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Chemical Engineering Journal 238 (2014) 129–139

Contents lists available at ScienceDirect

Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

Developing of the mathematical model for controlling the operation


of alkane dehydrogenation catalyst in production of linear alkyl benzene
E.V. Frantsina ⇑, E.N. Ivashkina, E.D. Ivanchina, R.V. Romanovskii
National Research Tomsk Polytechnic University, pr. Lenina 30, Tomsk 634050, Russia

h i g h l i g h t s

 Process model dehydrogenation of alkanes is predicting the deactivation of catalyst.


 The influence of raw material for the catalyst lifetime was obtained.
 The optimum working parameters for different Pt-catalysts were determined.
 The optimum flow rate of water in the reactor has been found.

a r t i c l e i n f o a b s t r a c t

Article history: The main results are presented on the modeling of the industrial process of catalytic dehydrogenation of
Available online 15 October 2013 C9–C14 n-alkanes which is one of the technological stages in the production of linear alkyl benzene used
in the synthesis of synthetic detergents. Application of the developed mathematical model in evaluating
Keywords: the influence of the raw material composition on the target product yield is considered. The calculation
Dehydrogenation results are given for the optimal technological modes with different dehydrogenation Pt-catalysts and
Pt-catalyst also for prediction of catalysts lifetime duration.
Linear alkyl benzene
Ó 2013 Elsevier B.V. All rights reserved.
Deactivation
Optimal activity
Mathematical model

1. Introduction operating modes is also of a great importance [6,7]. The application


of the process simulation systems determines a new level of oper-
The dehydrogenation of hydrocarbons is one of the most impor- ational efficiency of processes related, and allows optimizing the
tant processes in the organic synthesis. The process of dehydroge- operating modes of catalysts.
nation of C9–C14 n-alkanes into alkenes is used in the production of Therefore, our aim was to develop an intelligent system control-
linear alkyl benzene (LAB) that are the intermediate products in ling the operation of the alkane dehydrogenation catalyst in the
the synthesis of synthetic detergents and surfactants [1]. In an LAB production, and allowing the increase in the operational effi-
industrial reactor, this process is usually performed at the pressure ciency of an industrial unit.
of 0.2 MPa, and the temperature of 465–495 °C. Different catalysts
are used, usually containing platinum deposited on alumina or
2. Brief description of the technology
zeolite. A rather high selectivity of 90% is obtained at a relatively
low conversion of approx. 10–11%. The average catalyst operating
The LAB production complex includes five interconnected units:
cycle duration is 5–8 months. Even a slight increase in the selectiv-
PAREX unit, preliminary fractionation facility, dehydrogenation
ity, activity or stability of Pt-catalysts used in the alkane dehydro-
plant for converting alkanes into alkenes, unit for selective hydro-
genation can substantially influence the cost and the quality of the
genation of side products of dehydrogenation, and the alkylation
LAB produced [2–5]. Thus, the urgency of solving the problems re-
plant, where the LAB is produced from the alkenes and benzene
lated to the abovementioned changes is obvious.
(Fig. 1).
The modernization of this technology is not limited to the
development and the improvement of Pt-catalysts. The computer
assistance for industrial processes aimed at optimizing the 3. The mathematical model

⇑ Corresponding author. Tel.: +7 9050897129. The system for controlling the operation of gasoline reforming
E-mail address: evf@tpu.ru (E.V. Frantsina). Pt catalysts was recently developed, based on the hierarchical

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.09.049
130 E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139

Symbols

H enthalpy (kJ/mol) T0 start temperature (temperature of an environment) (K)


S entropy (J/mol K) Tin temperature of an input in a reactor (K)
Ci concentration of ith hydrocarbon (mol/m3) Cin entrance concentration of hydrocarbon (mol/m3)
e pore volume of catalyst layer V volume of catalyst (m3)
ri rate of reaction (mol/m3 h) G hour expenditure of raw material (m3/h)
wj rate of jth component in ith reaction transformation t time (h)
(mol/m3 h) z total volume of the processed raw material (m3)
T temperature of the process (K) x mass concentration of substance in hydrocarbons
DHj thermal effect of reaction (J/mol) (mass%)
Cp thermal capacity of a mixture (J/mol K) x molar fraction of substance in hydrocarbons (mol/l)
q density of a mixture (kg/m3) Mr molar weight (kg/mol).

