See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/226236142

Development and analysis of heterogeneous catalytic processes and reactors

Article  in  Theoretical Foundations of Chemical Engineering · June 2009

DOI: 10.1134/S0040579509030038

CITATIONS READS
4 1,602

1 author:

V. A. Makhlin
Karpov Institute of Physical Chemistry
23 PUBLICATIONS   60 CITATIONS   

SEE PROFILE

All content following this page was uploaded by V. A. Makhlin on 17 January 2017.

The user has requested enhancement of the downloaded file.

ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2009, Vol. 43, No. 3, pp. 245–259. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © V.A. Makhlin, 2009, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2009, Vol. 43, No. 3, pp. 261–275.

Development and Analysis of Heterogeneous

Catalytic Processes and Reactors
V. A. Makhlin
Karpov Institute of Physical Chemistry, ul. Vorontsovo pole 10, Moscow, 105064 Russia
e-mail: makhlin@bk.ru
Received September 15, 2008

Abstract—A retrospective review and a review of the current state are given for the problem of the
development and analysis of heterogeneous catalytic processes and reactors. Advanced approaches
to the study of kinetics and the engineering design of catalytic reactions are discussed. The advan-
tages and drawbacks of the main types and structures of industrial catalytic reactors are demonstrated
by the examples of present-day catalytic processes and reactors for basic organic and petrochemical
synthesis. The operation of several industrial catalytic reactors is analyzed in order to clarify the
causes of deterioration of design performance and/or to find ways for the process intensification in
operating plants.
DOI: 10.1134/S0040579509030038

INTRODUCTION PRESENT-DAY METHODS FOR DEVELOPING

The productions of nitric and sulfuric acids (the con-
tact process) developed in 1906 were the first in the his-
tory of industrial heterogeneous catalysis. Soon, in
1917, the industrial-scale production of synthetic
ammonia and, in 1923, the production of methanol
were developed. Thus, industrial catalysis has a nearly
100-year-long. In this period, basic large-scale produc-
tion of the nitrogen fertilizer industry and organic, pet-
rochemical, and polymer synthesis using reactors with
a large unit capacity were developed. Considerable
advances were made in oil refining due to the develop-
ment of high-silicon synthetic zeolites such as ZSM-5
[1, 2], in petrochemical synthesis due to the discoveries
of metal complex catalysis [3, 4], and in polymer syn-
thesis due to the development of Ziegler–Natta and
metallocene catalysts [5]. At the same time, the devel-
opment of the present-day chemical industry accompa-
nied with a continual rise in consumption, on the one
hand, and a rapid increase in the cost of raw materials
and energy carriers, on the other hand, requires design-
ing new catalytic processes and reactors and increasing
the efficiency of the existing ones.
In the present review, an attempt is made to summa-
rize experience in design and to reveal the main trends
in the development of scientific approaches and engi-
neering solutions in the creation of industrial catalytic
processes and reactors and methods for analyzing their
operation.
NEW PROCESSES AND CATALYSTS
Already at the early stage of the development of
industrial catalysis, it was evident that complex physi-
cal and chemical processes occur in catalytic reactors,
which include heat and mass transfer from the gas
phase to the surface of the catalyst grain and diffusion
in the pores accompanied by chemical conversion with
heat release or absorption and, in some cases, with a
change in the properties of a catalyst. To remove or sup-
ply heat, a reactor is equipped with heat exchangers.
Heat and mass transfer accompanied by a chemical
reaction and heat exchange with the surface of a cata-
lyst and the surface of a heat exchanger leads to the for-
mation of a nonuniform field of temperatures and con-
centrations both on a catalyst grain scale and on a cata-
lyst bed scale. As a consequence, the characteristics of
an industrial reactor depend not only on the properties
of a catalyst, but also on the conditions of heat and mass
transfer and aerodynamic conditions in the reactor. For
the same reason, the scale-up of a catalytic process
turns out to be extremely complicated: the results
obtained in laboratory-scale reactors are not necessarily
reproduced in industrial-scale reactors. In this connec-
tion, the development of industrial catalytic processes
requires solving a whole complex of scientific and tech-
nical problems.
The experience of many years' studies shows that
the most effective approach to the development of cat-
alysts is the approach that combines the study of activ-
ity and selectivity of a catalyst with controlling the
composition and condition of its surface. The instru-
mental methods of gas analysis developed in recent
decades and the studies of surfaces make it possible to

