Tubular Plug Flow Reactors

JO€ RG SAUER, Institute of Catalysis Research and Technology (IKFT),

Eggenstein-Leopoldshafen, Germany
NICOLAUS DAHMEN, Institute of Catalysis Research and Technology (IKFT),
Eggenstein-Leopoldshafen, Germany
EDMUND HENRICH, Institute of Catalysis Research and Technology (IKFT),
Eggenstein-Leopoldshafen, Germany

1. General Plug Flow Reactor 2.3. Multitubular PFR Configurations . . 11

Characteristics . . . . . . . . . . . . . . . 2 3. Technical Applications . . . . . . . . . . 12
1.1. Fundamental Types of Chemical 3.1. General Aspects. . . . . . . . . . . . . . . 12
Reactors . . . . . . . . . . . . . . . . . . . . 2 3.2. Large Scale Commercial Applications 13
1.2. Flow Patterns in Tubular Reactors . 2 3.2.1. Olefins by Steam Cracking of
1.3. PFR Heating and Cooling via Tube Naphtha . . . . . . . . . . . . . . . . . . . 13
Wall . . . . . . . . . . . . . . . . . . . . . . 3 3.2.2. Gas Oil Cracking in the FCC Riser
1.4. Mass and Energy Balance. . . . . . . . 4 Reactor . . . . . . . . . . . . . . . . . . . . 16
1.5. Adiabatic Temperature Increase . . . 5 3.2.3. Vinyl Chloride Production by EDC
1.6. Pressure Drop . . . . . . . . . . . . . . . . 6 Dehydrochlorination . . . . . . . . . . . 17
1.7. Residence Time Distribution . . . . . . 6 3.2.4. High Pressure Ethylene
1.8. Dimensional Analysis of PFRs for Polymerization for Low Density
Design and Scale-Up . . . . . . . . . . . 7 Polyethylene (LDPE). . . . . . . . . . . 17
2. PFR Types and Configurations . . . . 8 3.3. Other Commercial Applications. . . . 19
2.1. Adiabatic PFRs. . . . . . . . . . . . . . . 8 3.3.1. Gas Phase Halogenation of
2.1.1. Single-Stage Adiabatic PFR . . . . . . 8 Methane and Light Alkanes. . . . . . 19
2.1.2. Multistage PFRs with Interstage 3.3.2. HCN-Production in the Degussa
Heat Exchange . . . . . . . . . . . . . . . 9 BMA Process . . . . . . . . . . . . . . . . 19
2.1.3. Stepwise Cold Shot Cooling. . . . . . 9 3.3.3. Ketene via Acetic Acid or Acetone
2.1.4. Feed-Effluent Heat Exchange . . . . . 10 Cracking . . . . . . . . . . . . . . . . . . . 20
2.2. Polytropic PFRs . . . . . . . . . . . . . . 10 3.3.4. Ethylene Glycol via Ethylene Oxide
2.2.1. Jacketed PFRs . . . . . . . . . . . . . . . 10 Hydrolysis . . . . . . . . . . . . . . . . . . 21
2.2.2. Radiation Heating . . . . . . . . . . . . 11 3.3.5. Various Additional Applications . . 21
2.2.3. Tubular Loop Reactor . . . . . . . . . 11 3.4. Research and Development . . . . . . . 21

Abbreviations and Symbols: EDC ethylene dichloride

dc/dt feed rate
A area, m2 dz axial thickness
Arr Arrhenius number F molar flow rate, mol/s
Bo Bodenstein number FEHE feed-effluent heat-exchanger
ci concentration of key species i, HDPE high density polyethylene
mol/L k, k0 reaction rate coefficient for 1st order
cp specific heat, J kg
1 K
1 reactions, s
1
CSTR continuous stirred tank reactor L length, m
d diameter (inner), m L0 dispersion distance, m
D molecular diffusioncoefficient, LDPE low density polyethylene
m2/s LSCC Linde–Selas combined coil design
Da Damk€ ohler 1 number M mol mass, g/mol
De effective diffusion coefficient, m2/s m reaction order

# 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b04_181.pub2
2 Tubular Plug Flow Reactors

MRT mean residence time 1. General Plug Flow Reactor

MTR maximum temperature rise, K Characteristics
n amount, mol
p pressure, bar 1.1. Fundamental Types of Chemical
PE polyethylene
PFR tubular plug flow reactor
Reactors
PP polypropylene Tubular plug flow reactor (PFR) and continuous
Pr Prandtl number stirred tank reactor (CSTR) (see ! Stirred-
Q heat transfer rate J/s Tank and Loop Reactors) are the two funda-
r reaction rate, mol/s mental types of continuously operated chemical
r radius, m reactors (Fig. 1). Their essential characteristics
Re Reynolds number are compared in Table 1.
RTD residence time distribution For all positive reaction orders, the volume of
Sc Schmidt number the CSTR is larger than the volume of the PFR
T temperature, K for the same conversion. The reactor volume
t time, s ratios increase with the reaction order m and
tr reduced time t=t the conversion X. Reactor performance equa-
t mean residence time, s tions for the CSTR and the PFR for reactions of
tr mean reduced residence time mth order are tabulated in [1, p. 111–112].
u fluid velocity, m/s Reactor performance equations are relations
U overall heat transfer coefficient, between the rate r and extent X of a reaction,
J m
2 K
1 s
1 the reaction volume V and the feed rate dc/dt.
V reaction volume, L A homogeneously operated tubular reactor
VC vinyl chloride [2, p. 427–452] is a straight, bent, or coiled slim
X conversion cylinder with an inner diameter d, length L, and
z axial distance, m an aspect ratio (L/d) of usually > 30. The mean
r nabla operator residence time (MRT) of a reaction mixture is
calculated for homogenous operation by
Greek Letters: MRT ¼ t ¼ L=u.
The densities r and the specific heat per mass
DrG Gibbs reaction energy, J/mol of a liquid remain approximately constant
DrH reaction enthalpy, J/mol despite changes of temperature T and concentra-
DTad adiabatic T rise, K tions ci of species i during conversion. If gases
l heat conductivity coefficient: are involved the corresponding volume changes
J m
2 s
1 K
1 between inlet and outlet must be considered.
m dynamic viscosity kg m
1 s
1
ni stoichiometry coefficient of species 1.2. Flow Patterns in Tubular Reactors
i in reaction
n kinematic viscosity ¼ m/r m2/s Laminar flow in an empty cylinder pipe with
r density kg/m3 Re < 2 300 generates a parabolic velocity profile
r/d relative pipe roughness with axial symmetry; the maximum velocity in
t reaction time, s the center is twice the mean velocity. The result-
ing broad residence time distribution (RTD) is
Subscripts: without much interest for chemical reaction
engineering. RTD calculations for laminar
e effective flow in tubular reactors are reported in [3]. In
f fluid microreactors with small radial dimensions of <
i chemical key species i 10
4 m, molecular diffusion is able to create an
j chemical key reaction j almost uniform RTD over the cross section even
r radial at laminar flow conditions.
w wall
Turbulent flow patterns generate a flat,
z axial
almost uniform velocity profile over the tube
 Tubular Plug Flow Reactors 3

Figure 1. A) Continuous stirred tank reactor (CSTR); B) Tubular plug flow reactor (PFR)