approach, at the Department of Chemistry of Fuels and Chemical n-alkanes (0.01–0.50 wt.%) that are taken into account in the math-
Cybernetics in Tomsk Polytechnic University. It was then success- ematical formulation of the process. The mathematical model we
fully applied in the industry [8,9]. The mathematical formulation of developed for the n-alkane dehydrogenation on Pt-catalysts is sen-
the process of C9–C14 alkane dehydrogenation is based on the same sitive to the changes in the chemical composition of raw materials
approach. The mixture of n-alkanes with the difference of 1–4 car- [11]. For the ith component, the material balance can be written
bon atoms in their carbon chains, e.g. C10–C13 or C11–C14, is used as with the differential equation:
a raw material for dehydrogenation. In this case, the C10–C14 frac-
@C i @C i XN
tion is unsuitable. The restriction is dictated by the necessity to G þG ¼ ð1  eÞ r j ; i ¼ 1 . . . M; j ¼ 1 . . . N; ð1Þ
convert the light n-alkanes without boosting the cracking of the @z @V j¼1
heavier alkanes. Results of studies of the reactivity of the given
homologous group show that these hydrocarbons have substan- where G is the raw material flow rate, m3/h; Ci is the ith hydrocar-
tially different relative rates of dehydrogenation [10]: the lighter bon concentration, mol/m3; V is the catalyst volume, m3; e = 0–1 is
hydrocarbons are much more slowly dehydrogenated than the the catalyst layer porosity; rj is the jth reaction rate, mol/(m3 h);
heavier ones. Thus, in order to avoid a high yield of gases in the z = G  t is the total volume of raw material processed after catalyst
cracking of heavier hydrocarbons and high losses of the target regeneration, m3; t is the time, h; M is the number of components,
product, it is necessary to provide the required number of carbon and N is the number of reactions. The heat balance can also be writ-
atoms. Nevertheless, the raw material contains C9 and C14 ten with the differential equation:
PN
@T @T j¼1 ðDH j r j Þ
G þG ¼ ð1  eÞ ; ð2Þ
@z @V Cp
where T is the process temperature, K; DHj is the reaction heat,
J/mol; C is the heat capacity of the mixture, J/(kg K); q is the raw
material density, kg/m3.
The initial and boundary conditions are the following:

z ¼ 0 : C i ¼ 0; T ¼ T 0 ;
V ¼ 0 : C i ¼ C i;in ; T ¼ T in :

The basis for the considered mathematical model is the formal-


ized hydrocarbon conversion scheme that takes the hydrocarbon
reaction abilities under dehydrogenation conditions into account
(Fig. 2).
Known conceptions [12] of the dehydrogenation mechanism al-
lowed forming the presumable transformation scheme of the pro-
cess. We used the Gaussian program package with PM3 procedure
of NDDO (Neglect of Diatomic Differential Overlap) method based
on quantum-chemistry modeling to calculate the electron mole-
cule structures, and to estimate the thermodynamic characteristics
(DGr, DHr, DS) for the reactions conducted under 753 K and
0.2 MPa. The method under consideration takes into account oscil-
latory and rotator movements of atoms, electron orbit patterns, ef-
fects of double bonds conjugation, and reproduces the structure
and energy hyper valence compounds with high validity, providing
adequate accuracy for high-quality reproduction of molecule phys-
iochemical characteristics [13,14]. The results are illustrated in
Fig. 1. LAB production flow chart: (I) n-alkanes from Parex unit; (II) n-alkanes C10– Table 1.
C13; (III) n-alkanes C14–C17; (IV) n-alkanes C18 and higher; (V) hydrogenous gas; The calculated data on the component structures involved in
(VI) mixture of n-alkanes and monoalkenes; (VII) recycling n-alkanes; (VIII)
benzene from benzene reforming installation; (IX) alkylate bottom; (X) alkyl
the dehydrogenation process is compared with the experimental
benzene; (XI) sulfur from the elemental sulfur installation; (XII) LAB sulfonate; data [15]. In the absence of extensive information on higher al-
(XIII) alkali; and (XIV) sodium LAB sulfonate. kanes, the comparison is made on the basis of entropy and heat
E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139 131

Fig. 2. The formalized reaction network of the dehydrogenation process.