245
246 MAKHLIN
control in real time the composition of reaction gases
and the condition of the catalyst surface both at the
stage of development of a technology for its preparation
and at the stage of operation.
Shell’s recent experience in developing a technol-
ogy for preparation of a cobalt catalyst for the low-tem-
perature Fischer–Tropsch synthesis [6–9] can be con-
sidered as an example. Using photoelectron spectros-
copy, the authors were able to discover that the sizes of
the microparticles of cobalt oxide depend on the con-
centration and viscosity of the solution of cobalt salts
used for the impregnation of the support. In doing so,
they found that an increase in dispersity leads to a rise
in activity up to a certain limit. It turned out that excess
dispersity has an adverse effect on catalytic activity,
since cobalt forms a catalytically inactive compound
CoAl2O4 with the support. It also turned out that high
dispersity has an adverse effect on the selectivity of the
catalyst with respect to the formation of hydrocarbons.
The study of the influence of water formed in the
Fischer–Tropsch process was carried out using a com-
plex of methods: X-ray diffraction, photoelectron spec-
troscopy, temperature-programmed reduction, thermal
analysis, temperature-programmed desorption, and
pulsed adsorption of hydrogen and oxygen. At the same
time, kinetic studies were also performed. A tubular
reactor with d = 10 mm was used, into which a catalyst
predivided to 37–75 µm and diluted with SiC with the
same particle size in a ratio of 1 : 5 was charged to
reduce the temperature nonuniformity of the bed. For
the same purpose, the reactor was placed into an alu-
minium jacket.
DESIGN OF HETEROGENEOUS
CATALYTIC PROCESSES
The present-day approach to the development of
engineering design of heterogeneous catalytic pro-
cesses is based on the use of mathematical modeling
techniques. The first stage is the development of the
kinetic model of a reaction. In conducting experimental
kinetic studies, the so-called gradientless reactors are
used [10–13], which makes it possible to eliminate
under experimental conditions the influence of heat and
mass transfer processes on the rate of the reaction. In
processing the results of kinetic studies, mathematical
modeling techniques in combination with experimental
design methods are widely used (see, for example, [14,
15]). Such approaches make it possible at a minimum
scope of experiment to obtain an adequate mathemati-
cal description of the rate of the main and side reactions
as a function of the concentration of reactants, reaction
products, and temperature.
In constructing kinetic models, both formal models
as regression dependences of conversion and selectivity
on concentration and temperature and models based on
the knowledge of the mechanism of a reaction are used.
The latter are of great value, since they retain the ade-
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
quacy over a wide range of parameters. It is evident that
the development of such models is possible only under
conditions of the simultaneous study of the mechanism
of the reaction. One of the most informative methods
for studying the mechanism of catalytic reactions is the
technique based on conducting a reaction under non-
steady-state conditions (see, for example, [16]). An
example is the study of the reaction kinetics of metha-
nol hydrochlorination on active alumina [17], which
was performed within the development of a process for
producing methyl chloride in the fluidized bed of the
catalyst [18]. Under non-steady-state conditions, by
means of alternate supply of reactants and the subse-
quent estimation of relaxation times, it was found that
the main reaction—synthesis of methyl chloride—and
the side reaction—the production of dimethyl ether—
occur as a result of nucleophilic replacement of a mol-
ecule of water that is strongly adsorbed by active alu-
mina. Based on the revealed mechanism, kinetic mod-
els for the reactions of production of methyl chloride
and dimethyl ether on active alumina were constructed,
and numerical values of the parameters of the model
were obtained from the results of kinetic measurements
under steady-state conditions.
Based on the kinetic model, a theoretically optimum
mode without taking into account its feasibility is deter-
mined. The results of theoretical optimization make it
possible to formulate conditions for the optimum distri-
bution of concentrations of reactants, reaction products,
and temperature on catalyst grain and bed scales, and to
choose the type of a reactor.
At the next stage of engineering studies, the key
construction of a reactor is chosen and its mathematical
model is developed. In addition to a kinetic model, the
mathematical description of heat and mass transfer pro-
cesses in the catalyst grain and the entire space of the
reactor is necessary to construct a mathematical model
of the reactor. The regularities of heat and mass transfer
processes in dispersion media have been thoroughly
studied to date (see, for example, [19, 20]).
The main objective of mathematical modeling at the
stage of the construction of a model and its analysis is
to choose the most significant characteristics of a cata-
lytic process and evaluate the specific features of aero-
hydrodynamics and heat and mass transfer that form
the field of concentrations and temperatures in the grain
and the reactor space. Mathematically, such models are
sets of nonlinear differential equations, the solving of
which requires high-power computers. The study of a
process using a mathematical model makes it possible
to determine the optimum conditions of the process and
the dimensions of a granular bed taking into account the
size and shape of a grain and the method of heat
removal and to develop algorithms for controlling the
process taking into account the evolution of the proper-
ties of a catalyst during operation. The principles of the
construction of mathematical models and the modeling
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES
Fig. 1. Reactor for vinyl acetate synthesis: D = 3800 mm,
d = 38/2.5 mm, h = 6500 mm, and n = 4800.
and optimization of catalytic processes and reactors are
also well studied at present (see, for example, [21–26]).
It should be noted that the optimization of catalytic
reactors is mathematically a complex multiparameter
problem, the solving of which frequently requires the
development of special algorithms and software and the
use of high-power computers (see, for example, [27]).
MAIN TYPES OF INDUSTRIAL REACTORS
To implement optimum conditions for conducting
heterogeneous catalytic reactions, reactors of various
constructions are used in the practice of industrial catal-
ysis. At the same time, taking into account the special
significance of organizing a temperature field in the cat-
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
247
Fig. 2. Reactor for ethylene oxide synthesis: D = 4500 mm,
d = 25/2.0 mm, h = 7700 mm, and n = 14 500.
alyst bed, all constructions can be divided into two
types of reactors: isothermal and adiabatic reactors.
Among isothermal reactors are tubular fixed-bed reac-
tors and fluidized-bed reactors; among adiabatic reac-
tors are shaft, multiple-shell, and radial reactors, as
well as upflow reactors (riser reactors) and honeycomb
reactors. Multiphase trickle-bed and slurry-bed reactors
should be considered individually.
Let us consider the specific features of constructions
and operation and the main advantages and drawbacks
of these reactors using certain present-day industrial
reactors as examples.
Tubular reactors. As examples of tubular reactors,
Figs. 1 and 2 show present-day industrial reactors for
the synthesis of vinyl acetate and ethylene oxide, each
Vol. 43 No. 3 2009
248
(‡)
Fig. 3. Shapes of grains of present-day industrial catalysts: (a) pellet, (b) Raschig ring, and (c) Pall ring.
of them with a capacity of 50000 t/yr. The synthesis of
vinyl acetate via the oxidative acylation of ethylene on
a gold–palladium catalyst supported on spherical silica
gel particles with a diameter of 6–8 mm, is carried out
at a temperature of 140–190°ë and a pressure of
0.8 MPa. The catalyst is characterized by high selectiv-
ity (92–95%) and activity: the specific capacity is 250–
300 kg/(m3 h). The reactor is cooled by boiling water
with a pressure of 0.25–1.2 MPa.
Production of ethylene oxide via the partial oxida-
tion of ethylene by oxygen in excess ethylene on the sil-
ver catalyst applied onto corundum of the spherical
form with a diameter of 6–8 mm is carried out under
more severe conditions (the temperature is 220–260°ë
and the pressure is 2.0 MPa). The catalyst is character-
ized by a selectivity of 70–72% and an activity of
180 kg/(m3 h). The reactor is cooled with a high-boiling
heat transfer medium.
It should be noted that catalytic processes in tubular
reactors developed earlier were characterized by a sub-
stantially lower unit capacity. For example, the above
process for producing ethylene oxide was carried out at
the early stages of commercialization in reactors with a
capacity of 5000 t/yr that were cooled with boiling
water at a pressure of 4.0–5.0 MPa (the diameter of the
apparatus D is 3500 mm, the number of tubes n is 1470,
the diameter of the tube Hb is 25/2.0 mm, and the height
of the catalyst bed Hb is 3500 mm). Synthesis of vinyl
chloride according to the reaction of acetylene hydro-
chlorination is carried out in reactors with a capacity of
5000 t/yr (the diameter of the apparatus D is 3800 mm,
the number of tubes n is 480, the diameter of the tube d
is 89/8.0 mm, and the height of the catalyst bed Hb is
6000 mm). The capacity of the reactor for the synthesis
of vinyl acetate from acetylene and acetic acid is
5500 t/yr (D = 3400 mm, n = 2090, d = 57/2.5 mm, and
Hb = 3000 mm). The low-temperature Fischer–Tropsch
synthesis is carried out in a reactor with a capacity of
20000 t/yr (n = 2050, d = 57/2.5 mm, and Hb =
12000 mm).
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
MAKHLIN
(b) (c)
A considerable disadvantage of tubular reactors is
the high specific metal content (about 6–8 t/m3 of the
catalyst) and the high cost of manufacturing at a com-
paratively low unit capacity, which is due to the limita-
tion of the diameter and number of tubes and, conse-
quently, the dimensions of the apparatus. The choice of
the tube diameter is determined by the ratio of the
intensities of heat release and the removal of the reac-
tion heat to the cooling surface of the tube. The use of
tubes with small diameters creates the best conditions
for heat removal, but leads to the high specific metal
content. The use of tubes with larger diameters reduces
the specific metal content, but leads to the deterioration
of heat removal, which, in turn, leads to an increase in
the nonuniformity of a temperature field in the longitu-
dinal and cross sections of the catalyst bed.
In the case of highly exothermic reactions, an
increase in the diameter of the tube leads under certain
conditions to thermal runaway. In this connection, in
designing tubular reactors for conducting exothermic
reactions, it is necessary to estimate the parametric sen-
sitivity and conditions of the stability of a steady-state
thermal regime. Using ethylene oxidation to ethylene
oxide as an example, such a problem is studied in [28,
29]. As a result of the study, the criteria are found that
determine the stability margin of a tubular reactor with
respect to thermal runaway.
The choice of the size and shape of a grain is deter-
mined by the ratio of the rates of reaction and heat
release on the grain to the rate of heat and mass transfer
in the catalyst grain. A decrease in the size of the grain
and the diameter of the tube makes it possible to reduce
diffusional resistance and improve radial heat and mass
transfer, but leads to an increase in the hydraulic resis-
tance of the bed and undesired energy loss. In some
cases, a change in the form of a grain allows these prob-
lems to be solved without increasing hydraulic resis-
tance. Figure 3 shows the shapes of present-day indus-
trial catalyst grains
For example, the transition from the spherical shape
of a catalyst grain to Raschig rings and, then, to Pall
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES 249