Table 1. Comparison of CSTR and PFR

CSTR PFR

Design L/d ratio 1–2 25–10 000

Pressure drop negligible significant
Flow pattern turbulent turbulent
Fast mixing axial and radial radial
Mean residence time long short
Residence time distribution exponential Gaussian
Flow problems short cuts, dead volume dead volume
Dynamic response to disturbance immediate delayed

cross section; this is termed plug or piston flow. conversion X ¼ 1 with maximum temperature
All volume elements have about the same veloc- rise (MTR) including side reactions into
ity and MRT and a technically narrow RTD. account. Nonadiabatic, also termed polytropic
Turbulent transport and mixing by eddy diffu- PFRs, with a cooling jacket, are designed to
sion is characterized by an effective dispersion prevent reactant decomposition or reactor dam-
coefficient De. The transport time t ¼ d2/2De age by high temperatures. In nonadiabatic
over the small pipe diameter d compared to heated or cooled reactors, a temperature maxi-
transport over the tube length L is (L/d) 2 times mum or minimum can develop between inlet
faster, in typical PFRs at least 1 000 times. The and outlet at some intermediate axial position.
corresponding radial r and axial z dispersion Temperature is the most important control var-
coefficients Der and Dez can be different, but iable for PFRs. For safe operation, reliable
this difference is low in empty PFRs. The radial c model predictions are required for controlling
and T gradients in the cross section are quickly steady state as well as transient conditions.
equalized by turbulent mixing. Axial dispersion A disturbance or feed change in an ideal
smoothes also c and T profiles along the axis. CSTR causes an immediate change of reactor
Effective dispersion coefficients Der and Dez for composition or conditions. In an ideal PFR, the
turbulent transport and mixing are several orders response is delayed, because the disturbance
of magnitude larger than molecular diffusion moves downward with the flow velocity. The
coefficients D of ca. 10
5 m2/s (STP) in gases dynamic response between reaction rate and
or ca. 10
9 m2/s in liquids. heat removal can create highly complex situa-
tions, even oscillatory conversion rates [4, 5].
1.3. PFR Heating and Cooling via Tube Intuitive predictions are frequently misleading,
Wall due to the interplay of many variables. For
example, an increase of coolant temperature
In an adiabatic PFR, the temperature along the can result unexpectedly in a lower effluent
tube rises or falls monotonically between inlet temperature: Due to the higher initial reaction
and outlet by DTad ¼ X  MTR. A safe rate, the conversion is almost completed in the
design of an adiabatic PFR should take full first section and the temperature maximum is
4 Tubular Plug Flow Reactors

Figure 2. Differential volume in a PFR suited for balance equations

a) Area: 2pr  dr; b) dr; c) Corresponding differential pipewall area: 2pr  dz for heat exchange; d) Radius r; e) dz;
f) Differential annular ring volume: dV ¼ 2pr  dr  dz

shifted towards the inlet. Now more pipe wall reactors (! Fixed-Bed Reactors), balance
area is available downstream for efficient cool- equations are usually described for a differen-
ing of an almost completely converted reactor tial annular volume dV in the pipe cross section
mixture. Simulation models are available for with radius r and r þ dr and an axial thickness
isothermal conditions or co- or countercurrent dz as shown in Figure 2.
coolant flow in jacketed PFRs, including the In the generalized form of the balance equa-
more complex transient conditions with poten- tion, the mass and energy change in the annular
tial instabilities and multiple states [6, p. 251- reference volume dV ¼ 2pr  dr  dz,
406]. A frequent application is constant cooling designed as accumulation of a conserved quan-
with a liquid boiling under a certain pressure on tity is equal to the input minus output by
the shell side of a multitubular reactor. In convection u  ci plus axial and radial disper-
addition, internal cooling by evaporation of a sion Dez@ci =@z, Der@ci =@r plus an amount @ci
liquid spray is practiced for gas phase reactions of species i generated by chemical reactions j
or dilution with an entrained, fine, cold, and with rates rij within dV. The individual contri-
inert material for both gas and liquid phase butions for a key species i are shown as an
reactions. example:

change ¼ þ inflow
outflow þ chemical generation

dci  2  pr  dr  dz ¼ uci 2prdr jz dt
uci 2prdr jzþdz  dt þ ri  2p  r  dr  dz  dt
Dez @c
@z 2prdr
i
jz dt
Dez @c
@z 2prdr
i
jzþdz  dt (plus axial dispersion)
Der @c
@z 2prdr
i
jr dt
Der @c
@z 2prdr
i
jrþdr  dt (plus radial dispersion)

1.4. Mass and Energy Balance Sum after division by @V  @t ¼ 2pr

@r  @z  @t:


The balance equations for the conservation of @ci @ci  u @2 @ci @ @ci
¼ þ Dez þ Der r þri
mass, heat, and momentum for key species in @t @z @z2 @z @r @r
convection axial and radial dispersion chemical generation
combination with chemical kinetics and ther-
modynamics are the basis for reactor design [7]. The flow velocity for axial convective trans-
In empty or packed [2, chap. 11] tubular port is u and the effective dispersion (eddy
 Tubular Plug Flow Reactors 5

diffusion) with coefficients De in radial r and Steady-state—PFR with axial dispersion Dez
axial z direction are Der, Dez. Radial dispersion
over the small cross section is fast and the 0 ¼ Dez r2 ci
rci  u þ vir

concentration and temperature gradients are

negligible. Steady-state—ideal PFR without dispersion
The mass balance equation for species i is
0 ¼
rci  u þ vir
obtained by summation of the individual
contributions followed by division by dt and
by the differential reference volume Heat balance equations Dynamic balance
dV ¼ 2pr  dr  dz. The transient heat bal- equation, with heat conduction
ance equation for an adiabatic reactor can be @T X
obtained analogously by replacing the concen- rcp ¼ le r2 T
rcp rT  u þ
DHiri
@t
tration of chemical species ci by heat energy or
temperature T. Steady-state with heat conduction
X
Heat balance equation. 0 ¼ le r2 T
rcp rT  u þ
DHiri

P @T
P @T @
 @T
 P
i Mi  ci  cpi @t ¼ i Mi  ci  cpi  U @z þ @z le;z  @z
j D r H j rj þ d ðTw
Tf Þ
4U

heat change in balance volume convective heat flow conductive heat flow reaction heat heat flux via wall

Steady-state–no radial temperature gradient

Mi molecular mass of species i; U overall X
heat transfer coefficient; 0 ¼
rcp rT  u þ
DHiri
le effective thermal conductivity in axial (z)
direction, J m
1 s
1 K
1; Tw, Tf wall and fluid Radial dispersion is usually assumed infi-
temperature; ci molecular concentration of spe- nitely fast. This is equivalent with very rapid
cies i cpi specific heat of species i mixing over the small cross section, so that no
radial temperature and concentration gradi-
Q ¼ U  AðTw
Tf Þ ents are present, which is a reasonable
A surface area m2, Q heat transfer rate j/s, U assumption for small diameters d with large
overall convective heat transfer coefficient with L/d- ratios. A simplification of the dynamic
balance equation is obtained for steady state
U ¼ 0:01545 þ 0:6885  10
6 1=d  Re conditions @ci =@t ¼ 0, where c and T in a
Typical values for gases are U  1 J m
2 K
1 reference volume dV remain constant. The

1
s [8]. Values up to about 100 kW per m2 pipe last balance equation represents the ideal
surface area can be attained with external radi- PFR with infinitely fast radial mixing but do
ation heating. not change with time without axial dispersion
Heat transfer by axial conduction (dispersion) at steady state, which is a reasonable approxi-
is much smaller than convective axial heat flow mation for most practical applications. In an
and usually be neglected. In adiabatic reactors, ideal PFR, all differential disk-like axial vol-
the heat flux via the wall is zero. For steady state ume elements of the fluid move downward
conditions, the amount of heat in the reference without mutual interaction with exactly the
volume does not change: @T=@t ¼ 0 same velocity u, such as a plug or piston and
Balance equations using the nabla operator leave the reactor after exactly the same time;
r and stepwise simplification for individual they can be described as independent CSTRs.
cases are:
Mass balance equations Dynamic bal- 1.5. Adiabatic Temperature Increase
ance—PFR with axial dispersion Dez
@ci By combining mass and heat balance equations
¼ Dez r2 ci
rci  u þ vir
@t for an adiabatic reactor, the adiabatic
6 Tubular Plug Flow Reactors

temperature rise DTad can be calculated: formal balance equation in Section 1.4 Mass
and Energy Balance. Experimental Dez values
X
DTad ¼ Tout
Tin ¼ X  F in ð
Dr HÞ= F in  cpi of 0.1–10 are reported in [2, p. 559,
i
Figure 11.6.1]
cpi specific heat of constituent i, Dr H Dispersion model [1, p. 293–320]. Axial
enthalpy of reaction, Fin molar flow rate. dispersion is caused by the random turbulent
For a crude first estimate it can be assumed, eddy motion superimposed to the convective
that the mass specific heat of a reaction flow velocity u. During the MRT t, a volume
mixture does not change significantly during element randomly moves the mean axial dis-
conversion. tance L0 by eddy diffusion (¼ dispersion)
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1.6. Pressure Drop [9] L0 ¼  2  Dea  t ¼ 2  Dea  L=u

