well as commercial con-
straints on the plant. The essential advantages and disadvantages
of the three basic reactor types are discussed in
what follows.
2. Basic Types of Reactors (! Model
Reactors and Their Design Equations) Batch Stirred Tank (! Stirred Tank
Reactors)
A variety of reactor designs are used in industry,
but all of them can be assigned to certain basic Principal Applications:
types or combinations of these. The basic types
1. Liquid-phase reactions
are as follows (see ! Principles of Chemical
2. Liquid – solid reactions
Reaction Engineering, Section 4.2.):
Advantages:
1. Batch stirred-tank reactor
2. Continuous stirred-tank reactor 1. Quick production changeover possible; use
3. Tubular reactor for substances produced on a small scale
2. Process steps upstream or downstream of
Given certain flow and thermal conditions, the reaction can also be performed in the
these types are also referred to as ‘‘ideal’’ re- reactor
actors. With respect to flow conditions the ideal 3. Better process control than in continuous
stirred-tank batch reactor is characterized by operation when solid or highly viscous phases
complete mixing on microscopic and macro- form or are present
scopic scales. In the ideal tubular reactor, plug 4. Well-defined residence time
Vol. 31 Reactor Types and Their Industrial Applications 295

Disadvantages: 2. No moving mechanical parts, hence especial-

ly suitable for high-pressure service
1. Relatively high operating costs due to long
downtimes and high manpower requirements
Disadvantages:
2. Quality differences between charges because
reaction conditions are only partly 1. Very high degree of specialization, often with
reproducible complicated design and high investment costs
3. Limited temperature control capabilities, es- 2. Relatively large pressure drops
pecially with highly endothermic or exother-
mic reactions Reactors are interconnected to make up for the
drawbacks of a single reactor, especially to adapt
reaction conditions during scale-up capacity, as
Continuous Stirred Tank well as to optimize conversion and yield. Partial
Principal Applications: reactors can be combined in a single apparatus or
1. Liquid-phase reactions connected in a system of reactors; these partial
2. Gas – liquid reactions reactors may differ in shape and size.
3. Gas – liquid reactions over suspended Types of interconnections are series, parallel,
catalysts and recycle.

Series Connection:
Advantages:
1. Multibed reactors
1. Low operating costs, especially at high 2. Tower reactors, reaction columns
throughputs 3. Cascades of stirred tanks (! Stirred Tank
2. Consistent product quality due to reproduc- Reactors)
ible process control 4. Multiple-hearth reactors (! Metallurgical
3. Wide range of throughput Furnaces)
5. Different reactor types connected in series
Disadvantages: (e.g., stirred tank and tubular reactor)

1. Final conversions lower than in other basic Parallel Connection: Multitubular reactors
reactor types because of complete mixing
Recycle Connection: Loop reactors (!
(i.e., unreacted starting materials can get into
Stirred Tank Reactors)
the product stream)
Complicated reactor designs result, especially
2. High investment costs to implement continu-
when different reactor types are combined in a
ous operation
single apparatus. At the same time, such a combi-
3. Changeover to other products generally com-
nation offers maximum adaptability to the require-
plex and time-consuming because of reaction-
ments of a given reaction process. The designer
specific design
must, of course, examine every case individually to
ensure that the results justify the very high devel-
Tubular Reactor (! Tubular Reactors) opment and investment costs for such special
Principal Applications: reactors. The following survey of real reactors
includes these special types of reactor designs
1. Homogeneous gas-phase reactions only when their utility extends beyond a single
2. Liquid-phase reactions case.
3. Gas- and liquid-phase reactions over solid
catalysts (! Fixed‐Bed Reactors)
4. Gas – liquid reactions
3. Survey of Real Reactors and their
Advantages:
Uses
1. Favorable conditions for temperature control The phase relationships in the reaction space are
by heat supply or removal crucial in the design of reactors for catalytic,
296 Reactor Types and Their Industrial Applications Vol. 31

thermal, and polymerization processes and Table 2. Reactors for endothermic gas-phase reactions
accordingly form the top-level classification fea- Reactor type Features Examples of applications
ture for such reactors. Since many different
combinations of phases are possible, the survey Burner very high reaction Sachsse – Bartholom
e pro-
temperatures attain- cess for acetylene production
is based only on the state of the reactants at the able by partial com- high-pressure gasification for
inlet to the reactor or the beginning of the reac- bustion of reactants synthesis gas production
tion and the phase of the reaction site (catalyst short residence times (Texaco, Shell)
phase, liquid phase with dissolved reactant). Reformer high reaction tem- steam cracking of naphtha
peratures attainable and other hydrocarbons to
Reaction products that form additional phases mainly by radiation ethylene
and inert substances of all types (except for well-defined resi- vinyl chloride production
solvents, as just noted) are ignored. dence times by cleavage of
Reactors used in electrothermal, electro- dichloroethane
pyrolysis
chemical, biochemical, photochemical, and of acetic acid to ketene
radiochemical processes are treated separately. of 2-methyl-2-pentene
Reactor types for which no industrial application to isoprene (in presence
is currently known are not listed. of HBr)
of chlorodifluoromethane
to tetrafluoroethylene
Fluidized-bed heat supplied along Lurgi Sandcracker
3.1. Reactors for Gas-Phase Reactions reactor with solids
Moving-bed heat supplied along Langer – Mond process for
reactor with solids production of ultrapure
Homogeneous gas-phase reactions utilized in nickel
industry are generally characterized by large continuous removal
of solid products
Reactor with fixed bed ensures Kureha process for
Table 1. Reactors for exothermic gas-phase reactions fixed bed of heat storage acetylene and ethylene
inerts and intensive production
Reactor mixing production of CS2 from CH4
type Features Examples of applications and sulfur vapor
Regenerative battery operation gas generation from heavy
Burner for high reaction rates combustion of H2S to SO2 furnaces no dilution by heat- crudes
very high reaction (Claus vessel) transfer medium
temperatures explo- carbon black production
sion limits must be (furnace, gas,
taken into thermal carbon black
consideration processes) chlorine –
hydrogen reaction
chlorination of
methanenitration positive or negative enthalpies of reaction and
of propane
high reaction temperatures. To obtain the desired
Tubular well-defined resi- chlorination
reactor dence time (tubes up of methane product spectrum, residence times must usually
to 1000 m long) of propene to allyl be very short. The high reaction temperature can
intermediate injec- chloride be maintained or the requisite heat supplied by
tion possible of butadiene to
burning part of the feed.
pressure drops dichlorobutane
good temperature chlorolysis of chlorinated Tables 1 and 2 and Figures 1 and 2 summarize
control capability hydrocarbons the reactors used for such reactions as well as
Reactor suitable for low re- chlorination of methane their applications.
with action rates
recycle good mixing
cooling inside or
outside reactor 3.2. Reactors for Liquid-Phase
Fluid- nearly isothermal chlorination Reactions
ized-bed conditions of methane
reactor because heat trans- of 1,2-dichloroethane
port is very efficient to tri- and In general, liquid-phase reactions are exother-
intensive mixing perchloroethylene mic. In the case of multiphase systems, intensive
chlorolysis of chlorinated mass and heat transfer must be provided for; this
hydrocarbons
is possible only in reactors with compulsory
Vol. 31 Reactor Types and Their Industrial Applications 297