rings, made it possible to improve the characteristics of

the process for the synthesis of ethylene oxide in reac-
tors with a tube diameter of 25/2.0 mm (see Fig. 2).
Until recently, the manufacturers of silver catalysts (in
particular, Kholkon) used as supports for the catalyst
“silver on corundum” a coarse-pored corundum of the
spherical form with a diameter of 6–8 mm, the specific
surface area of which was 0.1–0.2 m2/g. At a silver con-
tent of 8–10 wt %, the selectivity of the catalyst was
70–72% and the specific capacity was 180 kg/(m3 h).
The corundum in the form of Raschig or Pall rings, the
specific surface area of which is higher by one order of
magnitude (1.0–2.0 m2/g) and the quantity of silver is
two times less (4–5 wt %), was used as a support for the
next-generation catalyst. The selectivity of the process
on this catalyst was increased up to 80%, and the capac-
ity was increased up to 200 kg/(m3 h) without changing
the hydraulic resistance of the bed of operating reac-
tors.
In this connection, the study [30] should be men-
tioned, in which the dependence of the activity and
selectivity of the catalyst on the distribution of an active
phase in the bulk of the support was investigated by a
mathematical modeling technique. The results of the
study made it possible to determine a theoretically opti-
mum profile of the distribution of the active phase along
the radius of the catalyst grain.
Note also that, under the effect of the reaction
medium, the activity and selectivity of the catalyst can
vary with time and along the length of the bed. The
deactivation of the catalyst in the frontal bed due to
coke formation or an irreversible change in the phase
composition is the most common. More interesting was
a reversible change in catalytic activity along the length
of the bed due to the effect of the reaction product dur-
ing the production of ethylene oxide on a silver catalyst
in gas-phase promotion [28, 31].
Fluidized-bed reactors. As was stated above, the
efficiency of a tubular reactor is substantially deter-
mined by the size and shape of the catalyst grains.
However, the size of a grain can be decreased only to a
certain limit imposed by aerodynamic resistance, and it
is not always possible to manufacture a catalyst of the Fig. 4. Reactor for oxidative chlorination of ethylene: D =
required form due to limitations caused by the mor- 3500 mm and Hb = 12 000 mm.
phology of catalytic mass or the material of a support.
At the same time, a considerable increase in the effi-
ciency of heat and mass transfer is possible in the case mented in the entire volume of the bed (see, for exam-
of the transition from granular fixed-bed reactors to flu- ple, [24]).
idized-bed reactors. In this case, there hardly exists any
limitation on the size of the catalyst grain, which elim- As an illustration of a fluidized-bed reactor, Fig. 4
inates the influence of internal diffusion limitations, shows an industrial reactor for oxidative chlorination of
and, to remove the heat of a reaction, coil heat exchang- ethylene in the production of ethylene dichloride with a
ers immersed into the fluidized bed are used that ensure capacity of 125000 t/yr. The process is carried out at a
a much higher heat transfer coefficient as compared temperature of 220–230°ë and a pressure of
with that for a fixed bed. Here, due to intensive longitu- 0.25−0.4 MPa on a microspheroidal catalyst—copper
dinal and cross mixing of a bulk material, temperature chloride on active alumina—with a particle size of 40–
conditions that are close to isothermal ones are imple- 60 µm and a copper chloride content of 5 wt %. The

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 43 No. 3 2009

250 MAKHLIN
catalyst charge is 60 t. The height of the fluidized bed is
12000 mm. The conversion of ethylene is 97%, the
selectivity is 92–94%, and the specific capacity is
270 kg/(m3 h) [32]. It should be noted that the reaction
conditions that are optimum in terms of the ratio of
reactants are in the explosive region. To prevent a volu-
metric explosion, the original design of a device for
mixing reactants, which simultaneously acts as a gas-
distribution device, is used. The device consists of
chambers for micromixing reactants, which rules out
the formation of large volumes of an explosive mixture
outside the fluidized bed.
Such reactors are used in a number of industrial cat-
alytic processes. For example, in producing acryloni-
trile by oxidative ammonolysis of propylene on a bis-
muth–molybdenum catalyst, the capacity of the reactor
is 75000 t/yr, the diameter of the reactor is 8500 mm,
the catalyst charge is 150–170 t, and the height of the
fluidized bed is 6500 mm. In producing vinyl acetate
from acetylene and acetic acid on a zinc acetate cata-
lyst, the capacity of the reactor is 12000 t/yr, the diam-
eter of the reactor is 3200 mm, the catalyst charge is
20 t, and the height of the fluidized bed is 6000 mm. In
producing isobutylene and isoamylenes by dehydroge-
nation of isobutane and isopentane on chromia–alu-
mina catalysts, fluidized-bed reactors sectioned by per-
forated plates are used. The capacity of such reactors is
100000–150000 t/yr, D = 5000–5500 mm, and the cat-
alyst charge is 70–80 t [33]. In the high-temperature
Fischer–Tropsch synthesis, the capacity of present-day
reactors reaches 900000 t/yr and D = 10700 mm [34].
At the same time, the results of extensive studies of
the regularities of mass transfer in the fluidized bed
show that the intensity of mass transfer of the gas to the
catalyst particle is limited by a two-phase structure of
the fluidized bed, which is caused by the formation of
the agglomerates of particles and large bubbles (see, for
example, [24]). To enhance interphase transfer, many
researchers and inventors proposed various internals in
the form of perforated partitions of various construc-
tions [35] and small-size packings in the form of rings
and spirals [36], the operating principle of which
reduces to the destruction of large bubbles and the
agglomerates of particles.
In [37], the influence of a small-size packing on the
intensity of mass transfer in the fluidized bed of a gran-
ular material of various granulometric compositions
and densities was investigated on a cold stand. Standard
Pall rings with dimensions of 50 × 50 mm and spiral
rings with dimensions of 50 × 70 mm manufactured
from a wire with a thickness of 3 mm were used as a
packing. As a result, it was found that the intensity of
interphase mass transfer in the presence of a small-size
packing indeed increases, and this effect gains in
strength with an increase in the velocity of a gas. At the
same time, it was found that the influence of various
packings on the intensity of interphase mass transfer for
various bulk materials was substantially different. For
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
bulk material of group A according to the Geldart clas-
sification [38], the intensity of mass transfer in the flu-
idized bed with a packing consisting of spiral rings at a
gas velocity of 0.4–0.5 m/s exceeds the intensity of
mass transfer with a packing consisting of Pall rings by
more than a factor of 2 at the same gas velocity. For
bulk material of group B, the reverse was true: the pack-
ing consisting of Pall rings was more effective.
However, in industrial practice, small-size packings
have not found application, and perforated grids are
used only in reactors for the dehydrogenation of isobu-
tane and isopentane, but their role reduces more likely
to the sectioning of the bed. The use of microspheroidal
catalysts, the fluid properties of which correspond to
group A according to the Geldart classification, was a
more effective method for enhancing mass transfer in
the fluidized bed.
Here, it is interesting to mention the study [39] in
which the process of oxidative ammonolysis of propy-
lene in the fluidized bed of the microspherical bismuth–
molybdenum catalyst of brand NS-733A, which relates
in its fluid properties to group A, was investigated. In
conducting the process in a pilot reactor with a diameter
of 400 mm using the above packing of the spiral type, a
five to six times expansion of the bed at a superficial gas
velocity of 0.3–0.5 m/s, which is characteristic of the
operation of such catalysts in a freely fluidized bed, was
observed at the moment of the supply of reactants. It
should also be noted that intensive circulation of the
catalyst was observed in this case, owing to which the
difference between temperatures along the height of the
bed did not exceed two to three degrees. The estimation
of the intensity of mass transfer performed by a mathe-
matical modeling technique on the basis of the known
kinetics of the reaction has shown a sharp increase in
the interphase mass transfer coefficient. Even more
unexpected was the fact that on a similar catalyst of
brand C-41 with the same granulometric composition
but slightly different chemical composition, a moder-
ate, approximately two times, expansion of the bed was
observed under the same conditions.
The disadvantage of fluidized-bed reactors is the
attrition of particles and increased losses of the catalyst
due to the entrainment of small particles with a gas
stream. In this connection, the use of expensive cata-
lysts and catalysts with a low mechanical strength is
almost ruled out in fluidized-bed reactors.
Upflow reactors (riser reactors). Reactors in
which a process is carried out in gas-transport flows of
the catalyst that are rare in a solid phase, the so-called
riser reactors, are promising for the intensification of
mass transfer in catalytic processes. Such reactors
enjoy widespread use for implementing the processes
of the cracking of petroleum products on high-activity
zeolite-containing catalysts [40, 41]. These reactors
with a circulating fluidized bed of the catalyst were
used until recently by Sasol for high-temperature Fis-
cher–Tropsch synthesis [34].
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES 251