For PFRs with turbulent flow at Re > 5 000, the After a certain time, e.g., after the MRT ¼ t,
pressure drop a symmetric Gaussian-shaped RTD is obtained
and described as
dp=dz ¼ 3:5=d  r  u2

1 t1
1
Eðtr Þ ¼ pffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  exp
p  4  Dea  u  L 4  Dea =u  L
increases in proportion to the kinetic energy per
fluid volume 1=2 r  u2 or the square of the fluid The relative width 2 L0 /L of the RTD at the
velocity. For highly viscous reaction mixtures inflection point and the dimensionless Boden-
with m > 1 Poiseuille (PL), turbulence condi- stein number, Bo, are
tions result in high flow velocities of minimum
umin > 2 300  m  d/r and unacceptable high 2l0 =L ¼ 2
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2  Dea =u  L ¼ 2  2=Bo;
pffiffiffiffiffiffiffiffiffiffiffi
Bo ¼ u  L=Dea
pressure drops. In addition, in long reactor
pipes, pressure drops by bends or other inter- This is a good approximation for Bo > 100
nals, such as static mixers, must be considered. with a narrow RTD. Because the RTD front
section of a pulse marker leaves the outlet of a
PFR first and the tail section some time later;
1.7. Residence Time Distribution
the symmetry measured in the effluent is some-
[10, p. 361–374] what distorted and shows a steeper rise and a
flatter tail. This causes a little increase in the
A unified description of the RTD for different relative width of the RTD, but only about 2% at
PFRs is possible by using a dimensionless Bo ¼ 100.
reduced residence time tr ¼ t=t, with the The RTD also changes somewhat with the
MRT t and mean reduced residence time boundary conditions if plug flow or turbulence
tr ¼ 1. In an ideal PFR, all volume elements
exists outside the inlet and outlet of the reactor
move with the same velocity u and have exactly volume. The relative RTD width (e.g., for so
the same MRT t ¼ L=u when leaving the called “open” boundary conditions with turbu-
reactor. In a real PFR, the diffusion-like statis- lent flow outside from inlet and exit) is
tical motion of the turbulence vertices is super-
imposed to the convective flow velocity u. This qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
causes an effective axial dispersion with a 2l0 =L ¼ 2 2  Dea =u  L þ 2  2  Dea =u  L ¼ 2 2=Bo þ 8=Bo2

coefficient Dez, which is several orders of mag-

nitude larger than molecular diffusion. The At Bo > 100 the difference of the half width
contribution of molecular diffusion to the is only < 2% and negligible.
0
dispersion coefficient Dez ¼ Dez þ D  Dez
becomes negligible. Tanks-in-Series-Model. This gives an
Dez in a packed PFR includes the different alternative description of the RTD [1, p. 321–
length of the tortuous pathways through the 338]. The PFR volume is divided into n equal
packing and can be described with the same CSTR volumes. The RTD for n serial tanks is
 Tubular Plug Flow Reactors 7

Figure 3. RTDs for the tanks-in-series model with n serial CSTRs [10, p. 367] t r Eðtr Þ ¼ residence time distribution or
distribution density function

visualized for various n in Figure 3. The num- ones. Input data are simultaneous mass, heat,
ber n in the model does not need to be an and momentum balance equations as well as
integer. kinetics, thermodynamics, and construction
and operating data. This is not a simple task
En ðtr Þ ¼
1

1
 tn
1  expð
tr Þ; and many approximations and simplifications
tr ðn
1Þ! r
are applied. Using the description of an ideal
PFR is a first significant simplification and
justified in many cases. Corrections for axial
The variance (L0 /L) 2 ¼ 1/n the relative RTD back mixing are frequently done later, e.g., by
width is increasing the reactor length by 10% to 50%.
pffiffiffiffiffiffiffiffi A large number of 15 geometry, material,
2L0 =L ¼ 2 1=n with Bo ¼ n=2 þ 1=2: and process parameters are relevant to describe
a simple irreversible first order reaction in an
Thus for Bo > 50, n > 100 CSTRs are in ideal PFR. The complete list is as follows: flow
series; the RTD width of < 30% of the mean velocity u, tube diameter d, L, fluid density r,
residence time still allows a satisfactory dynamic viscosity m, heat capacity cp, temper-
approximate representation by an ideal PFR. ature of the feed stream Tin, diffusion
The two models and the corresponding coefficient De, c0  Dr H, DT between fluid
RTDs are similar but not identical. A difference and inner wall; concentrations cin, cout. The
is backmixing that occurs in the dispersion dimensions of these variables are composed
model due to symmetrical diffusion; the of five basic quantities: length, time, mass,
tanks-in-series model allows only forward temperature, and particle number; here also
motion from vessel to vessel. the enthalpy difference DH is added as a sixth
basic quantity. Dimensional analysis is a sys-
tematic way to reduce and simplify physical
1.8. Dimensional Analysis of PFRs for relations to the minimum set of dimensionless
Design and Scale-Up [11, p. 144–156] variables pi. The theory of similarity says that
(! Scale-Up in Chemical Engineering) this complex problem with 15 dimensional
variables can be transformed to a simpler prob-
Dimensional analysis is a tool for designing and lem with only 15
6 (¼ number of basic
scaling-up new reactors and simulating existing quantities), i.e., nine dimensionless variables
8 Tubular Plug Flow Reactors

Table 2. Reduced dimensional matrix for PFR description

r L k0 Tin cin  Dr H n m D cp l

Mass 1 0 0 0 0 0 1 0
1 0
Length
3 1 0 0
3 1
1 2 0
1
Time 0 0
1 0 0
1
1
1 0
1
Temperature 0 0 0 1 0 0 0 0
1
1
Heat 0 0 0 0 1 0 0 0 1 1