Figure 1. Reactors for exothermic gas-phase reactions

A) Burner; B) Tubular reactor; C) Reactor with recycle;
D) Fluidized-bed reactor
a) Gaseous reaction mixture; a1, a2) Gaseous feed compo-
nents; b) Gaseous product; c) Coolant; d) Partial stream of
product; e) Catalyst Figure 2. Reactors for endothermic gas-phase reactions
A) Burner; B) Reformer; C) Fluidized-bed reactor; D) Mov-
ing-bed reactor; E) Reactor with fixed bed of inerts;
F) Regenerative furnaces
mixing, such as stirred tanks. Along with a num- a) Oxygen or air; b) Hydrocarbon; c) Fuel gas; d) Product;
ber of other reaction types, nearly all industrially e) Heat-transfer medium; f) Steam; g) Flue gas; h) Air;
important polymerization reactions take place in i) Quench; j) Reaction section; k) Regeneration section;
l) Catalyst; m) Convection zone
the liquid phase. For the sake of completeness,a
few important exceptions among polymerization
reactions are included in this section, even though reactions, the viscosity increases rapidly during
they do not fall under liquid-phase reactions the course of reaction and causes difficulties in
according to the classification principle stated heat and mass transport. In industry, this problem
above. These are, in particular, ‘‘gas-phase poly- is countered by (1) the use of special stirring and
merization’’ reactions, some of which take place kneading devices; (2) running the process in
over solid complex catalysts of the Ziegler – several stages; (3) raising the temperature as the
Natta type (high-density polyethylene, linear conversion increases; and (4) carrying out poly-
low-density polyethylene, and polypropylene). merization in thin films.
The essential feature of polymerization reac- Table 3 and Figures 3 and 4 summarize the
tions is that, in contrast to other liquid-phase types of reactors used in industry for liquid-phase
298 Reactor Types and Their Industrial Applications Vol. 31

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

Reactor type Features Examples of applications

Tubular reactor well-defined residence time polymerization reactions

good temperature control bulk polymerization to LDPE*
capabilities
polycondensation to PA 66* (2nd stage)
hydrolysis reactions
of ethylene oxide and propylene oxide to glycols
of chlorobenzene to phenol and chlorotoluene to cresol
of allyl chloride
production of ethyl acetate from acetaldehyde
production of isopropanolamine
dehydrochlorination of 1,1,2-trichloroethane to vinylidene
chloride
Reformer high reaction temperature visbreaking
well-defined residence time delayed coking
pyrolytic dehydrochlorination of tetrachloroethane to
trichloroethylene
high-pressure gasification of heavy crudes
Multitubular reactor large heat-transfer area bulk polymerization to PS*, HIPS*, and SAN*
multistage design with stirring
elements between stages is
possible
Sulzer mixer – reactor mixing elements consist of tubes bulk polymerization to PS* and polyacrylates
(plug-flow configuration) carrying heat-transfer medium
large heat-transfer area temperature-controlled starch conversion
suitable for processes in which
viscosity increases
intensive radial mixing with little
axial backmixing
very narrow residence-time
distribution
Reactor with external recirculation good mixing and heat-removal cleavage of cumene hydroperoxide to phenol and acetone
conditions (2nd stage of Hock process)
no moving parts Beckmann rearrangement of cyclohexanone oxime to
caprolactam
suitable for low reaction rates production of hydroxylamine sulfate (Raschig process)
heat exchanger can be placed production of phosphoric acid (wet process)
outside reactor
saponification of allyl chloride
bulk polymerization to PS*, HIPS*, SAN*, and PMMA*
Reactor with internal recirculation very intensive mixing production of melamine from molten urea (high-pressure
process)
production of aromatic nitro compounds
production of adipic acid from cyclohexanol and nitric acid
Bulk polymerization to PS*, HIPS*, and SAN*
Loop reactor for slurry polymerization polymerization reactions
suspension is circulated at high slurry polymerization to PP*
velocity to prevent buildup
production of HDPE* and LLDPE*
Powder-bed reactor liquid monomers supported on polymerization reactions
already polymerized granules
polymerization to HDPE* and PP*
block copolymerization to PE – PP*
for high conversion
evaporating and condensing
monomer acts as heat-transfer
agent (boiling, cooling)
vertical and horizontal designs
Stirred tank, batch or limited heat-transport capability polymerization reactions
semicontinuous
mechanical stirring means bulk polymerization to PS*, PMMA*,
Vol. 31 Reactor Types and Their Industrial Applications 299
Table 3 (Continued)

Reactor type Features Examples of applications

suitable for slow reactions HIPS*, ABS* (1st stage of each process)
polycondensation to PA 66*
solution polymerization to PVAC*, PAN*, PE*, PP*,
EPM*, EPDM*, SB*, SB – S*, EO – PO*
polycondensation to UF*, MF*, PF* resins
precipitation polymerization to PVC*, PAN*, PE*, PP*,
EPM*, EPDM* suspension polymerization to PVC*, EPS*,
PMMA*, PVAC*, and ion-exchange resins based on PS*,
HIPS*, ABS* (2nd stage)
emulsion polymerization to numerous polymer
dispersions
production of aromatic nitro compounds
sulfonation of benzene
esterification of PA* and alcohol to diphthalates
many other syntheses of dyes and pharmaceuticals
Stirred tank, continuous suitable for fast reactions with polymerization reactions bulk and solution polymerization to
large negative or positive heat of PS*, PMMA*, HIPS*, and ABS* (1st stage in each case);
reaction approximately complete copolymers with nonazeotropic monomer ratios
mixing conversion generally not
complete mechanical stirring
means
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
Cascade of stirred tanks suitable for slow reactions adapt- polymerization reactions transesterification of DMT* to
able to needed reaction conditions DGT* polycondensation to PETP* and PBT* solution po-
stage by stage residence-time lymerization to BR*, IR*, UP*, UF*, MF*, PF* resins
distribution close to that of tubular
reactor
solution or precipitation polymerization to PE*, PP*,
EPM*, EPDM*
emulsion polymerization to SBR*, CR*, NBR*
production of hydroxylamine sulfate (Raschig process)
production of cyclohexanone 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 tu-
bular reactor
production of methacrylamide from acetocyanohydrin
production of MDI* from MDA* and TDI* from TDA*
(Continued)
300 Reactor Types and Their Industrial Applications Vol. 31
Table 3 (Continued)