Figure 5 shows a reactor assembly for catalytic crack-

ing of heavy gas oil with a capacity of 2 million t/yr.
Cracking is carried out on a zeolite-containing micro-
spheroidal catalyst with a particle size of 40–70 µm.
The assembly consists of a reactor and a regenerator.
The reactor is an apparatus with an upflow of the cata-
lyst, the so-called riser reactor, and the regenerator is an
apparatus with a fluidized bed of the catalyst that is
designed for carbon burning and catalyst heating.
It should be noted that the specific capacity of the
catalyst in this process is about 20 kg/(dm3 h), which
exceeds similar characteristics of all known catalytic
processes of petrochemical synthesis by more than two
orders of magnitude. Such a high specific capacity of
the catalyst in a riser reactor is attained due to the com-
bination of the high activity of a zeolite-containing cat-
alyst and intensive heat and mass transfer in a gas-cat-
alyst flow.
The use of particles with such a small size almost
rules out the internal diffusion limitation on the rate of
a reaction, and the turbulent mode of motion of catalyst
particles in a solid-rare gas flow at a velocity of about
2–10 m/s almost rules out interphase limitations, which
are characteristic of fluidized-bed reactors. The disad-
vantage of riser reactors is the increased abradability of
catalysts and the height of the apparatus, which is more
than 50 m.
It should be noted that, in using upflow reactors for
conducting exothermic reactions, there arises a prob-
lem of the stability of steady-state thermal conditions in
the reactor–regenerator system. Specific features of the
operation of upflow reactors, including the problems of
the quasi-steady state of a catalyst and the stability of
steady-state thermal conditions in the case of exother-
mic reactions, are studied in [42–44].
Adiabatic shaft, multiple-shell, and radial reac-
tors. Adiabatic reactors are used to implement catalytic
processes, the selectivity of which varies only slightly
in a wide temperature range. Examples of such pro-
cesses are the synthesis of methanol, the dehydrogena-
tion of ethyl benzene, catalytic purification of gas emis-
sions, etc. Such reactors are designed as single-stage
columns, the so-called shaft reactors, or multistage col-
umns: multiple-shell reactors and reactors with the
arrangement of a catalyst in the annular space of a col-
umn—radial reactors.
Synthesis of methanol in present-day commercial Fig. 5. Reactor for catalytic cracking of gas oil. Riser reac-
plants is carried out on copper-containing catalysts at a tor: D = 1400 mm and H = 55 200 mm. Regenerator: D =
temperature of 230–280°ë and a pressure of 5.0– 8600 mm and H = 27 200 mm.
8.0 MPa. Figure 6 shows an industrial multiple-shell
reactor with adiabatic catalyst beds designed by ICI.
The reactor is a column with a diameter of 4450 mm cold gas with a hot flow of reaction gases and uniform
into which about 140 m3 of the pelleted catalyst is distribution in the cross section of the bed are carried
charged. The capacity of the reactor is 375 000 t/yr. The out directly in the bed using lozenge-shaped flow dis-
allowable temperature difference in each bed is 40– tributors developed by ICI. The advantage of such a
50°ë. To maintain the reaction temperature in a given design is the ease of catalyst charge and discharge.
range, the flows of cold gas (quenches) are introduced Such reactors have been operating for many years at
into the lower section of each catalyst bed. Mixing of many factories in different countries, including Russia.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 43 No. 3 2009

252 MAKHLIN
Fig. 6. Reactor for methanol synthesis: D = 4500 mm and
Hb = 9500 mm.
However, the studies conducted in recent years at
the Boreskov Institute of Catalysis have shown that in
the cross section of the granular bed of reactors
equipped with such devices for the mixing and distribu-
tion of gas flows, there are considerable nonuniformi-
ties of a temperature field that are caused by a nonuni-
form profile of the temperature of the inlet flow of gas
and the nonuniformity of the structure of a granular
bed. In addition, it is found that spatial nonuniformities
of the bed voidage are formed during charging of the
catalyst into the reactor. Temperature nonuniformities
in the bed lead to accelerated deactivation and a
decrease in the lifetime and capacity of the catalyst. To
create more uniform structures of the bed, special
devices and technologies for charging were developed
[45], and, to ensure the uniformity of the temperature
profile for gas flow at the inlet of each stage of the bed,
a new construction for gas mixing and distribution was
developed, which made it possible to increase the
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
capacity of the reactor and the lifetime of the catalyst
[46].
Honeycomb catalysts in adiabatic reactors. In
recent decades, monolithic honeycomb catalysts enjoy
wide use in industrial catalysis [47, 48]. The character-
istic size of channels in a monolith is 1.5–2.0 mm, the
number of channels is 100–400 per square inch, and the
thickness of the partition between the channels is 0.1–
0.2 mm. The geometry of the honeycomb structure
makes it possible to apply the active phase into the par-
titions of channels as a superfine layer and create a
highly developed surface for flowing around by a gas
stream. In the case of applying a high-activity phase,
the produced catalysts turn out to be effective at volu-
metric rates of gas supply of more than 10000 h–1, i.e.,
millisecond contact times and linear gas velocities at a
level of 20–30 m/s. Honeycomb structures in compari-
son with a granular bed create insignificant aerody-
namic resistance even at high gas velocities, which is
extremely important for reactors for catalytic purifica-
tion of gas emissions and setups for catalytic combus-
tion of fuels [49].
Attempts to use honeycomb catalysts in the pro-
cesses of millisecond reforming of methane [50] and
oxidation of ammonia in the production of nitric acid
[51] are also known.
Reactors for catalytic neutralization of gas emis-
sions. As was pointed out above, one of the specific fea-
tures of the overwhelming majority of sources of harm-
ful gas emissions is the low pressure of the gas stream,
which imposes the relevant requirement on the resis-
tance of the reactor for catalytic neutralization. Another
specific feature is the instability of its parameters. The
flow rate of the gas, the concentration of harmful impu-
rities in it, and, in some cases, the temperature of a gas
flow varies with time, as a rule, with uncertain ampli-
tude and frequency.
To maintain the required degree of separation, it is
necessary to ensure the process control in the reactor
for catalytic purification taking into account the
dynamic characteristics of a source. This problem is
studied in [52] for catalytic removal of carbon monox-
ide from gas emissions. Dynamic regimes of the perfor-
mance of an adiabatic reactor operating under external-
diffusion control were studied using a mathematical
modeling technique. The main regularities the process
were found. On the temperature–concentration phase
plane, the region of the stability of the external-diffu-
sion mode is determined at the inlet of the reactor, the
dependence of the region boundaries on the aerody-
namics of the flow and the geometry of the reactor was
found, and an algorithm for controlling the process tak-
ing into account a change in the temperature and con-
centration of fuel at the inlet of the reactor was devel-
oped.
Catalytic combustion chambers. The combustion
of fuels with an air excess factor of 3.0–3.1 is carried
out in the majority of present-day furnaces. During the
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES 253

burning of such mixtures, a temperature of higher than

1500°ë develops in the flame, as a result of which large
quantities of nitrogen oxides polluting the environment
are formed. Recent decades are characterized by the
wide use of gas-turbine plants both in aviation and in
power engineering. For example, more than 2000 gas-
turbine plants operate RAO Gazprom’s gas-transport
facilities alone. Gazprom data presented at the exhibi-
tion “Engines 2000” indicate the scale of pollution.
According to these data, at Gazprom’s gas-transport
facilities of gas-main pipelines, the total emission of
nitrogen oxides by gas-turbine plants is 280000 t/yr.
Attempts made earlier to solve the problem of emission
decontamination using catalytic purification methods
were ineffective, since the cost of setups for decontam-
ination was comparable with the cost of heat power set-
ups.
In this connection, over the past two decades, the
method of flameless catalytic combustion in thin, so-
called lean, mixtures with air at an excess coefficient at
a level of 9–10 increasingly attracts the attention of
researchers [53, 54]. This method makes it possible to
conduct combustion at a moderate temperature and
decrease the levels of the emissions of nitrogen and car-
bon oxides down to 3 ppm and hydrocarbons down to
5 ppm. The temperature in such chambers is regulated
by varying the excess air coefficient.
A device for the catalytic combustion for gas tur-
bines of the 20MW class has been recently developed
in Japan [54]. The burning of a methane–air mixture in
such a chamber is carried out at a pressure of 13.5 bar,
an inlet temperature of 360°ë, and an outlet tempera-
ture of 750–800°ë. The volumetric flow rate is 13000–
14000 h–1, which corresponds to a contact time of about
250 ms. The actual gas velocity in channels is about
30 m/s, and the pressure loss is about 2.5%.
Main features of adiabatic reactors. Summarizing Fig. 7. Trickle-bed reactor.
the main features of adiabatic reactors, that one of the
advantages of such reactors is the low specific metal The other type of multiphase reactors is slurry-bed
content. For example, for a reactor of methanol synthe-
reactors, in which the fine particles of a catalyst are sus-
sis, this characteristic is 2.25 t/m3 of the catalyst. pended in the liquid phase, through which a gas is
Another advantage is the relative simplicity of the con- passed. To remove the reaction heat, coil heat exchang-
structions, which allows apparatuses with a large unit
ers immersed into a bed (Fig. 8) are used in such appa-
capacity to be manufactured. Among the drawbacks are
the limited capabilities of such apparatuses for imple- ratuses. Recently, reactors with the suspended bed of a
menting reactions with a large thermal effect, the selec- cobalt catalyst are used in the production of synthetic
tivity of which depends on the nonuniformity of tem- liquid fuels in the low-temperature Fischer–Tropsch
perature over a catalyst bed. synthesis. The unit capacity of the reactors exceeds
20000 barrels per day, which is about 900000 t/yr [58].
Multiphase catalytic reactors. There are two main
types of reactors containing gas, liquid, and solid Despite widespread use, the development of the
phases. Trickle-bed reactors, in which a mixture of gas apparatus design of multiphase processes is associated
and liquid passes through a granular fixed bed of a cat- with considerable difficulties caused by the complexity
alyst (Fig. 7) enjoy the widest use in industry. Such of hydrodynamic conditions and the influence of inter-
reactors are used in the petroleum refining industry for phase mass transfer on the reaction rate. In trickle-bed
the hydrofining of petroleum fractions from sulfur and reactors, the rate of mass transfer depends on the degree
nitrogen compounds [55, 56], catalytic reforming of of the wetnwss of the catalyst grains, their size and
naphtha [57], etc. shape, the ratio of gas and liquid velocities, the proper-