Table 1
The mean values of reaction thermodynamic characteristics in dehydrogenation process (753 K, 0.20 MPa).

Reaction DGr (kJ/mol) DHr (kJ/mol) DS (kJ/(mol K))


1. Alkane ? Alken-1 + H2 47.94 49.89 0.13
2. Alkane ? Alken-2(n) + H2 70.34 33.04 0.14
3. Alkene-2(n) ? Alkadiene (cumul) + H2 5.44 90.37 0.13
4. Alkene-2(n) ? Alkadiene (conn) + H2 –69.26 32.49 0.14
5. Alkene-2(n) ? Alkadiene (sec) + H2 –47.69 49.89 0.13
6. Alkene-1 ? Alkadiene (cumul) + H2 –8.28 78.56 0.13
7. Alkene-1 ? Alkadiene (conn) + H2 –67.49 29.59 0.13
8. Alkene-1 ? Alkadiene (sec) + H2 –47.29 49.92 0.13
9. Isoalkane ? Isoalken + H2 –81.14 24.50 0.14
10. Isoalkene ? Isoalkadiene + H2 –67.91 33.38 0.14
11. Alkene ? Isoalkene –2.27 0.94 0.00
12. Alkane ? Isoalkane 3.06 2.51 0.00
13. Alkane ? Cycloalkane + H2 –64.21 –33.12 0.04
14. Alkane ? Arene + 4H2 –331.21 –58.68 0.36
15. Alkene ? Cycloalkane –7.86 –64.51 –0.07
16. Alkene ? Arene + 3H2 –289.29 –90.07 0.27
17. Cycloalkane ? Arene + 3H2 –333.12 –25.52 0.36
18. Alkadiene ? Arene + 2H2 –251.07 –137.45 0.15
19. Isoalkane ? Cycloalkane + H2 –76.48 –37.15 0.05
20. Isoalkane ? Arene + 4H2 –353.60 –49.66 0.40
21. Isoalkene ? Arene + 3H2 –289.56 –67.64 0.30
22. Isoalkene ? Cycloalkane –12.44 –55.13 –2.04
23. Alkane ? Cracking product –137.77 84.03 1.05
24. Alkane ? Cracking product –137.76 84.05 0.14
25. Alkadiene ? Cracking product –137.22 83.26 0.17
26. Isoalkane ? Cracking product –138.74 84.39 0.16
27. Isoalkene ? Cracking product –140.03 81.69 0.16
28. Isoalkadiene ? Cracking product –137.75 98.31 0.16
29. Arene ? Coke formation product –510.66 –425.15 0.56
30. Alkene ? Coke formation product –508.64 –423.12 0.56
31. Alkadiene ? Coke formation product –509.35 –424.17 0.56

capacity. Under average conditions of the process (733 K and cumulative double bonds is not allowed thermodynamically
2 atm), the mean relative error of the entropy component does ðDG0r  5 kJ=molÞ. The presence of isomeric alkanes in the prod-
not exceed 5%. Under standard conditions (298 K and 1 atm), the uct is determined by the dehydrogenation processes of iso-alkanes
relative error in calculating the entropy does not exceed 5%, the which are present in raw materials. All other possible reactions are
heat capacities – 7%. thermodynamically probable and have approximately the same
The results of the calculation show that aromatization reaction values of isobaric-isothermal potential ðDG0r  70 kJ=molÞ.
appears to be the most thermodynamically probable Dienes with conjugate and secured double bonds are produced in
ðDG0r  300 kJ=molÞ. Isomerization reactions of alkanes and al- the process, whereas the formation of dienes with cumulative
kenes do not run in the process. Also, the formation of dienes with double bonds is not thermodynamically allowed under these
132 E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139