pi. Four of these dimensionless numbers are only for fast reactions with residence times
trivial: from about 0.1 s up to a maximum of ca.
100 s. Disadvantages of PFRs are the possibility
p1 ¼ L=d of a larger pressure drop and a more complex
p2 ¼ cout =cin
p3 ¼ DT=Tin
process control.
p4 ¼ E=RT ðArrhenius number; ArrÞ The PFR types are divided into adiabatic and
polytropic PFRs either with or without heat
The remaining five dimensionless quantities exchange through the tube wall. Multitubular
can be obtained with standard algorithm from configurations, either adiabatic or polytropic,
the dimensional matrix in Table 2 [11, p. 144– are typical configurations for higher capacities
147]. in technical facilities. The adiabatic reactors
comprise the simple, single-stage base case and
p5 ¼ vðL  k0 Þ
1 ¼ ðk0 tÞ
1 ðL=v ¼ t reaction timeÞ some multistage configurations with heat
p6 ¼ mðr  L2  k0 Þ ¼ ðk0  t  Re  L=dÞ
1 exchange prior to each individual stage. The
p7 ¼ DðL2  k0 Þ
1 ¼ ðk0  t  Re  Sc  L=dÞ
1
p8 ¼ cp  r  Tin  ðc0 Dr HÞ
1 ¼ Da
1
nonadiabatic or polytropic PFRs are types with
p9 ¼ lT0 ðcinDr HL2 k0 Þ
1 ¼ ðk0tRePrDaL=dÞ
1 coolant surrounding the pipe wall and heat
transfer through the pipe wall surface area,
which can be achieved with a jacketed or
The total set of dimensionless numbers p1– radiation-heated PFR. Tubular PFRs share
p9 cannot be simplified further many common aspects with catalytic fixed
bed reactors e.g., in view to physico-chemical
L=d; cout =cin ; DT=Tin ; Arr; k0 t; Re; Sc; Pr; Da description and configuration [12, 2, p.
493–637].
With this set of dimensionless parameters,
only partial similarity is expected. Discussion
of PFR modeling and scaling problems is found 2.1. Adiabatic PFRs
in [6, p. 251–368]. Conversion-relations X for
first and second order reactions in a PFR are 2.1.1. Single-Stage Adiabatic PFR
reported in [1, pp. 312]. Conversion X depends
on reaction variable k  t  cn
1
0 , dispersion
Single stage adiabatic PFRs are attractive
Dez/u L, and reaction order m. because of their simple and cheap empty
pipe construction, often without thermal insu-
lation and thus easily accessible from the out-
2. PFR Types and Configurations side (Fig. 4). Cleaning operations or deposit
[6, p. 251–286] removal might be difficult, especially removal
or prevention of coke deposits on the inside of
PFRs are usually chosen due to their narrow the reactor. Technical PFRs have diameters in
RTD and their simple design and fabrication. the range of 0.01 to 1 m and the pipe length L
The large wall area to reactor volume ratios, ranges from few meters up to 1 000 m. Long
especially for small pipe diameters, assists heat pipes are usually bent to reduce the total length;
transfer. Small diameters are also well suited the term coil is frequently used to designate a
for high pressures. However, the volumes of tubular PFR. Some auxiliary equipment is
PFRs are usually relatively small and suited almost inevitable, especially to adjust the
 Tubular Plug Flow Reactors 9

Figure 4. Single-stage adiabatic PFR

a) Feed preheater; b) Separator

Figure 5. Multistage adiabatic PFRs with interstage heat exchange

a) Adiabatic PFR; b) Interstage heater or cooler

feed temperature as the most important process 2.1.2. Multistage PFRs with Interstage Heat
variable. A recycle pipe for the unreacted feed Exchange
after product separation from the effluent and a
feed preheater (or precooler) are mostly com- The maximum reactor temperature in an adia-
bined with heat recovery in a feed-effluent heat batic reactor can be limited by dividing the PFR
exchanger (FEHE). A minimum feed tempera- into a series of smaller adiabatic PFRs with
ture must be exceeded to attain a suitable initial lower conversions X  1 and correspondingly
reaction rate to reduce the reactor volume. A lower DTad ¼ X  MTR. Each of the individ-
maximum feed temperature should not be ual PFRs in series has its own feed cooler for
exceeded to prevent overheating with decom- new feed temperature adjustment. The multi-
position reactions and equipment damage. stage configuration allows a higher overall
Temperature and product concentrations average reaction temperature with a higher
along the axis of an adiabatic PFR with a single average reaction rate and with a lower reactor
irreversible reaction change monotonically volume (Fig. 5).
until the exit. For a complex reaction network
concentration extrema are possible, e.g., for 2.1.3. Stepwise Cold Shot Cooling
successive reactions A ! B ! C; concentra-
tion B can go through a maximum. A partial This mode of operation is similar to interstage
conversion X < 1 can prevent an adiabatic cooling. The PFR is subdivided into smaller
temperature rise to dangerous levels, but at adiabatic PFRs. Stepwise cooling is achieved
the expense of a higher recycle rate of by injecting unconverted cold feed before each
unconverted feed and a larger reactor. individual PFR-stage (Fig. 6). However, the

Figure 6. Cold shot cooling (liquid spray evaporation or heat carrier)

a) Adiabatic PFR; b) Cooler
10 Tubular Plug Flow Reactors

Figure 7. PFR with feed-effluent heat exchanger (FEHE)

a) FEHE; b) Control of feed temperature; c) Adiabatic PFR

cooling capacity is limited by the available 2.2. Polytropic PFRs

amount of feed. The injected unconverted
feed streams may be subcooled to below the 2.2.1. Jacketed PFRs [6, chap. 5.7–8, 6.8–10]
minimum temperature required for reaction
ignition. The ignition temperature is then In nonadiabatic PFRs, heat is transferred
attained after mixing with the hot converted through the tube wall into a heating or cooling
feed stream. medium surrounding the tubes (Fig. 8). The
Multistage cooling (or heating) can also be smaller the tube diameter, the higher is
obtained by stepwise injection and mixing an the specific surface area for heat transfer.
inert gas, liquid or solid heat carrier feed The increased pressure drop in the tubes has
stream. Evaporation cooling with a liquid spray to be considered and more energy is needed for
injected into a reaction gas phase is also fre- pumping.
quently applied. In cooled or heated PFRs, there can be
temperature maxima or minima at intermediate
axial positions. To acquire a feeling for these
2.1.4. Feed-Effluent Heat Exchange complex phenomena is difficult; model calcu-
lations are more reliable. A simple example
Countercurrent heat exchange between a cold illustrates a temperature maximum develop-
feed stream and a hot effluent combines heat ment: Heat generation decreases with decreas-
recovery with feed preheating (Fig. 7). This is ing conversion rate dX/dt toward the exit and if
now a standard method for feed temperature the coolant temperature between feed and efflu-
adjustment and combined with a controlled ent temperature is constant, a temperature max-
feed (or effluent) bypass for better temperature imum can develop. A dynamic response
control. An additional feed preheater is usually between heat generation and removal can gen-
needed for start-up but is not shown in Figure 7. erate oscillatory reaction rates.
Integration of an FEHE into a process requires Coolant flow in the jacket is cocurrent,
special attention, because energy feedback countercurrent, or crosscurrent with the same
can create dynamic control problems [6, p. temperature at each axial point. Multitubular
254, p. 369–405]. reactors with many parallel tubes are designed

Figure 8. Jacketed PFR

a) Jacket; b) PFR
 Tubular Plug Flow Reactors 11

Figure 9. Radiation heated PFR

a) Gas or oil burners, b) PFRs; c) Furnace

for high capacities. The design corresponds to a is recycled together with the products (Fig. 10).
shell-and-tube-bundle heat exchanger. Constant Heat exchange in the loop section allows pre-
temperature cooling is obtained with a boiling cise temperature control of the reactor temper-
liquid at the shell side, normally pressurized ature. At high recycle rates or loop–effluent
water from 100 C to ca.300 C. High heat transfer flow ratios, the residence time behavior
coefficients are achieved by boiling; vapors are approaches the CSTR; the initially narrow
condensed and recycled in a closed loop. RTD broadens up. For applications with heat
transfer through the pipe wall, the diameters are
2.2.2. Radiation Heating usually below 0.1 m. A series of tubular loop
reactors corresponds to a tanks-in-series con-
Large-scale PFRs are frequently used for endo- figuration with very efficient cooling.
thermic decomposition reactions at higher tem-
perature. The processes are operated at elevated
temperatures to shift the thermodynamic equi- 2.3. Multitubular PFR Configurations
librium to the product side. Usually several
reactor pipes are arranged in a furnace and The capacity is increased by parallel operation
are heated by a number of oil and gas burners of up to > 1 000 PFRs. To determine suitable
installed at the sidewalls and the bottom of the design data, experiments with a single pipe are
furnace (Fig. 9). Care must be taken to radiation sufficient, but care must be taken to maintain
“shadowing” to prevent uneven heating of the the same flow in each of the parallel tubes. The
pipe surfaces. Elliptical tube cross sections give reactor design corresponds to a shell-and-tube
more uniform pipe skin temperatures and inter- bundle heat exchanger, with a cocurrent or
nal coke deposits. This results in longer run countercurrent (crosscurrent) heat exchange
length and tube life times [13, 14]. medium on the shell side (Fig. 11). A conve-
nient method with a good overall heat transfer
2.2.3. Tubular Loop Reactor is a shell-side liquid, boiling at a controlled
temperature and pressure. In a radiation furnace
This configuration should not be confused with several PFR tubes are arranged in such a way,
recycling of unconverted feed after product that uneven heating by radiation shielding is
separation. Here, the whole reaction mixture minimized.