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 43 No. 3 2009

254 MAKHLIN
Fig. 8. Slurry-bed reactor.
ties of a liquid, and the solubility of the gas in the liq-
uid.
In slurry-bed reactors, the rate of mass transfer
depends on the size of particles, the physical properties
of a liquid, the solubility of a gas in the liquid, and the
intensity of stirring. One of the merits of slurry-bed
reactors is the ease of removing the heat of reaction,
which is especially important for highly exothermic
reactions. These reactors are also very convenient for
processes on a rapidly deactivated catalyst, where the
continuous reactivation of the catalyst is required.
The disadvantage of these reactors is the difficulty
of isolating the fine catalyst from the reaction mixture,
which seriously limits their application in the case of
expensive catalysts.
Reactors for catalytic distillation. Over the past
two decades, catalytic distillation processes, in which a
chemical process is combined with the process of dis-
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
tillation or distillation, enjoy widespread use in indus-
try. Reactors used for conducting such processes are
called reactive distillation columns, and reactors for
conducting catalytic reactions are called catalytic distil-
lation columns.
According to [59, 60], at present, there are more
than 150 commercial-scale plants with a capacity of
0.1–3 million t/yr in which various catalytic processes
of reactive distillation are used. Among them are pro-
cesses for the production of methyl acetate, ethyl ace-
tate, etc. (see, for example, [61, 62]); the production of
methyl tert-butyl ether (see, for example, [63, 64]); the
hydrogenation of benzene to cyclohexane [65]; the
alkylation of benzene and toluene (see, for example,
[66, 67]); the hydrocracking of heavy oil fractions [68];
the hydrodesulfurization of oil fractions [69]; the
hydration of ethylene oxide to monoethylene glycol
[70], etc.
This wide use of catalytic distillation processes is
caused by more favorable conditions of conducting
many catalytic processes in the case of their combina-
tion with the processes of distillation and distillation.
For example, in the case of benzene hydrogenation, the
technique of catalytic distillation ensures effective con-
tact of hydrogen dissolved in benzene with the catalyst
and effective heat removal from the reaction zone,
which makes it possible to attain a degree of benzene
conversion of more than 90% at a selectivity close to
100%. In addition, due to the “washing effect,” the dep-
osition of polymeric compounds and coke on the sur-
face of catalyst grains is almost completely prevented,
which substantially increases the lifetime of the cata-
lyst [65].
The design of catalytic distillation columns for most
processes is the know-how of developers, though the
key designs are described in the literature. In some
devices for carrying out a three-phase process, the cat-
alyst in packages made of a grid is charged into down-
comers of distillation columns as a granular fixed bed
[71]. Such a construction creates conditions for con-
ducting the successive processes of liquid saturation
with gas on plates and the contacting of a saturated
solution with the catalyst in overflow lines. Rapid dis-
solution of gas occurs due to good gas–liquid contact
on plates, and good liquid–solid contact is attained due
to an increased flow rate of liquid in a catalyst bed,
which, as a rule, limits the rate of the reaction.
There are designs in which a catalyst is placed into
horizontally located mesh troughs [72] or tubes made
of metal screens located as a hurdle packing [73]. Sand-
wich constructions are known in which a catalyst is
placed into the space between corrugated perforated
plates and is sealed along the perimeter. “Sandwiches”
produced in this way are stacked into cubic or cylindri-
cal units and charged into columns [74–76]. After expi-
ration of the catalyst lifetime, such units are discharged
from a column and replaced with fresh ones. Such
designs are licensed by Sulzer under the KATAPAK-S
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES
trademark and by Koch–Glitsch under the KATAMAX
trademark.
The introduction of the function of separation into
the reaction zone leads to complex contact between the
vapor–liquid equilibrium, vapor–liquid mass transfer,
internal diffusion, and chemical kinetics. Therefore, the
modeling of reactive distillation and columns is consid-
erably more complex problem than that associated with
conventional catalytic processes and separation pro-
cesses and requires obligatory verification in laboratory
and pilot plants [77].
ANALYSIS OF INDUSTRIAL CATALYTIC
PROCESSES AND REACTORS
During the operation of industrial catalytic reactors,
there is quite often a necessity for analysis of their oper-
ation for evaluating and eliminating the causes of a
decrease in design characteristics on the productivity,
selectivity, lifetime of the catalyst, etc., or development
of ways for the intensification and/or conversion of
operating productions. In most cases, conducting such
analysis is an extremely complex chemical engineering
problem, for solving which it is necessary to study the
influence of many factors before it is possible to deter-
mine the most significant. Let us consider the essence
of solving such problems using the following exam-
ples.
Ethylene oxide production. As was stated above,
present-day industrial production of ethylene oxide is
carried out by partial oxidation of ethylene by oxygen
on silver catalysts in gas-phase promotion. Ethylene
dichloride is used as a promoter. Two versions of the
process are known: “air” and “oxygen” processes,
which are named depending on the form of oxygen
used—air or pure oxygen. The second version is eco-
nomically more preferable for high-capacity setups.
In our country, two plants producing ethylene oxide
via the oxygen process operate: one in Dzerzhinsk and
the other in Nizhnekamsk. The design unit capacity of
a reactor in both productions is 50000 t/yr. The first to
be built and introduced into operation was the produc-
tion in Dzerzhinsk. After three years from the moment
of startup, frequent stops of the process induced by sud-
den, without visual causes, sharp jumps of temperature
and pressure in the outside-catalyst space of the reactor,
which were called “decomps,” happened in this produc-
tion. Frequent stops and the involved downtime of pro-
duction led to a considerable decrease in capacity.
To investigate the causes of stops, an analysis of the
process in active production was performed by the Kar-
pov Institute of Physical Chemistry together with PO
Kaprolaktam (Dzerzhinsk) [78]. At the first stage, anal-
ysis of a technological strategy for controlling the pro-
cess under conditions of long-term operation of the cat-
alyst was performed. As a result, it was found that as a
catalyst aged, to maintain the capacity of production
and the selectivity of the process, regular correction of
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
255
control parameters—an increase in temperature and
promoter concentration—was carried out in accor-
dance with the operating procedure. In this case, after