Reactor type Features Examples of applications

Reaction column reaction and separation in a single aldol condensation of n-butyraldehyde to 2-ethylhexenal
apparatus
equilibrium can be modified by saponification
removing one or more components
from reaction space
of chloropropanol with milk of lime
of fatty acids
esterification
of acetic acid with butanol
of phthalic anhydride with alcohols
decomposition
of amalgam
of ammonium carbamate to urea and water
Multichamber tank virtually identical to cascade of polymerization to LDPE* (ICI)
stirred tanks
requires little space
chamber-by-chamber feed injec- alkylation of isoparaffins with olefins (Kellogg)
tion possible
Tower reactor for continuous processes bulk and solution polymerization of PS*, HIPS*, ABS*,
SAN*, PA 6*
section-by-section temperature
control possible
little backmixing at high viscosity
also in cascade or with upstream
stirred tank
Ring-and-disk reactor narrow residence-time distribution final stage in production of PETP* and PBT*
Extruder for highly viscous media polymerization reactions
production of POM* from trioxane
final stage in production of PA 66*
Fluidized-bed reactor very good heat- and mass-trans- polymerization to HDPE*, LLDPE*, PP*
port conditions
fluid coking of heavy residual oils (Exxon)
melamine production from molten urea
Mixing head with injection mold special design for bringing several production of PUR*
liquid reactants together
Belt reactor with mixing head for fabrication of sheets and films production of PIB*, PMMA*, PUR*, PVAL*
Spinning jet (with coagulating for production of strands viscose spinning
bath)
Spray reactor direct heating in hot stream of gas thermal H2SO4 cleavage
production of MgO from MgCl2 (spray calci- nation)
Falling-film reactor gentle temperature control due to sulfation of fatty alcohols
large heat-transfer area
diazotization of aromatic amines
diazo coupling
*
The following abbreviations are used: ABS ¼ acrylonitrile – butadiene – styrene copolymer; BR ¼ butadiene rubber;
CR ¼ chloroprene rubber; DGT ¼ diglycyl terephthalate; DMT ¼ dimethyl terephthalate; EO – PO ¼ ethylene oxide –propylene oxide
block copolymer; EPDM ¼ ethylene – (propene – diene) copolymer; EPM ¼ ethylene – propene copolymer; EPS ¼ expandable
polystyrene; HDPE ¼ high-density polyethylene; HIPS ¼ high-impact polystyrene; IIR ¼ isobutylene – isoprene rubber (butyl rubber);
IR ¼ isoprene rubber (synthetic); LDPE ¼ low-density polyethylene; LLDPE ¼ linear low-density polyethylene; MA ¼ maleic
anhydride; MDA ¼ 4,40 -diaminodiphenyl methane; MDI ¼ methylene diphenylene isocyanate; MF ¼ melamine – formaldehyde;
NBR ¼ butadiene – acrylonitrile copolymer (nitrile rubber); PA ¼ polyamide; PAN ¼ polyacrylonitrile; PBT ¼ poly(butylene
terephthalate); PE ¼ polyethylene; PE – PP ¼ polyethylene – polypropylene copolymer; PETP ¼ poly(ethylene terephthalate);
PF ¼ phenol – formaldehyde; PIB ¼ polyisobutylene; PMMA ¼ poly(methyl methacrylate); PO ¼ poly(propylene oxide);
POM ¼ polyoxymethylene; PP ¼ polypropylene; PS ¼ polystyrene; PUR ¼ polyurethane; PVAC ¼ poly(vinyl acetate);
PVAL ¼ poly(vinyl alcohol); PVC ¼ poly(vinyl chloride); SAN ¼ styrene – acrylonitrile copolymer; SBR ¼ styrene – butadiene
rubber; SB ¼ styrene –butadiene block copolymer; SB – S ¼ styrene – butadiene – styrene block copolymer; TDA ¼ toluene diamine;
TDI ¼ toluene diisocyanate; UF ¼ urea – formaldehyde; UP ¼ unsaturated polyester.
Vol. 31 Reactor Types and Their Industrial Applications 301

Figure 3. Reactors for liquid-phase reactions

A) Tubular reactor; B) Reformer; C) Sulzer mixer – reactor; D) Reactor with external recirculation; E) Reactor with internal
recirculation (draft tube); F) Stirred tank; G) Cascade of stirred tanks; H) Column reactor; I) Multichamber tank; J) Fluidized-
bed reactor; K) Spray reactor; L) Falling-film reactor
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

302 Reactor Types and Their Industrial Applications Vol. 31
 Vol. 31 Reactor Types and Their Industrial Applications 303

reactions. Figure 4 shows special reactor designs Figure 5 illustrates reactor types for gas –
for polymerization reactions. liquid reactions. Important applications are listed
in Table 4.

3.3. Reactors for Gas – Liquid 3.4. Reactors for Solid-Catalyzed

Reactions Reactions

Gas – liquid reactions include many industrially Heterogeneous catalytic processes play a major
important processes, such as oxidation, alkyl- role in chemical technology, because many key
ation, chlorination, and flue-gas scrubbing. The products and intermediates can be manufactured
prerequisite for an efficient reaction is rapid mass in this way. Fluid reactants react in the presence
transport between gas and liquid. Important cri- of a solid catalyst, the mechanism as a whole
teria for assessment include consisting of the reaction proper and a series of
upstream and downstream transport steps.
1. The interfacial area
2. The mass or volume ratio of gas to liquid
3. The energy required to mix the phases 3.4.1. Reactors for Heterogeneous Gas
Catalysis

Other important factors are temperature con- Reactors with a fixed catalyst bed are distin-
trol, heat removal, and residence time (especially guished from those with moving catalyst.
that of the liquid phase).
Reactor design is dictated largely by the way Fixed-Bed Reactors (! Fixed-Bed Reac-
in which the interface is generated. The following tors) The characteristic features of a reactor
methods are possible: with fixed catalyst are the pressure drop of the
flowing gas in the catalyst bed and the danger of
1. Reactors with continuous liquid-phase and unstable operation points, especially with strong-
fixed gas distribution devices [bubble col- ly exothermic reactions, when flow through the
umns (! Bubble Columns), packed and tray catalyst bed becomes nonuniform. Fixed-bed
reactors (! Reaction Columns)] reactors must be shut down after a certain time
2. Reactors with mechanical gas dispersion onstream to regenerate or replace the catalyst.
(sparged stirred tanks) Fixed-bed reactors can be classified by the
3. Reactors with continuous gas phase and liquid type of temperature control:
dispersing devices (spray reactors, liquid-ring
pumps) 1. Reactors with no special temperature control
4. Thin-film reactors (! Thin-Film Reactors) features (adiabatic operation)

tFigure 4. Special reactor designs for polymerization reactions

A) Multitubular reactor; B) Multistage multitubular reactor with interstage stirring; C) Reactor with external recycle
(multitubular or screw-conveyor type); D) Reactor with external recycle (annular); E) Reactor with internal recirculation;
F) Sulzer loop reactor (see Fig. 3 C for detail of a single reactor); G) Loop reactor; H) Tower reactor; I) Ring-and-disk reactor;
J) Extruder reactor; K) Powder-bed reactor; L) Mixing head; M) Belt reactor with mixing head; N) Spinning jet with coagulating
bath
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
304 Reactor Types and Their Industrial Applications Vol. 31