Figure 10. Tubular loop reactor

12 Tubular Plug Flow Reactors

Figure 11. Multitubular PFR with shell-side heat exchange medium

a) PFRs; b) Shell side

3. Technical Applications geometrical characteristics are the simple

design, the small diameter d and the high L/d
3.1. General Aspects aspect ratio, the small volume with a high
surface area per volume, and the narrow RTD
The most important technical applications of for turbulent flow. Design aspects are treated in
PFRs are summarized in Table 3. [15a]
Additional technical applications with lower Tubular reactors with high L/d ratio > 30
production capacity are: and small diameter d < 0.1 m have a large
surface area per volume equal to 4/d and are
 Gas-phase halogenation of CH4 and light well suited for highly exothermal or endother-
alkanes mal reactions. The small diameters ease the
 HCN production via the Degussa BMA construction of high-pressure reactors. How-
process ever, the vessel volume needs to be small in
order to minimize the pressure loss in the
 Ethylene glycol via ethylene oxide
turbulent regime, which is suited only for suf-
hydrolysis ficient fast conversions in the range from < 1 s
 Ketene via acetic acid or acetone cracking up to ca. 100 s.
 PFR reactors for highly exothermic The temperature at which the reaction equi-
reactions (nitration, sulfonation, fluorina- librium shifts from the educt to the product side
tion, amination, etc.) can be estimated from thermodynamic reaction
data with DrG ¼ DrH
TDrS at DrG ¼ 0 (for
The special geometry of tubular reactors negligible temperature dependence of DrH and
favor their use for certain reactions. Essential DrS). Typical decomposition reactions produce

Table 3. Important technical applications of PFRs

Reaction type Phase Dr p, bar T,  C geometry L/d MRT, s

Steam cracking of naphtha for C2-C5 pyrolysis gas endo 10 800–900 80/ 0.1 0.2–1
olefin production
Gas oil cracking in the FCC riser reactor catalytic pyrolysis gas, solid endo 1þ 500 30/ 1 few s
VC production by EDC dehydrochlorination dechlorination gas endo 10-30 500 20–30
LDPE production by high pressure polymerization liquid exo ca. 2000 up to 300 1 000/0.06 ca. 100
PE polymerization
 Tubular Plug Flow Reactors 13

more molecules and are endothermic with pos- diameter and creates the same characteristics as
itive DrH. They proceed more rapidly at higher turbulent flow in larger tubes. Commercial
temperatures above T > þDrH/þDrS usually in applications are NOx removal from the huge
the gas or vapor phase at moderate or atmo- flue gas volumes of fossil-fired power stations
spheric pressure. For high temperatures above and the numerous exhaust gas catalysts in
ca. 600 C, tubes are heated externally by radi- automobiles.
ation. Metallic construction materials such as
special Ni-alloys are used up to 900 C and
special ceramic tubes up to 1 300 C. 3.2. Large Scale Commercial
Typical synthesis or partial combustion Applications
reactions are exothermal and exergonic and
prone to runaway. Control of the risk of run- 3.2.1. Olefins by Steam Cracking of Naphtha
away with damage of product and reactor [16 vol. 4, p. 546–550]
requires careful temperature control. With neg-
ative reaction enthalpy
DrH and entropy DrS, At present about 0.3  109 t/a crude oil is used
the reaction becomes exergonic below T < as feed for steam cracker plants to generate 0.15

DrH/
DrS. Because of the low conversion  109 t/a ethylene and propene, in addition to
temperature, usually < 500 C to prevent some higher olefins and gasoline byproducts.
C

C bond scission, the reaction must often This large-scale olefin production supplies
be accelerated by catalysts. The multitude of more than half of the reactive starting material
commercial applications of PFRs packed with for the organic chemical industry especially for
catalyst pellets is treated in ! Fixed-Bed thermoplastics polyethylene (PE) and poly-
Reactors and [2, p. 493–637]. For empty tubular propylene (PP) production (0.13  109 t in
reactors with a catalyst coating at the wall, see 2010). Steam crackers are therefore among
Section 3.3.2 HCN-Production in the Degussa the largest chemicals facilities. Figure 12 shows
BMA Process. the steam cracker facilities at BASF, Antwerp,
Ceramic monolith catalysts have long chan- Belgium. The arrangement comprises several
nels with small ca. 1 mm square cross section. furnaces, each with several coils to ensure
There is laminar flow, but molecular diffusion reliable production security. A simplified
is fast enough for rapid mixing over the small flow sheet is shown in Figure 13. The main

Figure 12. Photo of the steam cracker facilities at BASF, Antwerp, Belgium
14 Tubular Plug Flow Reactors

Figure 13. A) Simplified flow sheet of a naphtha steam cracker; B) Furnace side view
a) Coil; b) Radiation zone; c) Convection zone; d) Sidewall burner; e) Quench cooler; f) Evaporation chamber; g) Quench
oil preheater; h) Quench oil feed preheater; i) Economizer; j) Feed preheater; k) Steam heater; l) Feed and steam heater;
m) Furnace

feedstock for steam crackers in the EU is and four years [16 vol. 4, p. 546]. The PFR
naphtha with a boiling point range of 40– pipes are bent to reduce the length of the
190 C. In the United States and the Gulf States, furnace casing of the reactor. Two or more
ethane is a frequent feedstock for ethylene.
Examples of product spectra from different
feedstocks at the same pyrolysis conditions are
presented in [17; 16 vol. 5, p. 191; 18] and
Figure 14.

Reactor Design. The first commercial steam

crackers for olefin production in Europe have
been designed in the 1950s and indicate the
transition from coal to oil as the major carbon
raw material for organic chemistry. An old and
now abandoned process concept was naphtha
cracking with hot sand as a heat carrier [16c].
An actual steam cracker design is an empty
PFR with an inner pipe diameter of d ¼ 0.1 
0.03 m, a length L  40–100 m and a wall
thickness in the range of 0.01 m. Highly tem-
perature resistant pipe construction materials
are SS 18% Cr, 8% Ni for maximum wall
temperatures of 830 C and Incoloy 800 up to
900 C. Lifetimes for pipes with a low relative Figure 14. Approximate yields of major steam cracker
roughness d=d < 2  10
4 are between two products
 Tubular Plug Flow Reactors 15