the next correction of process parameters, decomps
occurred at certain time points.
To understand the nature of this phenomenon, an
analysis of the studies by various researchers into the
kinetics and mechanism of the reaction of ethylene oxi-
dation on silver catalysts was performed, and a kinetic
model was developed which takes into account the
influence of the temperature and composition of the
reaction medium on the activity and selectivity of a sil-
ver catalyst under conditions of gas-phase promotion. It
is found that under the effect of components of the reac-
tion mixture, the nonuniformity of the activity and
selectivity of the catalyst action can develop along the
length of a catalyst bed [28, 31].
At the next stage, a mathematical model for a cooled
tubular reactor was developed taking into account the
nonuniform activity of the catalyst along the length of
the bed, and the modeling of the process was performed
under conditions similar to industrial ones on the
assumption of the isothermality of the intertubular
space. The results of modeling have shown that the cat-
alyst located closer to the end of the tube, in the hottest
zone of the bed, has the highest activity, which
increases the nonuniformity of a temperature profile
present in this section. As a result, a so-called hot spot
forms in which the process is close to thermal runaway.
The mathematical modeling of the process taking
into account the nonisothermality of the intertubular
space of a heat exchanger has shown that the noniso-
thermality of a heat transfer medium in the intertubular
space increases the nonuniformity along the length of
the bed and leads to an additional increase in the para-
metric sensitivity of the reactor.
At the same time, the calculation of a stability crite-
rion from average parameters for the entire bundle of
tubes has shown that the process remains stable to ther-
mal runaway. In this connection, the causes of origina-
tion of nonuniformities in the bundle of tubes were
studied, and it was found that during long-term opera-
tion of the reactor, the nonuniformities of distribution
of the activity of a catalyst and the efficiency of heat
exchange over the entire bundle of the reactor tubes are
formed in individual tubes. Tubes with anomalously
high activity and low efficiency of heat exchange have
increased parametric sensitivity, and, in the case of
small disturbances, thermal runaway occurs in these
tubes. The ejection of reaction gases with a high tem-
perature into the outside-catalyst volume causes the
ignition of the reaction mixture accompanied by a sharp
increase in temperature and pressure (decomp).
Based on the results of performed analysis of the
operation of an active reactor, an algorithm for control-
ling the process to prevent repeated decomps was pro-
posed, and ways for improving the process were devel-
Vol. 43 No. 3 2009
256 MAKHLIN
oped that considerably increase its stability to thermal
runaway [79].
Process for producing ethylene dichloride by eth-
ylene oxychlorination. As was noted above, a process
for producing ethylene dichloride by ethylene oxychlo-
rination is carried out in the fluidized bed of the catalyst
(copper chloride on active alumina) in a reactor with a
capacity of 125 000 t/yr. To remove heat, reactors are
equipped with a heat exchange device with a developed
heat exchange surface: the specific surface area of the
heat exchange device is 10 m2/m3 of the catalyst. The
heat exchanger consists of vertical coils in which boil-
ing water circulates under pressure. Such plants operate
at the factories of PO Khlorvinil and PO Khimprom.
To find ways for enhancing the process and reducing
harmful emissions, works on the analysis of operating
plants were conducted at the Karpov Institute of Physi-
cal Chemistry [80, 81]. Based on the known kinetics of
the reaction, the mathematical modeling of the reactor
was conducted and the dependence of the degree of the
use of the catalyst on the intensity of mass transfer in
the fluidized bed was studied at various concentrations
of an active phase—copper chloride. As a result of the
studies, it is shown that the degree of the use of the cat-
alyst at a rated content of copper chloride (5 wt %)
under industrial conditions is extremely small: no more
than 13%. As calculations showed, the cause of such a
low degree of the use of the catalyst is the insufficiently
effective interphase mass transfer in existing fluidized-
bed reactors. In this case, a negative influence of the
excess content of copper chloride on the quality of flu-
idization was noted, and recommendations on the opti-
mum content of the active phase taking into account the
porous structure of the support were developed. The
optimization of the process with respect to a flow
scheme and a scheme with the recycling of reactants
was performed. Recommendations were developed for
increasing the capacity of setups and decreasing harm-
ful emissions due to an increase in the concentrations of
reactants by using oxygen-rich air mixtures or com-
pletely replacing air by oxygen. Heat engineering cal-
culations were conducted, the results of which showed
that the present heat exchange device allows the capac-
ity of reactors to be increased by approximately 30%
due to a decrease in the temperature of a heat transfer
medium. It is also shown that the lower limit of the tem-
perature of the heat transfer medium is set by the dew
point.
CONCLUSIONS
Present-day heterogeneous catalytic processes of
basic organic and petrochemical synthesis developed in
recent decades are characterized by a high level of the
selectivity and activity of catalysts and a high unit
capacity of reactors. Success in the development of cat-
alysts was attained due to the advancement of the sci-
ence of surfaces and wide use of up-to-date physical
and physicochemical methods in conducting the studies
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
of catalysts, and success in the development of effective
catalytic reactors was attained due to the use of modern
achievements in the field of the aerodynamics of disper-
sion media, the theory of combustion and explosion,
and mathematical modeling techniques.
NOTATION
D—diameter of the reactor, mm;
d—diameter of the tube, mm;
H—height of the reactor, mm;
Hb—height of the catalyst bed, mm;
h—height of the tube, mm;
n—number of tubes.
REFERENCES
1. Rabo, J.A., Zeolite Chemistry and Catalysis, Washing-
ton: Am. Chem. Soc., 1976, vol. 1.
2. Romanovskii, B.V., Nanosystems in Molecular Sieves,
Sb. tr. Mezhdunarodnoi shkoly povysheniya kvalifikatsii
v oblasti inzhenernoi khimii. Sed’maya sessiya “Prob-
lemy i dostizheniya fiziko-khimicheskoi i inzhenernoi
nauki v oblasti nanomaterialov" (Proc. Int. Continuing
Education School in the Field of Chemical Engineering,
Seventh Session: Problems and Achievements of the
Physicochemical and Engineering Science in the Field
of Nanomaterials), Makhlin, V.A., Ed., Moscow:
NIFKhI, 2002, vol. 2, p. 58.
3. Moiseev, I.I., π-Kompleksy v zhidkofaznom okislenii ole-
finov (π-Complexes in Liquid-Phase Alkene Oxidation),
Moscow: Nauka, 1970.
4. Moiseev, I.I, Metal Complex Catalysis of oxidation reac-
tions. Catalysis with Palladium Complexes, Proc. Int.