Figure 5. Reactors for gas – liquid reactions

A) Tubular reactor with injector; B) Bubble column; C) Liquid-ring pump; D) Sparged stirred tank; E) Buss loop reactor;
F) Sulzer mixer – reactor in loop configuration; G) Reaction column; H) Spray reactor; I) Falling-film reactor; J) Rotary kiln;
K) Cascade of stirred tanks
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 (see Fig. 3 C for detail of a single reactor); n) Static mixer
Vol. 31 Reactor Types and Their Industrial Applications 305

Table 4. Reactors for gas – liquid reactions

(Continued)
306 Reactor Types and Their Industrial Applications Vol. 31
Table 4 (Continued)

2. Reactor systems with stagewise temperature Reactor systems with stagewise temperature
control (chiefly for equilibrium reactions) control are used primarily for equilibrium reac-
3. Reactors with continuous heat exchange tions. Such a reactor consists of simple adiabatic
along the flow path (polytropic operation) reactor elements connected in series and takes the
form of several units or a system housed in a
Fixed-bed reactors without equipment for common reactor shell. Temperature control is
temperature control are marked by a particularly accomplished by heat transfer between reactor
simple construction and low flow resistance, stages or by the injection of tempered gas or
which makes them suitable for high gas through- vapor streams at points along the flow path.
puts. A summary of these reactors appears in Table 6 and Figure 7 present reactor systems of
Table 5 and Figure 6. this type along with applications.
Vol. 31 Reactor Types and Their Industrial Applications 307

Table 5. Fixed-bed catalytic reactors for gas-phase reactions with no

special provisions for temperature control

Reactor type Features Examples of applications

Simple fixed-bed very simple design reforming (Platforming,

reactor (axial not suitable for reac- Rheniforming, etc.)
flow) tions with large hydrotreating
positive or negative CO converting
heat of reaction amination of methanol to
and high temperature methylamines
sensitivity desulfurization and
methanation in synthesis-
gas path upstream of
primary reformer
hydrogenation of nitro-
benzene to aniline
(Allied, Bayer) produc-
tion of vinyl propionates
from acetylene and
propionic acid isomeri-
zation of n-alkanes
dehydrogenation of
ethylbenzene to styrene
disproportionation of
toluene to benzene
and xylene
Fixed-bed reac- direct heating by methane cleavage in sec-
tor with com- combustion ondary reformer
bustion zone of part of hydro-
carbon feed
Radial-flow much lower pressure ammonia synthesis (Top-
reactor drop than soe, Kellogg)
axial-flow reactor dehydrogenation of eth-
multistage configu- ylbenzene to styrene
ration possible (Dow)
enhanced backmix- reforming
ing due to small
thickness of bed
uniformity of flow
requires exact sizing
of distributing and
collecting ducts
Shallow-bed used for high reaction oxidation of ammonia to
reactor rates and unstable NOx
products oxidative dehydrogena-
very short residence tion of methanol to
time formaldehyde
catalyst can also be in production of hydrocya-
gauze form nic acid from ammonia,
suitable for autother- methane,
mal operation and air (Andrussow
process)
Regenerative suitable when cata- dehydrogenation of bu-
furnace lyst ages rapidly tane to butadiene (Houdry
Figure 6. Fixed-bed catalytic reactors for gas-phase reac-
and can be process)
tions with no special provisions for temperature control
regenerated
A) Simple fixed-bed reactor; B) Fixed-bed reactor with
by burning off
combustion zone; C) Radial-flow reactor; D) Shallow-bed
reaction heat can be SO2 reduction with
reactor; E) Regenerative furnace
supplied by methane (Andrussow
a) Gaseous reaction mixture; b) Gaseous product; c) Catalyst;
catalyst regeneration process)
d) Air; e) Hydrocarbon; f) Flue gas; g) Reaction section;
battery operation
h) Regeneration section; i) Condensate; j) Steam; k) Steam
generator; l) Burner; m) Inert guard bed
308 Reactor Types and Their Industrial Applications Vol. 31

Table 6. Fixed-bed catalytic reactors for gas-phase reactions with

stagewise temperature control

Reactor type Features Examples of applications

Cascade of large pressure and tem- reforming of heavy

fixed-bed perature differences are gasoline
reactors possible hydrocracking
conversion of H2S and
SO2 to elemental sulfur
(Claus process)
isomerization of five-to-
six-ring naphthenes
Multibed used for exothermic ammonia synthesis
reactor with equilibrium reactions methanol synthesis
cold-gas injection of reaction hydrocracking
injection mixture leads to lower hydrogenation of benzene
conversion and thus desulfurization of vacu-
increased number um gas oil
of stages
injection of water lowers
concentration at constant
conversion
adaptation of bed depth to
progress of reaction
Multibed re- used for exothermic ammonia synthesis
actor with equilibrium reactions (ÖSW, Fauser,
interstage internal or external heat Montecatini)
cooling exchangers SO2 oxidation (with
no dilution effects interstage adsorption)
adaptation of bed depth to hydrodealkylation of
progress of reaction alkyl aromatics
Multibed re- used for endothermic dehydrogenation of
actor with equilibrium reactions ethylbenzene to styrene
heat supply interstage heating or in- (Dow)
terstage injection of su-
perheated steam

Figure 7. Fixed-bed catalytic reactors for gas-phase reac-

tions with stagewise temperature control
If the reaction process imposes special A) Cascade of simple fixed-bed reactors; B) Multibed reactor
requirements on temperature control, heat- with cold-gas or steam injection; C) Multibed reactor with
transfer surfaces must be located throughout intercooling (internal); D) Multibed reactor with intercooling
the reactor volume. The best-known design for (external)
a) Gaseous reaction mixture; b) Gaseous product; c) Catalyst;
such a reactor is the multitubular reactor, d) Heating agent; e) Cold gas; f) Coolant
which is frequently used in the chemical in-
dustry. The drawbacks relative to other fixed- trol medium before it flows through the catalyst
bed reactors include the much more compli- bed. Fixed-bed reactors with continuous heat
cated design and the limitation on throughput exchange are described in Table 7 and Figure
due to the smaller cross-sectional area avail- 8, along with applications.
able for flow.
Temperature control is achieved by the use of Moving-Bed and Fluidized-Bed Reactors
gaseous and liquid heat-transfer media. One (! Fluidized-Bed Reactors). In moving-bed
highly effective approach is the use of boiling reactors, transport of the catalyst is influenced
liquids (e.g., pressurized-water and evapora- by gravity and the drag force exerted by the
tively cooled reactors). A special case is the flowing reaction fluid on the catalyst particles.
autothermal process regime, in which the reac- The regime in the reactor can vary widely, de-
tion mixture itself is used as a temperature con- pending on the ratio of these forces. The fol-
Vol. 31 Reactor Types and Their Industrial Applications 309

Table 7. Fixed-bed catalytic reactors for gas-phase reactions with continuous temperature control

lowing features must be taken into consideration 2. Increased mechanical loads on the catalyst
when using reactors of this type: and reactor materials
3. The favorable conditions for heat and mass
1. The possibility of continuous catalyst re- transport, resulting from rapid movement of
generation solids and small catalyst grain size
310 Reactor Types and Their Industrial Applications Vol. 31