conditions. Cracking ðDG0r  140 kJ=molÞ and coke formation Dehydrogenation reactor (Fig. 1) is a capacitive device with a
ðDG0r  510 kJ=molÞ are the main by-reactions. radial entering of the raw material. Its overall dimensions are:
Based on these results, the formalized scheme of higher alkanes D – 1675 mm, H – 7555 mm. The volume of the catalyst load is
C9–C14 dehydrogenation process was formed (Fig. 2). Substances 3.14 m3. The application of an ideal plug flow model is suitable to
are combined into several groups of pseudo components according describe the higher alkanes dehydrogenation process in a fixed-
to their reactionary ability evaluated according to isobaric–isother- bed reactor. According to the calculation of Reynolds (Re = 965.88,
mal potential DGr. Thus, 11 groups of pseudo components take part laminar flow) and Peclet numbers (Pe = 2494, PeT/PeD = 1.05  1.5)
in 22 types of chemical reactions (see Fig. 3). we can assume that diffusion plays insignificant role in the process
This level of mechanism formalization allows cutting the math- of mass transfer which occurs by means of convection. For the
ematical description of passing reactions and time solution of dehydrogenation process, the reaction limited regime is observed
material and thermal balance equations down, as well as keeping (Thiele modulus Uj < 1, internal effectiveness factor gj = 0.98–1).
the sensitivity concerning raw feed components, and the self- For the mathematical description of hydrodynamic and heat
descriptiveness concerning products of passing reactions. model of industrial reactor dehydrogenation, some assumptions
The target reactions (dehydrogenation of alkanes into alkenes) are accepted:
and the side reactions (dehydrogenation of alkanes into dienes,
dehydrocyclization, coking) pass on the surface of a dehydrogena-  The industrial reactor is considered an ideal plug flow reactor.
tion catalyst. In this case, dienes and aromatic hydrocarbons are  Mass and heat transport occur by means of convection.
the main sources of coke. The kinetic model of the dehydrogena-  There is an adiabatic operation.
tion process, according to the law of active mass is written down  The formalized mechanism of hydrocarbons transformation
in the following way (Table 2). (Fig. 2).
The initial conditions are s = 0 and Ci = C0i, where i is respective
hydrocarbon (alkane, alkene, diene, etc.). The developed mathe- We put the value of the porosity of the catalyst layer (0.19–
matical model is used as the basis for the dehydrogenation process 0.58) for industrial dehydrogenation catalysts to take the charac-
simulation system that allows not only to optimize calculations, teristics of the catalyst layer in the model into account. It shows
but also to predict the lifetime of Pt-catalysts. The kinetic model the proportion of the free volume, the unemployed solid phase
developed is formalized and quasihomogeneous. Therefore, the for each particular type of catalyst. We assume that the conversion
rate constants shall be regarded as effective, i.e. they are combina- occurs only in the volume of the solid catalyst. Results are shown
tion of constants of all intermediate stages. for a linear velocity of 12.74 m/s.
An example of the kinetic equations for n-decane is given
below:
8
> k1
>
> C 10 H22 ¢ C 10 H20 þ H2
>
>
>
<
k1
k5
> C 10 H22 ¢ i  C 10 H22
>
> k5
>
>
>
: k8
C 10 H22 þ H2 ! C 5 H12 þ C 5 H12

dC C10 H22
¼ k1 C C 10 H22 þ k1 C C10 H20 C H2  k5 C C10 H22 þ k5 C iC10 H22
dt
 k8 C C10 H22 C H2 t ¼ 0; C C 10 H22 ¼ C 0C 10 H22

All the reactions are shown in Fig. 2 and Table 3.


Modeling the process of C9–C14 hydrocarbons dehydrogenation
represents a difficult task. Fair quantities of passing reactions cause
high dimensionality of mathematical model, and demand determina-
tion of a great number of kinetic parameters (preexponential factors k0
and activation energies Ea) for all types of chemical reactions. For tech-
nical reasons, it is impossible to realize the kinetic experiment at the
industrial installation. Therefore, a more effective option of determin-
ing the k0 Ea values is solving the reverse kinetic task [16].
When a finite-difference method of calculation is to be used to
solve the differential equations system that describes a real chem-
ical process, we use the net method [16].
Having the reactants concentrations as the input data, the reac-
tions rates as the responses and an initial guess of unknown
parameters (taken from the literature), the least square parameters
estimate was found. Using this approach, the rate constants for the
reactions at the industrial unit were defined (apparent rate con-
stants). To verify the parameters found, the data from the indus-
trial isomerization unit (Russian-based) was computed, starting
from 2005 and up to now. The conditions in the simulations were
the same as they were at the industrial unit. The simulation data
therefore can be directly compared to the experimental data. The
Fig. 3. Reactor for catalytic transformations of the radial type. calculated composition of dehydrogenation (simulation results)
E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139 133

Table 2
Normal alkanes dehydrogenation process kinetic model on basis of formalized scheme of hydrocarbons transformation.