Continuing Education School. Second Session,
Makhlin, V.A., Ed., Moscow, 1996, p. 1.
5. Zakharov, V.A., Present-Day Catalytic Systems and New
Possibilities in the Production of Polyolefins, Sb. tr.
Mezhdunarodnoi shkoly povysheniya kvalifikatsii v
oblasti inzhenernoi khimii. Chetvertaya sessiya “Sovre-
mennye problemy i tendentsii razvitiya proizvodstva
polimernykh materialov” (Proc. Int. Continuing Educa-
tion School in the Field of Chemical Engineering, Fourth
Session: Current Problems and Trends in the Develop-
ment of Polymer Production), Makhlin, V.A., Ed., Mos-
cow: NIFKhI, 1998, p. 31.
6. Wilson, J.H. and de Groot, C.P.M., Atomic-Scale
Restructuring in High-Pressure Catalysis, J. Phys.
Chem., 1995, vol. 99, p. 7860.
7. Loosdrecht, J., Haar, M., Kraan, A.M., Dillen, A.J., and
Geus, J.W., Preparation and Properties of Supported
Cobalt Catalysts for Fisher-Tropsch Synthesis, Appl.
Catal., A, 1997, vol. 150, p. 365.
8. Geerlings, J.J.C., Wilson, J.H., Kramer, G.J.,
Kuipers, H.P.C.E., Hoek, A., and Huisman, H.M.,
Fischer-Tropsch Technology − from Active Site to
Commercial Process, Appl. Catal., A, 1999, vol. 186,
p. 27.
9. Hilmen, A.M., et al., Study of the Effect of Water on Alu-
mina Supported Cobalt Fischer-Tropsch Catalysts, Appl.
Catal., A, 1999, vol. 186, p. 169.
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES
10. Berty, J.M., Laboratory Reactors for Catalytic Studies,
in Applied Industrial Catalysis, Leach, B., Ed., New
York: Academic, 1983, vol. 1.
11. Lipiaeinena, K., et al., Novel Equipment for Testing Cat-
alytic Cracking and Catalyst Regeneration with Short
Contact Times, Appl. Catal., A, 1999, vol. 183, p. 411.
12. Shah, Y.T., Gas-Liquid-Solid Reactor Design, New York:
McGraw Hill, 1979, p. 149.
13. Ajmera, S.K., et al., Microfabricated Differential Reac-
tor for Heterogeneous Gas Phase Catalyst Testing, J.
Catal., 2002, vol. 209, p. 401.
14. Snagovskii, Yu.S. and Ostrovskii, G.M., Modelirovanie
kinetiki geterogennykh kataliticheskikh protsessov (Sim-
ulation of Kinetics of Heterogeneous Catalytic Pro-
cesses), Moscow: Khimiya, 1976.
15. Gorskii, V.G., Planirovanie kineticheskikh eksperimen-
tov (Design of Kinetic Experiments), Moscow: Nauka,
1984.
16. Wang, S.-N and Hofman, H, Dynamic Experiments for
Analysis of Complex Heterogeneous Catalytic Reaction,
Proc. International Conf. “Unsteady State Processes in
Catalysis,” Matros, Yu.Sh., Ed., Novosibirsk: 1990,
p. 286.
17. Ivanov, S.I. and Makhlin, V.A., Catalytic Reaction of
Methanol with Hydrogen Chloride onγ-Al2O3: Kinetics
and Mechanism of the Reaction, Kinet. Katal., 1996, vol.
37, no. 6, p. 873 [Kinet. Catal. (Engl. Transl.), vol. 37,
no. 6, p. 812].
18. Makhlin, V.A., Evenchik, A.S., Romanchuk, S.V.,
Ivanov, S.I., and Kolesnikov, S.E., Method for Produc-
tion of Methyl Chloride, RF Patent 2051885, 1992.
19. Satterfil’d, Ch.N., Massoperedacha v geterogennom
katalize (Mass Transfer in Heterogeneous Catalysis),
Moscow: Khimiya, 1976.
20. Frank-Kamenetskii, D.A., Diffuziya i teploperedacha v
khimicheskoi kinetike (Diffusion and Heat Transfer in
Chemical Kinetics), Moscow: Nauka, 1967.
21. Aris, R., Analiz protsessov v khimicheskikh reaktorakh
(Analysis of Processes in Chemical Reactors), Lenin-
grad: Khimiya, 1967.
22. Ioffe, I.L. and Pis’men, L.M., Inzhenernaya khimiya
geterogennogo kataliza (Engineering Chemistry of Het-
erogeneous Catalysis), Moscow: Khimiya, 1972.
23. Aerov, M.E., Todes, O.M., and Narinskii, M.A., Appa-
raty so statsionarnym zernistym sloem: gidravlicheskie i
teplovye osnovy raboty (Fixed-Bed Apparatuses:
Hydraulic and Thermal Principles of Their Operation),
Moscow: Khimiya, 1979.
24. Swaaij, W.P.M.Van, The Design of Gas-Solids Fluid Bed
and Related Reactors, ACS Int. Symp. Ser., 1978, vol. 72,
p. 193.
25. Yates, J.G., Fundamentals of the Fluidized-Bed Chemi-
cal Processes, London: Butterworths, 1983.
26. Slin’ko, M.G., Modelirovanie khimicheskikh reaktorov
(Modeling of Chemical Reactors), Novosibirsk: Nauka,
1968.
27. Ostrovskii, G.M. and Volin, Yu.M., Metody optimizatsii
khimicheskikh reaktorov (Methods of Optimization of
Chemical Reactors), Moscow: Khimiya, 1967.
28. Evenchik, A.S. and Makhlin, V.A., Gas-Phase Promo-
tion of a Silver Catalyst and Parametric Sensitivity of a
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
257
Tubular Reactor for Synthesis of Ethylene Oxide, Khim.
Prom-st., 1988, no. 3, p. 135.
29. Evenchik, A.S. and Makhlin, V.A., Parametric Sensitiv-
ity of a Catalytic Tubular Reactor, Teor. Osn. Khim.
Tekhnol., 1991, vol. 25, no. 6, p. 828.
30. Evenchik, A.S. and Makhlin, V.A., Optimum Structure
of a Catalyst for the Reaction of Partial Oxidation in a
Tubular Reactor, Teor. Osn. Khim. Tekhnol., 1993, vol. 27,
no. 4, p. 398 [Theor. Found. Chem. Eng. (Engl. Transl.),
vol. 27, no. 4, p. ].
31. Evenchik, A.S. and Makhlin, V.A., Change in Activity
along the Length of a Catalyst Bed during Production of
Ethylene Oxide in Gas-Phase Promotion, Kinet. Katal.,
1989, vol. 30, p. 830.
32. Navorski, Dzh. and Velez, E., Oxidative Chlorination of
Ethylene, Kataliz v promyshlennosti (Catalysis in Indus-
try), Lich, B., Ed., Moscow: Mir, 1986, vol. 1.
33. Steilz, A., Dehydrogenation and Oxidative Dehydroge-
nation, Kataliz v promyshlennosti (Catalysis in Indus-
try), Lich, B., Ed., Moscow: Mir, 1986, vol. 2.
34. Steynberg, A.P., Espinoza, R.I., Jager, B., and Vos-
loo, A.C., High Temperature FisÒHer-Tropsch Synthe-
sis in Commercial Practice, Appl. Catal., A, 1999, vol.
186, p. 41.
35. Harrison, D. and Grace, J.R., Fluidized Beds with Inter-
nal Baffels, in Fluidixation, Devidson, I.F. and Harrison, D.,
Eds., London: Academic, 1971, ch. 13.
36. Tamarin, A.I. and Borodulya, V.A., Study of Thermal
Diffusivity of the Fluidized Bed Stagnated by Grids,
Inzh.-Fiz. Zh., 1963, vol. 6, no. 11, p. 26.
37. Romanchuk, S.V., Zolotarskii, V.A., Evenchik, A.S., and
Makhlin, V.A., Influence of a Small-Size Packing on the
Intensity of Mass Transfer in the Fluidized Bed of a
Granular Material, Teor. Osn. Khim. Tekhnol., 1993,
vol. 27, no. 3, p. 296 [Theor. Found. Chem. Eng. (Engl.
Transl.), vol. 27, no. 3, p. ].
38. Geldart, D., Gas Fluidization Technology, New York:
Wiley, 1986.
39. Makhlin, V.A., Salamov, R.G., Serebryakov, B.R., and
Slin’ko, M.G., Influence of a Reaction on Expansion and
Mass Transfer in the Organized Fluidized Bed of a Cat-
alyst, Kinet. Katal., 1982, vol. 33, p. 252.
40. Miracca, I. and Piovesan, L., Light Paraffins Dehydroge-
nation in Fluidized Bed Reactor, Catalysis Today, 1999,
vol. 52, p. 259.
41. Landeghem, F.Van., Nevicato, D., and Potault, I., Fluid
Catalytic Cracking: Modeling of An Industrial Riser,
Appl. Catal., A, 1996, vol. 138, p. 381.
42. Evenchik, A.S., Makhlin, V.A., Volin, Yu.M., and
Slin’ko, M.G., Capacity and Stability of a Reactor
Assembly with an Upflow, Dokl. Akad. Nauk SSSR,
1984, vol. 275, no. 3, p. 677.
43. Evenchik, A.S., Makhlin, V.A., Timoshenko, V.I., and
Slin’ko, M.G., On the Quasi-Steady State of a Heteroge-
neous Catalytic Reaction in an Upflow Reactor, Dokl.
Akad. Nauk SSSR, 1982, vol. 265, no. 5, p. 1209.
44. Makhlin, V.A., Evenchik, A.S., and Slin’ko, M.G., Pecu-
liarities of Catalytic Processes Realization in Transport