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. The crucial factor
for the efficiency of catalytic processes is the
wetting of the catalyst by the liquid. Since
reactors of this type are usually operated adia-
batically, local overheating is a danger, espe-
cially with exothermic reactions. Fixed-bed
reactors are well suited to high-pressure pro-
cesses by virtue of their simple design.
A second important group includes suspen-
sion reactors, in which very fine catalyst
particles are distributed throughout the volume
of the liquid (stirred tanks and bubble columns
with suspended catalyst). Because transport
resistances are reduced, these reactors offer
a close approach to isothermal operating con-
ditions and a favorable utilization of the cata-
lyst volume.
Sophisticated techniques are required to sep-
arate the finely divided catalyst from the liquid.
Equipment for this purpose can be installed
inside or outside the reactor. At the same time,
this arrangement permits continuous catalyst re-
placement. All suspension reactors have the
disadvantage of increased backmixing, especial-
ly of the liquid phase, which affects product
distribution.
The fluidized-bed reactor differs from
Figure 8. Fixed-bed catalytic reactors for gas-phase reac-
tions with continuous temperature control
the suspension reactor in the use of coarser
A) Multitubular reactor; B) Tubular reformer; C) Fixed-bed catalyst particles and the formation of a well-
reactor with heating or cooling elements defined agitated catalyst bed below the liquid
a) Gaseous reaction mixture; b) Gaseous product; c) Heating level.
agent or coolant; d) Catalyst; e) Cooling tubes; f) Circulating
water; g) Steam; h) Tube sheet; i) Fuel gas for burners; j) Off-
Industrially important reactors for liquid-
gas phase and gas – liquid reactions over solid
catalysts are listed, together with their appli-
cations, in Tables 9 and 10 and Figures 10
Table 8 and Figure 9 list reactor types and and 11.
applications.

3.4.2. Reactors for Liquid-Phase and 3.5. Reactors for Noncatalytic

Gas – Liquid Reactions over Solid Catalysts Reactions Involving Solids

Fixed-bed Reactors (trickle-flow reactors A variety of specialized reactors are available for
and packed bubble columns) are used for liquid- noncatalytic reactions involving solids. The dis-
phase reactions, as well as gas – liquid reac- cussion that follows deals only with the industri-
tions over solid catalysts. The presence of a ally important types.
Vol. 31 Reactor Types and Their Industrial Applications 311

Table 8. Moving-bed catalytic reactors for gas-phase reactions

Reactor type Features Examples of applications

Moving-bed gravity transport of catalyst cracking (TCC, Houdry flow process)

reactor reaction conditions largely similar to those in dehydrogenation of butane
fixed-bed reactor
advantageous when catalyst can be regenerated
by burning off residues
Fluidized-bed catalyst agitated by gravity and resistance force cracking (Kellogg, FFC, Flexicracking)
reactor of gas flow
almost isothermal conditions can be achieved in hydrocracking
fluidized bed
pressure drop independent of gas throughput reforming
over a wide range
form of fluidized bed can be varied as a function ammoxidation
of geometric and hydraulic conditions
strong backmixing internals to improve mass of propene to acrylonitrile (Sohio process)
transport and heat transfer are common
catalysts must have high abrasion resistance of o-xylene to o-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 o-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
dehyrogenation
of isopropanol
of n-butane to n-butene
production of chloromethylsilanes from chloro-
methane (catalytic gas – solid reaction)
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
Entrained-flow uses very fine-grained catalyst Fischer – Tropsch process (Synthol process)
reactor
whole quantity of catalyst circulates continu-
ously between reaction section and tempering
or regeneration unit
*
For abbreviations, see footnote to Table 3

3.5.1. Reactors for Noncatalytic high process temperatures; in addition, the struc-
Gas – Solid Reactions ture and geometry of the solid can change during
the reaction.
In general, noncatalytic gas – solid reactions are Reactors for this service can essentially be
characterized by low overall reaction rates and grouped into those for semicontinuous opera-
312 Reactor Types and Their Industrial Applications Vol. 31

Table 9. Fixed-bed catalytic reactors for liquid-phase and gas – liquid

reactions

Reactor type Features Examples of applications

Trickle-flow can operate in cocur- desulfurization and refin-

reactor rent or countercurrent ing of petroleum products
temperature control hydrocracking
by intermediate production of butynediol
injection or from acetylene and
recirculation formaldehyde
danger of uneven
liquid distribution
and incomplete wet-
ting of catalyst
narrow residence- direct hydration of pro-
time distribution pene to 2-propanol
(Texaco)
hydrogenation
of organic intermedi-
ates (butynediol, adipo-
nitrile, ethylhexenal)
of aldehydes, esters,
and carboxylic acids to
alcohols
of natural fats to fatty
acids
of residues (low-tem-
perature hydrogenation of
tars)
posthydrogenation
Packed bubble danger of flooding amination of alcohols
column limit throughput cobaltizer and decobalti-
capacity zer in oxo synthesis
catalyst subject to disproportionation of tol-
greater mechanical uene to benzene and
stress xylene
(retention necessary)
Figure 9. Moving-bed catalytic reactors for gas-phase high liquid propor-
reactions tion promotes heat
A) Moving-bed reactor; B) Fluidized-bed reactor; C) Entrained- removal
flow reactor large amount of
a) Reaction mixture; b) Gaseous product; c) Catalyst; d) Air; backmixing in liquid
e) Flue gas; f) Blocking steam; g) Reaction section; phase
h) Regeneration section

tion, that is, with no solids transport (vertical heat transport between gas and solid phases,
shaft kilns and rotary drums), and those for and heat-input capabilities. The first group
continuous operation, that is, with continuous includes moving-bed reactors. Since the gas
solids transport. The second type, in turn, can be has to flow through the bed of solids, mass and
divided into heat transport between the phases is relatively
good. Temperature control can be effected by
1. Reactors with gravity transport of solids simultaneously carrying out exothermic and
2. Reactors with mechanical transport of endothermic reactions in the same reactor.
solids Reactors with mechanical transport of solids
3. Reactors with pneumatic transport of solids include rotary kilns and multiple-hearth furnaces
(! Metallurgical Furnaces, Chap. 1.). Transport
These three groups differ widely with re- of gas and solid phases through the reactor
spect to residence time, conditions of mass and largely occurs separately. Intensive heat and
Vol. 31 Reactor Types and Their Industrial Applications 313