pipes are installed in a hot furnace and heated parameter to characterize the cracking condi-
by oil or gas burners at the side and the bottom. tions is the severity, which increases with the
Impurities in the oil, in particular sulfur and final temperature and the residence time. The
vanadium can cause serious corrosion; thus, dimensionless kinetic severity function is k  t,
natural gas is preferred at higher temperatures. where k is a first order rate coefficient and t the
If several pipes are present, uneven radiation mean residence time. At low severity condi-
heating by shadowing needs to be avoided. tions (ca. 2) with 760–810 C and 1–1.5 s MRT,
An industrial steam cracker plant is a central the higher C3 and C3þ olefin yields are favored.
unit in a chemical complex for a very reliable At high severity conditions (ca. 5) with 810–
continuous supply of subsequent facilities. Sev- 880 C and < 1 s MRT, ethylene yields are at a
eral furnace units, each equipped with several maximum, C3þ olefin yields decrease, and coke
coils are switched together to maintain the deposits increase. Modern crackers prefer high
required high reliability and availability. Alter- severity conditions. A typical product spectrum
natives to the conventional PFR design have not for high severity naphtha cracking with ethane
been successful [18, 20]. and propane recycle is ethylene 35%, propene
15%, C4-hydrocarbons, remaining gases H2,
Operating Data. Heat for the endothermal and CH4.
naphtha cracking reactions may be supplied via
the tubular reactor wall by external radiation Chemical Reaction Mechanism. Hydro-
with up to 900 C effluent temperature with a carbon cracking is s endothermic and proceeds
heat load of 3  1011 J m
2 h
1; ca. 2.9  109 J in homogeneous gas phase as a free radical
are needed per kg feed. The capacity of a new chain reaction. A simple and technically impor-
single pipe is thus in the range of 3 t/h or 2.5  tant example is ethane cracking to ethylene,
104 t/a. The technical ranges of design data of described in detail in [2, p. 349–355; 29–31].
PFRs for naphtha cracking are reported in [16 
Initiation : C2 H6 ! CH3 þ  CH3
vol. 4, p. 554]. Propagation : C2 H6 þ  CH3 ! 
C2 H5 þ CH4
Efficient steam crackers operate at gas C2 H5 ! C2 H 4 þ  H
velocities approaching the velocity of sound. C2 H5 þ  H ! C2 H 4 þ H 2
This corresponds to mean residence times t < Termination : CH3 þ  H

C2 H5 þ  C2 H5
!
!
CH4
C4 H10
1 s in ca. 100 m long pipes with pressure drops
of 1 bar or more. Because cracking proceeds The dissociation energy of the C

H bond
under volume increase lower pressure is (f 40040 kJ/mol) is higher than that of the
favored. Initial operating pressures of several C

C (35020 kJ/mol) [32]. The chain is
bar compensate for the pressure drop. Hot therefore initiated with the homolytic scission
steam in a molar steam-to-hydrocarbon ratio of a C

C bond. The chain propagates via
of about 0.5 is added as an inert diluent, to radical reactions and is terminated by
lower the partial pressure of hydrocarbons, and recombination of two hydrogen atoms or
to increase the product yields. Water vapors are any two other radicals; termination reactions
easily removed from the effluent by condensa- generate byproducts, such as methane or
tion. Steam above 800 C removes much of the butane.
coke deposits by gasification. However, after
one or few month, the increasing pressure drop Olefins from High Boiling Hydrocar-
becomes too high and the coke deposits must be bons. Gas oil pyrolysis can be performed
removed by combustion during a shut-down in a PFR at 800  50 C [22, 33, 34] with short
period [23, 24]. Methods for online decoking residence times of 0.2 s. Pyrolysis of high
are described [25, 26]. Modeling of coke boiling hydrocarbons in a tubular PFR pro-
formation during steam cracking is covered duces much carbon deposits. The steam-to-
in [27, 28]. hydrocarbon mole ratio is therefore increased
The olefin product spectrum with ethylene from about 0.5 for naphtha to about 1 for gas
and propene as the main products depends on oil. The Linde–Selas combined coil design
feedstock, pressure, temperature, and residence (LSCC) furnace proved to be well suited for
time and amounts to about half. The essential this process.
16 Tubular Plug Flow Reactors

Figure 15. Simplified flow sheet of a FCC-unit [6]

a) Air blower; b) Regenerator; c) Cyclones; d) Riser reactor

3.2.2. Gas Oil Cracking in the FCC Riser simplified FCC flow sheet is shown in
Reactor [35] Figure 15.

In 2012, about 80% of the crude oil was cracked Re ¼ u  d=n  10  1=300  10
6  3  104
mainly in the form of heavy gas oil in riser
reactors of the FCC units with the primary aim Hot gas oil is preheated, vaporized in a
to improve fuel yields. Gasoline yields of 35– furnace, and mixed at the bottom of the riser
50% have been obtained. In addition, the inter- with steam and a 10–20-fold mass excess of hot
est in propene production increased. Propene zeolite catalyst particles [35]. The catalyst par-
yields up to 25% can be obtained [36]. With ticles are entrained with negligible slip upwards
various catalysts and operating conditions, FCC with about 10 m/s at ca. 500 C and about 3 bar.
units are flexible to serve various aims. This mode of operation is termed transport
The FCC units in modern oil refineries have reactor. The bulk flow is turbulent:
a throughput of ca. 200 t/h. Because of the fast With an axial dispersion coefficient assump-
reactions with MRTs of few seconds, the reactor tion of Dea  1 the relative RTD-width can be
volume remains relatively small. The riser estimated to be 2  L0 =L ¼ 2ð2Dea =u  LÞ1=2
reactor in the FCC unit is a vertical pipe with  0:17 or ca. 17% of the reactor length, which
about 1 m diameter and ca. 30 m height. The is compatible with plug flow conditions.
regenerator for the spent catalyst is a large The hot, slightly overheated catalyst with cp
fluidized bed for char combustion from the 1 kJ kg
1 K
1 provides the heat for the
catalyst particles with oxygen deficient air. A endothermal cracking reactions by cooling
 Tubular Plug Flow Reactors 17

down by about 40 K to 800  30 K. During consider several conflicting factors and operat-
cracking, coke deposits are formed up to ca. ing details for optimum integration into the
0.5% of the catalyst mass. At the top of the riser whole VC production process. Multitubular
reactor, the hot coked catalyst particles are PFR consists of several layers of horizontal
efficiently separated by cyclones and routed Inconel pipes that are heated externally by
into the fluidized bed regenerator for reheating radiation; small tube diameters of few centi-
and simultaneous burning down the majority meters are used to improve heat transfer. Dur-
of the coke to ca. 0.2%. The catalyst is thus ing operation, the pressure drop increases
regenerated and recycled in a closed loop. gradually by soot deposits. Deposits must be
About 0.1 kg of catalyst is consumed per removed periodically by burning, steaming, or
ton of feed. Process control must consider shot blasting with steel pellets.
the interactions within the coupled riser–
regenerator system [37, 37a]. Other Dehydrochlorination Products.
Comparable PFR technologies are used for
3.2.3. Vinyl Chloride Production by EDC the production of tri (CCl2¼CHCl) and tetra
Dehydrochlorination (CCl2¼CCl2) chlorinated ethylene with usually
> 90% conversion. They are used for dry
In 2011 ca. 36  106 t/a of vinyl chloride (VC) cleaning and as inflammable solvents.
were polymerized to PVC worldwide. Until
800 K
1950, VC was produced by HCl addition to CH2 Cl
CH2 Cl þ 2 Cl2




! CHCl ¼ CCl2 þ3 HCl Dr H ¼ 54:4 kJ=mol
acetylene. In modern VC plants, vinyl chloride
is produced through direct chlorination of eth-
ylene to form 1,2-dichloroethylene (ethylene 3.2.4. High Pressure Ethylene Polymeriza-
dichloride ¼ EDC) followed by endothermal tion for Low Density Polyethylene (LDPE) !
decomposition to VC in tubular reactors. The Polyethylene
reactors are operated at about 750–800 K and
10–30 bar in the gas phase. Commercial facili- Predominance of PE Thermoplastics.
ties have production capacities above several Ethylene is the most important organic base
106 t/a. chemical per mass. In 2010, the majority of ca.
8  107 t/a ethylene was used for polyethylene
Oxychlorination: CH2 ¼ CH2 þ 2 HCl þ 12 O2 ! (PE) production. PE has worldwide the highest
CH2 Cl
CH2 Cl þ H2 O production rate of all polymers. Optimum
ca: 800 K;10
30 bar
Dehydrochlorination: CH2 Cl
CH2 Cl