Line Reactors (TLR), Proc. World Congress III of Chem-
ical Engineering, Tokyo, 1986, vol. 4, p. 255.
Vol. 43 No. 3 2009
258 MAKHLIN
45. Klenov, O.P., Aerodynamics of Catalytic Reactors and
Methods for Their Charging, Sb. tr. “Kursy povysheniya
kvalifikatsii po katalizu” (Continuing Education Courses
on Catalysis), Noskov, A.S., Ed., Moscow, 2003, part. 2,
p. 177.
46. Klenov, O.P., Zolotarskii, I.A., Daut, V.A., and Tsuker-
man, M.Ya., Reactor for Conducting Heterogeneous
Exothermic Synthesis, RF Patent 2136359, 1999.
47. Cybulski, A. and Moulin, J.A., Monoliths in Heteroge-
neous Catalysis, Catal. Rev. Sci. Eng., 1994, vol. 36,
no. 2, p. 179.
48. Ismagilov, Z.R., Development, Manufacture and Pros-
pects of Using Honeycomb Catalysts for Environmental
Protection in Russia, Khim. Prom-st., 1996, no. 4, p. 283.
49. Pfefferle, L.D. and Pfefferle, W.C., Catalysis in Combus-
tion, Catal. Rev.-Sci. Eng., 1987, vol. 29, nos. 2-3, p. 219.
50. Schmidt, L.D., Modeling Millisecond Reactor, Proc. VI
Congress of Natural Gas Conversion, Alaska, USA,
2003, p. 17.
51. Noskov, A.S., Catalysts and Processes for Deep and
Selective Oxidation, Sb. tr. “Kursy povysheniya kvali-
fikatsii po katalizu” (Continuing Education Courses on
Catalysis), Noskov, A.S., Ed., Moscow, 2003, part. 2,
p. 111.
52. Okunev, B.N., Zolotarskii, V.A., and Makhlin, V.A.,
External-Diffusion Mode of a Catalytic Process for Puri-
fication of Gas Emissions in an Adiabatic Reactor, Teor.
Osn. Khim. Tekhnol., 1994, vol. 28, no. 4, p. 388 [Theor.
Found. Chem. Eng. (Engl. Transl.), vol. 28, no. 4, p. 388].
53. Curtone, M.B., Beebe, K.W., Dalla Betta, R.A., Schlat-
ter, J.C., Nickolas, S.G., and Tsuchiya, T., Development
of a Catalytic Combustor for a Heavy-Duty Utility Gas
Turbine, Catal. Today, 1999, vol. 47, p. 391.
54. Ozava, Y., Fujii, T., Sato, M., Kanazawa, T., and Inoue,
H., Development of a Catalytically Assisted Combustor
for a Gas Turbine, Catal. Today, 1999, vol. 47, p. 399.
55. Mak-Kolloch, D., Catalytic Hydroprocessing in Petro-
leum Refining, Kataliz v promyshlennosti (Catalysis in
Industry), Lich, B., Ed., Moscow: Mir, 1986, vol. 1, p. 80.
56. Kurganov, V.M., Development of Hydrogenation Pro-
cesses in Foreign and Domestic Oil Refining, Sb. tr.
Mezhdunarodnoi shkoly povysheniya kvalifikatsii v
oblasti inzhenernoi khimii. Tret’ya sessiya (Proc. Inter-
national Continuing Education School in the Field of
Chemical Engineering. Third Session), Makhlin, V.A.,
Ed., Moscow: NIFKhI im. L.Ya. Karpova, 1997, p. 69.
57. Edgar, M., Catalytic Reforming of Naphtha in Oil Refin-
ing, Kataliz v promyshlennosti (Catalysis in Industry),
Lich, B., Ed., Moscow: Mir, 1986, vol. 1, p. 135.
58. Espinoza, R.I., Steynberg, A.P., Jager, B., and Vos-
loo, A.C., Low Temperature FisÒher-Tropsch Synthesis
from a Sasol Perspective, Appl. Catal., A, 1999, vol. 186,
p. 13.
59. Rameshwar, S., Hiwale, NitinV., Bhate, YogeshS., and
Mahajan, Sanjay M., Mahajani. Industrial Applications
of Reactive Distillation: Recent Trends. Review R1, Int.
J. Chem. Reactor Eng., 2004, vol. 2, p. 1.
60. Harmsen, G.Jan., Reactive Distillation: The Front-Run-
ner of Industrial Process Intensification. A Full Review
of Commercial Applications, Research, Scale-Up,
Design and Operation, Chem. Eng. Process., 2007,
vol. 46, p. 774.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
61. Gorak, A. and Hoffmann, A., Catalytic Distillation in
Structured Packings: Methyl Acetate, AIChE J., 2001,
vol. 47, no. 5, p. 1067.
62. Vora, N. and Daoutidis, P., Dynamics and Control of An
Ethyl Acetate Reactive Distillation Column, Ind. Eng.
Chem. Res., 2001, vol. 40, no. 3, p. 833.
63. Rix, A., Grund, G., and Bueschken, W., Process for Pre-
paring Highly Pure Raffinate II and Methyl tert-Butyl
Ether, US Patent 6657090, 2003.
64. Li, Y., Yu, S., Yuan, X., and Wang, H., The Etherification
of Methanol and Isobutene in a Catalytic Distillation
Column Packed with Zeolite-Beta-Coated Catalytic
Packing, Ind. Eng. Chem. Res., 2002, vol. 41, no. 20,
p. 4936.
65. Gildert, G.R., Hydrogenation of Benzene to Cyclohex-
ane, US Patent 6187980, 2001.
66. Netzer, D., Method for Producing Ethyl Benzene, US
Patent 6252126, 2001.
67. Zhang, J., Li, D., and Cao, G., Apparatus and Method for
Alkylation of Benzene/Toluene with Propylene by Cata-
lytic Distillation, Faming Zauanli, cf CA 137 : 95516,
2001.
68. Mukherjee, U. and Louie, W., Hydrocracking of Vacuum
Gas and Other Oils Using Post-Treatment Reactive Dis-
tillation System, US Patent 6547956, 2003.
69. Groten, W.A. and Loescher, M.E., Process for the Pro-
duction of an Ultra Low Sulfur. US Patent 6416659,
2002.
70. Liu, H., Qu, Y., and Wang, W., Simulation of Hydration
Process of Water and Ethylene Oxide by Reactive Distil-
lation To Produce Glycol, Beijing Huagong Daxue Xue-
bao, cf CA 137: 156380, 2002.
71. Carland, R.J., Fractionation Tray for Catalytic Distilla-
tion. US Patent 5308451, 1994.
72. Van Hasselt, B., The Three-Levels-Of-Porosity Reactor,
Ph.D. Dissertation, Delft: Delft Univ. of Technology,
1999.
73. Buchholz, M., Pinaire, R., and Ulowetz, M.A., Structure
and Method for Catalytically Reacting Fluid Streams in
Mass Transfer Apparatus, EEC Patent 448884B1, 1995.
74. Stringaro, J.P., Reactor Including a Catalyst Body for
Performing a Heterogeneous Reaction, EEC Patent
433222A1, 1991.
75. Gelbein, A.P. and Buchholz, M., Process and Structure
for Effecting Catalytic Reactions in Distillation Struc-
ture, US Patent 5073236, 1991.
76. Stringaro, J.P., Catalyzing Fixed Bed Reactor, US Patent
5470542, 1995.
77. Taylor, R. and Krishna, R., Modeling Reactive Distilla-
tion, Chem. Eng. Sci., 2000, vol. 55, no. 22, p. 5183.
78. Makhlin, V.A., Evenchik, A.S., Groshev, G.L., and
Slin’ko, M.G., Parametric Sensitivity, Thermal Run-
away, “Decomps”, and Ultimate Loads of a Tubular
Reactor for Synthesis of Ethylene Oxide, Khim. Prom-
st., 1987, no. 8, p. 479.
79. Evenchik, A.S. and Makhlin, V.A., Modeling and Anal-
ysis of a Process for Producing Ethylene Oxide by Oxi-
dizing the Ethylene–Oxygen Mixture in a Cooled Tubu-
lar Reactor, Teor. Osn. Khim. Tekhnol., 1992, vol. 26,
no. 2, p. 212.
Vol. 43 No. 3 2009
 DEVELOPMENT AND ANALYSIS OF HETEROGENEOUS CATALYTIC PROCESSES
80. Slin’ko, M.G., Gel’bshtein, A.I., Treger, Yu.A., Makh-
lin, V.A., Bakshi, Yu.M., Gel’perin, E.I., Romanchuk, S.V.,
Sonin, E.V., and Flid, M.R., Matematicheskoe modeliro-
vanie i izuchenie vozmozhnosti intensifikatsii protsessa
oksikhlorirovaniya etilena v proizvodstve khlorvinila na
Kaluzhskom PO “Khlorvinil” (Mathematical Modeling
and Study of the Possibility of Enhancing the Process of
Ethylene Oxychlorination in the Production of Vinyl
Chloride at Kaluga PO Khlorvinil), Moscow: NIFKhI
im. L.Ya. Karpova, 1985.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
View publication stats
259
81. Makhlin, V.A., Zolotarskii, V.A., Okunev, B.N., Roman-
chuk, S.V., and Evenchik, A.S., Razrabotka opti-
mal’nogo rezhima i skhemnogo resheniya protsessa
oksikhlorirovaniya etilena s ispol’zovaniem kislorodo-
vozdushnykh smesei proizvodstve Sayanskoe PO “Khim-
prom” (Optimum Regime and Process Flowsheet for
Ethylene Oxychlorination Using Oxygen–Air Mixtures
at Sayanskoe PO Khimprom), Moscow: NIFKhI
im. L.Ya. Karpova, 1991.
Vol. 43 No. 3 2009