Table 10. Suspended-bed and fluidized-bed reactors for liquid-phase

and gas – liquid reactions over solid catalysts

Reactor type Features Examples of applications

Bubble column simple design hydrogenation

with small pressure drop of CO (Fischer –
suspended danger of undesired Tropsch synthesis)
catalyst liquid-phase of tars and coals
reactions (bottom phase)
inhomogeneous cat- of benzene to
alyst distribution cyclohexane
must hydrodesulfurization
be prevented
suitable if product
drops out as solid
Reactor with heat-exchange and hydrogenation of organic
external mixing devices in intermediates (nitroben-
recirculation external loop zenes, nitriles, nitro-
for continuous and naphthalenes, etc.)
batch operation
catalyst separation
outside reactor
Sparged stirred can also be operated hydrogenation of organic
tank with sus- in semicontinuous intermediates (nitro com-
pended catalyst and batch modes pounds, aromatics,
ensures intensive butynediol)
mixing of all phases fat hydrogenation
increased cost for catalytic refining
sealing and main-
taining stirrer drive
Cascade of higher final conver- hydrogenation of NO to
sparged stirred sions than in single hydroxylamine
tanks with sus- stirred tank continuous hydrogena-
pended catalyst suitable for slow re- tion of fats
action rates hydrolysis of fats to fatty
adaptable to inter- acids and glycerol pro-
mediate injection and duction of toluenedia-
other mine from dinitrotoluene Figure 10. Fixed-bed catalytic reactors for liquid-phase and
interconnections gas – liquid reactions
Fluidized-bed small pressure drop hydrocracking and A) Trickle-flow reactor (countercurrent); B) Trickle-flow
reactor catalyst must have desulfurization of heavy reactor (cocurrent); C) Packed bubble column
very high mechanical petroleum fractions and a) Liquid reactants; b) Gaseous reactants; c) Liquid product;
strength still residues (H-Oil d) Off-gas; e) Catalyst; f) Rupture disk
process; three-phase
fluidized bed)

group includes fluidized-bed and entrained-

flow reactors, dust roasters, and suspension
mass transfer occurs only at the surface of the bed furnaces. Because of the favorable conditions
of solids. Complete involvement of the solid for heat and mass transport, these reactors
phase in the reaction process depends on contin- offer shorter residence times and thus higher
uous, intensive mixing of the solids. Heat is often throughputs than other types. The installation
supplied directly by burners. More than one unit of heat-transfer surfaces, supplementary solid
can be in operation in a single apparatus (e.g., heat-transfer media, and direct heating is
drying, heating, cooling, and various reaction possible.
steps). Industrially important reactor types for
Solids transport by the gas stream is possi- noncatalytic gas – solid reactions are listed
ble only with small particle sizes and the in Table 11 and Figure 12 along with
narrowest possible grain-size distribution. This applications.
314 Reactor Types and Their Industrial Applications Vol. 31

Figure 11. Suspended-bed and fluidized-bed reactors for liquid-phase and gas – liquid reactions over solid catalysts
A) Bubble column with suspended catalyst; B) Fluidized-bed reactor; C) Buss loop reactor; D) Sparged stirred tank with
suspended catalyst; E) Cascade of sparged stirred tanks with suspended catalyst
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

3.5.2. Reactors for Noncatalytic Liquid – gas – solid reactions. Long residence times and
Solid Reactions high reaction temperatures are necessary, espe-
cially for reactions between different solids,
Reactors used for noncatalytic liquid – solid re- because of the low transport rates therein. Heat
actions must be designed for the transport and can be supplied by indirect or direct heating or by
mixing of phases, sometimes at high solids con- burning solid fuels.
tents. Batch and semicontinuous designs are Inert gases are employed for heat transport
therefore dominant. Table 12 and Figure 13 and agitation of the solids. Important applica-
present a survey of important reactor types for tions are listed in Table 13.
noncatalytic liquid – solid reactions and sample
applications.

3.6. Electrothermal Reactors

3.5.3. Reactors for Noncatalytic A variety of electrical heating schemes are used
Solid-Phase Reactions for some important noncatalytic reactions be-
tween gases and solids when very high reaction
Reactors used for noncatalytic solid-phase reac- temperatures and large quantities of heat are
tions are similar to those used for noncatalytic required. In the simplest case, heating elements
Vol. 31 Reactor Types and Their Industrial Applications 315

Table 11. Reactors for noncatalytic gas – solid reactions

(rods, strips, etc.) are used for this purpose. A The very high temperatures produced by the
much more efficient method, however, is direct , arc cause ionization in gases and thus activate
electric heating. Options here include arc, resis- the reactants; this feature is utilized in
tance, and induction heating. plasma processes for high-temperature pyrolysis
316 Reactor Types and Their Industrial Applications Vol. 31

Figure 12. Reactors for noncatalytic gas – solid reactions

A) Shaft kiln; B) Moving-bed reactor; C) Multiple-hearth reactor; D) Rotary kiln; E) Fluidized-bed reactor; F) Spray reactor;
G) Entrained-flow reactor
a) Solid feed components; b) Gaseous feed components; c) Solid product; d) Off-gas; e) Air; f) Cyclone; g) Drive unit
Vol. 31 Reactor Types and Their Industrial Applications 317

Table 12. Reactors for noncatalytic liquid – solid reactions

Reactor type Features Examples of applications

Stirred tank batch or semicontinuous operation predominant production of alkali cellulose and nitrocellulose
solids content limited by power of stirring apparatus reduction of nitrobenzene with metals
to aniline or hydrazobenzene
bauxite digestion
production of salicylic acid 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 stirred tanks for low reaction rates and high final conversions apatite digestion
Tank with liquid semicontinuous operation with solids cellulose digestion
recirculation fixed in tank and liquid recirculating
production of ammonium sulfate from ammonium
carbonate and gypsum
Rotary drum for batch operation, high solids content production of cellulose acetate and cellulose ethers
production of AlF3 by wet process
Fluidized-bed reactor Semicontinuous operation water treatment
intensive liquid circulation
Steeping press combination of reaction and liquid separation production of cellulose ether
batch operation
Kneader used for highly viscous media production of nitrocellulose, cellulose ether,
and cellulose acetate
for batch operation production of celluloid from nitrocellulose
production of superphosphate
Screw-conveyor reactor used for highly viscous media digestion of rutile or ilmenite with H2SO4
batch operation
Multiple-hearth reactor continuous operation production of acetylene from carbide
(dry gas generator)
long solids residence time
Rotary kiln direct heating for high reaction temperatures digestion of fluorspar or phosphate with
H2SO4reducing decomposition of H2SO4
in presence of carbon

(! Plasma Reactions, Section 2.1.; ! Metallur- 3.7. Reactors for Electrochemical

gical Furnaces, Section 5.5.). Processes (! Electrochemistry,
Equipment used for solid reactions includes 2. Inorganic Electrochemical Processes;
arc and resistance-heated reduction furnaces and
! Metallurgical Furnaces)
the Acheson furnace (! Metallurgical Furnaces,
Section 5.2., ! Metallurgical Furnaces, Section
In electrochemical reactions, electrons are sup-
5.3.). The Acheson furnace is a resistance-heated
plied to a reactant in the electrolyte or re-moved
device for pure solid – solid reactions; that is, in
from it with the aid of an electric current. A
contrast to other processes, no melting of the
minimum voltage called the decomposition
solid charge occurs. All electrothermal processes
voltage must be applied to the electrodes for this
are characterized by very high equipment cost
purpose. In addition to the electrochemical reac-
and high electric power consumption. The pre-
tions occurring on the electrode surface, trans-
requisite for their economical operation is a low
port processes and chemical reactions in the
unit price for energy.
electrolyte bath are important.
This group of reactors and their applications
Electrochemical processes have the following
are summarized in Table 14 and Figure 14.
advantages:
318 Reactor Types and Their Industrial Applications Vol. 31