!
material properties for a variety of applications
CH2 ¼ CHCl þ HCl Dr H ¼ 72:4 kJ=mol
can be preselected by the PE polymerization
mode: Either high-pressure process for LDPE
The large amounts of HCl couple product or suspension, solution, or gas phase processes
are exploited via oxychlorination of ethylene to for HDPE and other PE types.
recycle the chlorine. The EDC decomposition
mechanism proceeds in thermally initiated free LDPE Properties and Applications. Due
radical reactions [39, 16, vol. 5, p. 25–27]. A to its flexibility and transparency, soft LDPE is
high 99.9% EDC purity is required. Trace the preferred packaging material. The packag-
impurities inhibit the dehydrochlorination ing films are manufactured mainly by extrusion
[40] and thus a wide range of rate coefficients blowing and take the shape of the packed
are reported [41–44]. The higher the conversion material during vacuum packaging. LDPE is
the more byproducts are generated. Conversion also used extensively for coating cardboard,
is limited to 50–60% at MRTs of 20–30 s, to paper, and aluminum foils for milk containers
keep byproducts below 1% and to prevent or as a wire and cable insulation.
excessive coking. Rapid quenching of the efflu-
ent is important to prevent tar formation [45]. High Pressure PE—Polymerization of
Ethylene in Tubular Reactors. The share
Tubular Reactors. A technical PFR of LDPE is about a quarter of the worldwide PE
designed for EDC decomposition must production (ca. 20  106 t/a in 2012) [46].
18 Tubular Plug Flow Reactors

LDPE is produced in a high-pressure process at LDPE Production Process. A simplified

1 500–3 000 bar. About one half is produced in flow sheet for high pressure PE production in
slim autoclave reactors with stirrer and the a tubular PFR is shown in Figure 16.
other half in long tubular PFRs. The following The capacity of modern plants is about 2 
description confines to ethylene polymerization 105 t/a. The flow velocity of the reaction mix-
in the high pressure process using tubular ture is several m/s and Re ¼ u  d/n > 20 000,
reactors. e.g., for n > 10
5 and u ¼ 3 [49]. The reactor is
a 500–1 000 m long jacketed stainless steel
nðCH2 ¼ CH2 Þ ! ðCH2 Þn Dr H ¼
93:6 kJ=mol pipe, subdivided by several 180 bends into
shorter sections. Typical inner and outer pipe
The polymerization is exothermal. At the diameters are 60 and 150 mm.
specific heat of gaseous ethylene of 2.08 kJ Ethylene gas is compressed in two stages,
kg
1 K
1, an adiabatic temperature rise DTad of first to 150–350 bar and then to 1 500–3 000
ca. 16 K results for only 1% conversion. The bar. The highly compressed gas is heated to
risk of exothermal decomposition reactions about 200 C in the first pipe section of the PFR
such as to start polymerization in the presence of 20–
200 ppm O2 and some organic peroxides as
C2 H4 ! C þ CH4 Dr H ¼
127 kJ=mol initiators. The heat of reaction is removed
C2 H4 ! 2 C þ 2 H2 Dr H ¼
53 kJ=mol through the pipe wall and by stepwise shot
cooling with unreacted, supercooled ethylene
must therefore be carefully controlled [47]. feed [50]. To prevent decomposition to carbon,
The process is operated at high pressures of methane, and hydrogen, the maximum temper-
ca. 2 000 bar where PE is soluble in super- ature is kept below 330 C; the usual reactor
critical ethylene. The critical temperature of effluent temperature is around 300 C.
ethylene is 9 C. Under the given process Conversions between 10–20% can be
conditions, the rate of polymerization is 12 attained in one pass. Higher values are possible
times faster than at 1 bar [48]. 20% conversion with additional cold shot cooling or other mea-
can be attained in 40 s; the activation energy is sures. Unconverted ethylene is recovered for
32 kJ/mol. recycling by pressure reduction of the liquid

Figure 16. Simplified flow sheet of a high pressure LDPE production process
a) Compression 1st stage, 250 bar; b) Compression 2nd stage 3 000 bar; c) Cooler; d) Zone 1; e) Zone 2; f) Zone n; g) Pressure
regulation valve; h) Cooler; i) Separator, 1st stage; j) Separator, 2nd stage; k) Extruder; l) Dryer; m) Silo
 Tubular Plug Flow Reactors 19

product to 150–300 bar. In a second product Coking and Soot Formation. Hard carbon
expansion step to 1–10 bar, the residual ethyl- deposits are formed slowly on all internal sur-
ene is recovered completely and recycled in a faces and can be removed during routine plant
separate low pressure loop. During pressure shutdown either mechanically or by combus-
reduction, the temperature of the reaction mix- tion. During accidental product decomposition,
ture rises due to a negative Joule–Thompson large amounts of fluffy soot is formed and
effect. Precooling is therefore necessary prior to accumulats in downstream equipment.
expansion to prevent thermal decomposition.
Reliable temperature control is achieved by a Perchlorination is used on a large scale for
combination of jacket cooling, stepwise cold the production of tetrachloromethane (CCl4)
feed shot cooling combined with controlled and tetrachloroethylene (C2Cl4). Propane per-
addition of initiators and modifiers (H2, hydro- chlorination is an example:
carbons or alcohols, ketones), usually at the
600 C; 3 bar
easily accessible bend sites of the pipe. Tubular C3 H6 þ7 Cl2








! CCl4 þ C2 Cl4 þ 6 HCl Dr H ¼
695 kJ=mol
reactors have also been investigated for emul-
sion polymerization in general [51]. A wide range of C1–C3 feedstocks and other
Ethylene polymerization involves more than organic waste streams are suited; undesired
just pressure and temperature control. products are separated and recycled. Reactor
Customer specifications include PE properties, cooling is achieved by injection and evapora-
such as thermal stability, tensile strength, crack tion of a cold liquid product mixture [55]. It is
resistance, color, clarity, and many others, possible to produce exclusively CCl4 and
which are not directly related to reactor oper- C2Cl4. A sophisticated PFR has been designed
ating conditions. These relations are not well and developed by Hoechst [56, 57]. In this
understood theoretically and rely on the man- reactor even stable waste materials, such as
ufacturers’ experience. hexachlorobenzene can be converted to CCl4
in an excess of chlorine at 620 C and 150 bar
[58].

3.3. Other Commercial Applications

Substitutive Bromination. Anesthetics
and fire retardants are commercially important
3.3.1. Gas Phase Halogenation of Methane
brominated organics. The reactions are carried
and Light Alkanes
out in PFRs at ca. 500 C and up to 3 bar
[59, 60].
Substitutive chlorination reactions of methane
and higher alkanes (see ! Chloroethanes and 500 C; 3 bar
Chloroethylenes) and perchlorination of CF2 HCl þ Br2







! CF2 BrCl
organic wastes are conducted in tubular
reactors, whose design and operation is tuned Such brominations are almost thermo neu-
for each individual application. The reaction tral with DrH of only 10–15 kJ/mol; this low
mechanisms of these exothermic reactions are value simplifies reactor design considerably.
well known [52–54]. Substitutive bromination is a free radical mech-
anism similar to chlorination.
R
H þ Cl2 ! RCl þ HCl Dr H 100 kJ=mol

3.3.2. HCN-Production in the Degussa BMA

Chlorination is too fast to be controlled by Process [61] (! Cyano Compounds,
heat exchangers, and the reactions proceed Inorganic, Chap. 1)
adiabatically. Chlorination is therefore con-
ducted stepwise and controlled via interstage Various HCN production processes from
cooling or evaporative cooling by injection of ammonia and methane or higher hydrocarbons
perhalogenated liquids. Another option is a were developed after 1950. They are based on a
single PFR with recycling unconverted feed strongly endothermic reaction, which proceeds
via a cooler [16, vol. 6, p. 9–24]. freely with negative
DrG only at higher
20 Tubular Plug Flow Reactors

temperatures above ca. T > DrH/DrS 1 000 C 3.3.3. Ketene via Acetic Acid or Acetone
Cracking (! Ketenes)
>1000 C
CH4 þ NH3