Figure 13. Reactors for noncatalytic liquid – solid reactions

A) Stirred tank; B) Cascade of stirred tanks; C) Tank with liquid recirculation; D) Rotary drum; E) Fluidized-bed reactor;
F) Steeping press; G) Kneader; H) Screw-conveyor reactor; I) Multiple-hearth reactor; J) Rotary kiln
a) Liquid feed components; b) Solid feed components; c) Liquid product; d) Solid product; e) Drive unit
Vol. 31 Reactor Types and Their Industrial Applications 319

Table 13. Reactors for noncatalytic solid-phase reactions

Reactor type Features Examples of applications

Shaft reactor see Table 11 metallurgical processes, e.g.,

powder boriding of iron-based materials
direct reduction of iron ores with carbon (Kinglor – Metor process)
Multiple-hearth reactor see Table 11 calcination
Rotary kiln see Table 11 cement production
burning of lime, dolomite, gypsum, and magnesite
calcination
thermal decomposition of FeSO4 and BaCO3
reduction of barite with carbon to BaS
reduction of ores with carbon (e.g., to ZnO)
Fluidized-bed reactor see Table 11 burning of lime (multistage)

1. High product purity (no secondary reactions) For these reasons, electrochemical processes
2. Low reaction temperature (except for fused- are used only when no available thermal or
salt electrolysis) catalytic process can accomplish the same pur-
3. Easy control of reaction rate through variation pose, which is especially true in the production of
of electrode voltage chlorine, aluminum, and copper. A survey of
important applications for electrolytic processes
They have the following disadvantages: is given in the following:

Chlorine production by chlor – alkali

1. High energy losses in the system electrolysis
2. Large space requirements . Mercury amalgam process
3. High investment costs . Diaphragm-cell process

Table 14. Electrothermal reactors

320 Reactor Types and Their Industrial Applications Vol. 31

Metal refining
. Copper
. Nickel

Electrolysis of inorganic materials

. Electrolysis of water
. Fluorine production by electrolysis of hydro-
gen fluoride
. Production of sodium chlorate by electrolysis
of sodium chloride
. Electrochemical oxidation of sodium chlorate
to perchlorate
. Recovery of persulfuric acid
. Production of ozone

Electrolysis of organic materials

. Production of adiponitrile from acrylonitrile
. Production of dimethyl sebacate
. Reduction of nitrobenzene to aniline
. Production of perfluorocaprylic acid
. Production of dihydrostreptomycin

The design of the reaction system (i.e., cell

geometry and flow configuration), the elec-
trode arrangement and material, and control
of phases and concentrations are highly pro-
cess specific.
Typical designs are illustrated in
Figure 15.

3.8. Reactors for Biochemical

Processes (! Biochemical Engineering;
! Biotechnology, 1. General)

Some important biochemical processes, such as

Figure 14. Reactors for electrothermal processes
A) Plasma torch; B) Fluohm reactor; C) Arc-heated reduction
those used in making beer, wine, alcohol, and
furnace; D) Resistance-heated reduction furnace; E) Acheson baker’s yeast, have been known for centuries.
furnace; F) Reactor with indirect electric heating Typical of these reactions is their use of enzymes
a) Solids; b) Molten product; c) Gaseous reaction mixture; as biocatalysts. The enzymes can be present as
d) Gaseous product; e) Catalyst; f) Carrier gas; g) Electrodes;
h) Plasma; i) Slag; j) Resistive charge; k) Off-gas
cell constituents of living microorganisms, or
they can be isolated in dissolved form or bound
to inert supports (! Biocatalysis, 2. Immobi-
lized Biocatalysts). The prerequisite for the use
. Membrane process of live microorganisms is the provision of favor-
able living conditions. Such conditions include
Metal winning by fused-salt electrolysis the presence of optimal amounts of nutrients and
. Aluminum oxygen (in aerobic processes); maintenance of
. Magnesium the temperature, pressure, maintenance of pH in
. Sodium certain ranges, and sterile conditions.
Vol. 31 Reactor Types and Their Industrial Applications 321

Figure 15. Reactors for electrochemical processes

A) Metal winning by fused-salt electrolysis; B) Electrolytic metal refining; C) Electrolysis of inorganic material; D) Electrolysis
of organic material; E) Mercury amalgam process; F) Diaphragm-cell process; G) Membrane process
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 þ 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

In addition to these factors, metabolism sion of gas from outside must be prevented;
is important for reactor design. Aerobic gases and solvent vapors resulting from the
processes require an adequate supply of reaction must also be removed from the
oxygen. In anaerobic processes, the admis- reactor.
322 Reactor Types and Their Industrial Applications Vol. 31

Table 15. Reactors for submerged aerobic processes

Reactor type Features Examples of applications

Sparged stirred tank various stirring and circulation apparatus production of antibiotics amino acids yeast
suitable for higher viscosities
Reactors with forced circulation
Bubble column very broad residence-time distribution production of yeast
good dispersion properties aerobic wastewater treatment
Jet reactor free jet, jet nozzle, or central tube designs
possible
for low viscosities
high gas velocities, good mass transfer
Submerged-jet reactor very broad residence-time distribution processing of spent sulfite liquor
good mass transfer fermentation of waste substrates
danger of slime settling out
Reactors with natural
circulation
Bubble column much backmixing, broad residence-time production of biomass citric acid
distribution
for low viscosities
simple construction
Loop reactor for low viscosities
little dispersive action
Sieve-tray tower good mass transfer due to fine bubble
structures
Surface reactors
Trickle-bed reactor low mass-transfer coefficients and negli- production of acetic acid aerobic waste-
gible dispersive action water treatment
Reactor with rotating internals use of paddles, cylinders, etc. suitable for aerobic wastewater treatment
viscous media

Reactors for these processes can be classified cations of these reactor types include fermenta-
as follows: tion processes (e.g., lactic acid fermentation,
alcohol production, mash fermentation).
1. Reactors with dissolved or suspended bioca- The immobilization of enzymes on suitable
talysts (submerged processes) for aerobic or supports enables the use of reactor designs simi-
anaerobic conditions lar to those for heterogeneous catalytic process-
2. Reactors with immobilized biocatalysts for es. If the enzymes are supported on semiperme-
aerobic or anaerobic conditions able membranes, separation and reaction can be
combined in membrane reactors.
Reactors for use in submerged aerobic pro- Reactors with immobilized biocatalysts, to-
cesses have provisions for efficient aeration and gether with their applications, are listed in Ta-
intensive liquid circulation. Aeration is accom- ble 16 and Figure 17.
plished with fixed or moving distributors, noz-
zles, or submerged or rotating jets. Liquid circu-
lation is ensured by various stirring systems or by 3.9. Reactors for Photochemical and
forced or natural convection. Radiochemical Processes
A summary of the most important reactor
types and their applications is given in Table The photochemical and radiochemical princi-
15 and Figure 16. ples are used to a very limited extent in indus-
Reactors for anaerobic conditions do not have try because conditions for economical opera-
aeration equipment. Usually, sealed vessels with tion (e.g., high quantum efficiency) are seldom
or without stirrers are used (fermenters). Appli- met.
Vol. 31 Reactor Types and Their Industrial Applications 323