! HCN þ 3 H2 ;
Dr H ¼
251:6 kJ=mol; Dr G ¼ þ190:4 kJ=mol The world production capacity of ketene
CH2¼C¼O and diketen is about 1  106 t/a.
The heat of reaction is supplied in a PFR Diketene formation:
heated by external radiation. A bundle of
alumina tubes is mounted in a furnace to 2 H2 C ¼ C ¼ O@ Dr H ¼
189 kJ=mol
heat the methane–ammonia mixture up to 1
300 C. The tubes hang freely because of the
considerable thermal expansion. The inner wall
is coated with a promoted Pt catalyst; special
coating and catalyst activation steps are needed.
Special tubes from high temperature ceramics Ketene is the intermolecular anhydride of
[62] have lifetimes of two to three years. A ca. acetic acid and a reactive intermediate for many
5% NH3 excess prevents soot formation and applications, above all for the production of
deposits of carbon black. acetic anhydride:
Practical yields are 90% with regard to
CH4 and 85% with regard to NH3. The only CH2 ¼ C ¼ O þ CH3 COOH ! ðCH3 COÞ2 O Dr H ¼
63 kJ=mol
side reactions are NH3 decomposition to the
elements. The CH4-feed can be substituted by In the Wacker process for acetanhydride,
methanol, ethanol, or any other hydrocarbons. ketene is generated by pyrolysis of acetic
The specific energy consumption can be acid at 700–750 C in the presence of triethyl-
decreased to < 40  106 J per kg HCN. The phosphate:
thermal PFR load by radiation is near the upper
700 C
limit for externally heated tubular reactors. CH3 COOH




! CH2 ¼ C ¼ O þ H2 O Dr H ¼ þ147 kJ=mol
The essential difference to the other impor-
tant manufacturing processes for HCN is the
supply of the reaction heat. In the Andrussow
ammonoxidation process developed at IG-Far- Acetone Cracking to Ketene. Acetone
ben (BASF) in 1930 [16, vol. 2, pp. 190], this is vapors are fed to a tubular reactor and decom-
achieved by internal combustion of the product- posed at about 700 C and atmospheric pressure
coupled hydrogen with a stoichiometric amount to reactive ketene and inert methane.
of air at atmospheric pressure. The reaction is 700 C
performed in ca. 10
4 s. Combustion does not CH3
CO
CH3



! H2 C ¼ C ¼ O þ CH4

interfere with HCN formation. Side reactions :

CH3
CO
CH3 ! 2 C þ CO þ 3 H2
>1000 C; Pt; Rh
CH4 þ NH3 þ 1:5 ðO2 þ 3:7 N2 Þ











! HCN þ 3 H2 O;
Dr H ¼
474 kJ=mol:
At about 25% conversion, a selectivity of 75
 5% can be obtained. The rate equation for
ketene formation from acetone is reported with
HCN recovery is similar in all processes. To r ¼ expð22:8
26 600=TÞp1:5 a [ref 2, p. 447–
avoid HCN decomposition, the product gases 450]. The ketene is unstable and decomposes
must be quickly cooled in a waste heat boiler to further to ethylene and CO. The hot effluent
generate steam for the process. To prevent HCN gases from the tubular reactor are therefore
polymerization, residual NH3 can be removed rapidly quenched to ca. 80 C with an excess
by scrubbing with dilute sulfuric acid. Disposal of acetic acid and react to acetic anhydride. The
costs for the ammonium sulfate solution can be bulk of unreacted acetone is condensed and the
saved by NH3 absorption in monoammonium rest is recovered by absorption in acetic acid.
phosphate solution and regeneration of the Acetic anhydride production via ketene from
diammonium phosphate by NH3 desorption acetone is of minor importance, the process via
and recycle via steam injection. acetic acid decomposition dominates.
 Tubular Plug Flow Reactors 21

3.3.4. Ethylene Glycol via Ethylene Oxide nitration of paraffins, or side-chain fluorina-
Hydrolysis (! Ethylene Glycol) tions in Ni pipes e.g.,

The world production capacity of ethylene 90
130 C

Ar
CCl3 þ 3 HF








! Ar
CF3 þ 3 HCl
glycol was ca. 20  109 t/a in 2011. The major
applications are as raw material for polyester
fibers, films, and containers (PET) as well as Another example is the exothermic conver-
automotive antifreeze. sion of aromatic chlorine with ammonia into
The noncatalytic hydrolysis of ethylene amino groups, e.g., continuous, highly selective
oxide is simple and reliable and the most widely nitroaniline production [63, vol. 6, p. 197]
used ethylene glycol production process, [16, p. Ammonia is used as 25–40% aqueous solution
95–96]. in 10-fold molar excess

Hydrolysis : ðCH2 Þ2 O þ H2 O ! ðCH2 OHÞ2 Dr H ¼
80 kJ=mol

Diethylene glycol : ðCH2 Þ2 O þ ðCH2 OHÞ2 ! ðHOCH2 CH2 Þ2 O
Triethylene glycol : ðCH2 Þ2 O þ ðHOC2 H4 Þ2 O ! HOCH2 CH2 ðOCH2 CH2 Þ2 OH

Diethylene glycol and higher homologues 100
250 C; up to 250 bar

are formed in consecutive reactions. The for- O2 N
phenyl
Clþ NH3
















! O2 N
phenyl
NH2 þ HCl

mation of the undesired higher oligomers is

suppressed by a ca. 10-fold excess of water
in the reaction mixture. Commercial tubular DrH ¼
213 kJ/mol for p- and DrH ¼
172 kJ/
reactors operate at 20–40 bar and 150– mol for o-nitroaniline
250 C. Temperature control by cooling and Other applications of tubular reactors
sufficient residence time ensures almost com- include ethyl acetate production from acetalde-
plete conversion. Yields of about 90% for hyde and the dehydrochlorination of 1,1,2-
mono-, 10% for di-, and ca. 1% for tri- and trichloroethane to 1,1-dichloroethylene
higher polyglycols are almost independent (! Reactor Types and Their Industrial Appli-
from temperature and pressure. cation).
Water is removed from the product mixture
to 100–200 ppm in a multistage evaporator Cl2 CH
CH2 Cl ! Cl2 C
CH2 þ HCl
system at stepwise decreasing pressure. Final
vacuum distillation separates the homologues.
Water is recycled for feed preparation. The
highest purity specifications are required for 3.4. Research and Development
fiber-grade ethylene glycol.
Other production routes of minor impor- Microreactors (! Micro Process Technology,
tance (e.g., acetoxylation) proceed via glycol 1. Introduction) having the characteristics of
acetate or ethylene carbonate as intermediates, tubular reactors are investigated very inten-
followed by hydrolysis; production routes via sively especially for two-phase and three-phase
syngas are also under way. reactions. The reactions are carried out in indi-
In presence of a homogeneous acid catalyst, vidual capillaries or monoliths that may be
e.g., 0.1–1% H2SO4, ethylene oxide hydrolysis coated with catalytic material on the inside
proceeds already at 50–70 C and at normal of the capillary. The microreactors utilize the
pressure with improved selectivity. excellent mixing behavior of two-phase taylor
flow-vortices in capillaries. An excellent over-
3.3.5. Various Additional Applications view is given in [64].
Tubular photobioreactors (! Microalgae
Tubular reactors are for several exothermic Reactors) are investigated for microorganism
sulfonation reactions of aromatics, gas-phase growth [65, 66].
22 Tubular Plug Flow Reactors

29 K.M. Sundaram, G.F. Froment, Ind. Eng. Chem. Fundam. 17

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 Tubular Plug Flow Reactors 23

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