Figure 16. Reactors for submerged aerobic processes

A) Sparged stirred tank; B) Bubble column with forced circulation; C) Jet reactor with forced circulation; D) Submerged-jet
reactor with forced circulation; E) Bubble column with natural circulation; F) Loop reactor; G) Sieve-tray tower; H) Trickle-bed
reactor; I) Reactor with rotating internals
a) Gas; b) Fermentation medium; c) Product; d) Off-gas; e) Recycle stream
324 Reactor Types and Their Industrial Applications Vol. 31

Table 16. Reactors for biochemical processes over immobilized biocatalysts (for aerobic and anaerobic conditions)

3.9.1. Photochemical Reactors (! Photo- evolved and supplemental cooling devices must
chemistry, Chap. 3.) be employed.
A survey of reactor types and their indus-
The rate of a photochemical reaction is deter- trial applications appears in Table 17 and
mined by the concentration of reactants and by Figure 18.
the intensity, quantity, and wavelength of light
supplied. Light in the wavelength range that is
absorbed by the reaction mixture can be formal-
3.9.2. Radiochemical Reactors (! Radia-
ly treated as a reactant. As a consequence,
tion Chemistry)
photochemical reactions exhibit a position de-
pen-dence of the reaction rate, even with com-
Radiochemical reactions are induced by the
plete mixing, because the flux density of light
action of ionizing radiation. In addition to high
quanta decreases with increasing distance from
energy consumption, the extremely complex
the light source. The feasible thickness of the
design of radiation sources and shielding
reaction space, and thus the type and size of
works against the wider use of this reaction
reactor that can be used, depend not only on the
principle.
power of the emitter, but also on the optical
The following are known applications:
properties of the reactor material and the reac-
tion medium. Intensive mixing must be ensured,
especially for thick beds. Light can be supplied 1. Production of ethyl bromide (Dow process,
from outside (through the reactor wall) or by Fig. 19)
submerged light sources. When high-power 2. Radiative cross-linking of poly(vinyl chlo-
light sources are used a large amount of heat is ride) and polyethylene
Vol. 31 Reactor Types and Their Industrial Applications 325

Figure 17. Reactors for biochemical processes over immobilized biocatalysts (for aerobic and anaerobic conditions)
A) Stirred tank with suspended catalyst; B) Fixed-bed reactor; C) Fluidized-bed reactor; D) Membrane reactor
a) Biocatalyst; b) Fermentation medium; c) Product; d) Off-gas; e) Permeate; f) Membrane tube; g) Retentate

Table 17. Reactors for photochemical processes

Reactor type Features Examples of applications

Tubular reactor for homogeneous gas- and liquid-phase reactions chlorination of benzene to hexachlorocyclohexane
sulfochlorination
chlorination of methane to dichloromethane
Bubble column requires favorable optical conditions and low viscosity sulfochlorination of paraffins (cascade)
also used in cascades and with central tube side-chain chlorination of aromatics
production of dodecanethiol from 1-dodecene and H2S
Stirred tank optically induced differences in reaction rate oximation of cyclohexane with nitrosyl chloride
equalized by intensive stirring
production of provitamin D3
Falling-film reactor suitable for poor optical conditions because production of vitamin D2
film is very thin
Belt reactor especially for highly viscous media polymerization to PAN, PAC, PVC, PVAC*
*
PAN ¼ polyacrylonitrile; PAC ¼ polyacrylate; PVC ¼ poly(vinyl chloride); PVAC ¼ poly(vinyl acetate).
326 Reactor Types and Their Industrial Applications Vol. 31

Figure 19. A reactor for a radiochemical process (production

of ethyl bromide by the Dow process)
a) Gaseous reaction mixture; b) Liquid product; c) Shielding

References
1 ‘‘Chemische Reaktoren-Ausr€ustungen und ihre Berech-
nung’’, Verfahrenstechnische Berechnungsmethoden, part
5, VEB Deutscher Verlag f€ur Grundstoffindustrie, Leipzig
1981.
2 H. Gerrens: ‘‘Über die Auswahl von Polymerisationsreak-
toren, ’’ Chem. Ing. Tech. 52 (1980) 477 – 488.
3 K. H. Reichert, W. Geiseler (e ds.): Polymer Reaction
Engineering, VCH Verlagsgesellschaft, Weinheim, Ger-
many 1989.
Figure 18. Reactors for photochemical processes 4 W.-D. Deckwer: ‘‘Bioreaktoren, ’’ Chem. Ing. Tech. 60
A) Tubular reactor; B) Bubble column; C) Stirred tank; (1988) 583 – 590.
D) Falling-film reactor; E) Belt reactor 5 K. Sch€ugerl: ‘‘Characteristic Features of Bioreactors’’,
a) Gaseous feed components; b) Liquid feed components;
Bioreaction Engineering, vol. 2, John Wiley and Sons,
c) Product; d) Emitter; e) Coolant; f) Off-gas; g) External
reflector; h) Falling film; i) Belt New York 1990.
6 A. Heger: Technologie der Strahlenchemie von Polymeren,
Carl Hanser Verlag, M€unchen 1990.

Further Reading
3. Production of alkyltin compounds
4. Degradation of polymers A. Cybulski, J. A. Moulijn, A. Stankiewicz: Novel Concepts
in Catalysis and Chemical Reactors, Wiley-VCH, Wein-
heim 2010.
Some reactions, such as chlorinations, can be G. F. Froment, K. B. Bischoff J. De Wilde: Chemical Reactor
implemented in either photochemical or radio- Analysis and Design, 3rd ed., Wiley, Hoboken, 2010.
chemical form. H. A. Jakobsen: Chemical Reactor Modeling, Springer,
Berlin 2008.
Vol. 31 Reactor Types and Their Industrial Applications 327

W. L. Luyben: Chemical Reactor Design and Control, Wiley, Sons, Hoboken, NJ, online DOI: 10.1002/
Hoboken, NJ 2007. 0471238961.1805010320011813.a01.pub2.
U. Mann: Principles of Chemical Reactor Analysis and E. B. Nauman: Chemical Reactor Design, Optimization, and
Design, 2nd ed., Wiley, Hoboken, NJ 2009. Scaleup, 2nd ed., Wiley, Hoboken, NJ 2008.
U. Mann: Reactor Technology, ‘‘Kirk Othmer Encyclopedia
of Chemical Technology’’, 5th edition, John Wiley &