Compound group Time dependency of the compound’s concentration


Alkanes dC C n H2nþ2
¼ k1 C C n H2nþ2 ðnparaffinÞ þ k17 C C n H2n ðolefin1Þ C H2  k2 C C n H2nþ2 ðnparaffinÞ þ k18 C C n H2n ðolefin2ðnÞÞ C H2  k6 C Cn H2nþ2 ðP paraffinÞ
dt
 k7 C C n H2nþ2 ðP paraffinÞ  k11 C C n H2nþ2 ðP paraffinÞ

Isoalkanes dC Cn H2nþ2
¼ k4 C C n H2nþ2 ðisoparaffinÞ  k6 C C n H2nþ2 ðP paraffinÞ  k7 C C n H2nþ2 ðP paraffinÞ  k11 C C n H2nþ2 ðP paraffinÞ
dt

dC Cn H2n
Alkenes-1 ¼ k1 C Cn H2nþ2 ðnparaffinÞ  k17 C C n H2n ðolefin1Þ C H2  k3 C Cn H2n ðnolefinÞ þ k19 C C n H2n2 ðndienÞ C H2  k9 C C n H2n ðP olefinÞ  k12 C C n H2n ðP olefinÞ  k15 C C n H2n ðP olefinÞ
dt

dC Cn H2n
Alkenes-2(n) ¼ k2 C Cn H2nþ2 ðnparaffinÞ  k18 C C n H2n ðolefin2ðnÞÞ C H2  k21 C C n H2n ðolefin2ðnÞÞ  k9 C C n H2n ðP olefinÞ  k15 C Cn H2n ðP olefinÞ  k12 C C n H2n ðP olefinÞ þ k22 C C n H2n2 ðndienÞ C H2
dt

dC Cn H2n
Isoalkenes ¼ k4 C Cn H2nþ2 ðisoparaffinÞ  k5 C Cn H2n ðisoolefinÞ þ k20 C C n H2n2 ðisodienÞ C H2  k9 C Cn H2n ðP olefinÞ  k12 C C n H2n ðP olefinÞ  k15 C C n H2n ðP olefinÞ
dt

dC Cn H2n2
Dienes ¼ k3 C C n H2n ðolefin1Þ  k19 C Cn H2n2 ðndienÞ C H2 þ k21 C C n H2n ðolefin2ðnÞÞ  k13 C C n H2n2 ðP dienÞ  k22 C C n H2n2 ðndienÞ C H2  k10 C Cn H2n2 ðP dienÞ  k16 C C n H2n2 ðP dienÞ
dt

dC Cn H2n2
Isodienes ¼ k5 C C n H2n ðisoolefinÞ  k20 C Cn H2n2 ðisodienÞ C H2  k13 C C n H2n2 ðP dienÞ  k10 C Cn H2n2 ðP dienÞ  k16 C C n H2n2 ðP dienÞ
dt

dC Cn H2n
Cyclohadrocarbons ¼ k6 C Cn H2nþ2 ðP paraffinÞ  k8 C Cn H2n ðCycloparaffinÞ
dt

dC Cn H2n6
Arenes ¼ k8 C C n H2n ðcycloparaffinÞ þ k7 C C n H2nþ2 ðP paraffinÞ þ k9 C C n H2n ðP olefinÞ þ k10 C C n H2n2 ðP dienÞ  k14 C Cn H2n6 ðarenÞ
dt

dC Cracking products
Cracking gases ¼ k11 C C n H2nþ2 ðP paraffinÞ þ k12 C Cn H2n ðP olefinÞ þ k13 C C n H2n2 ðP dienÞ
dt

dC CokeFormation products
Coke ¼ k14 C C n H2n6 ðarenÞ þ k15 C C n H2n ðP olefinÞ þ k16 C C n H2n2 ðP dienÞ
dt

Hydrogen dC H2
¼ k1 C C n H2nþ2 ðnparaffinÞ  k17 C C n H2n ðolefin1Þ C H2 þ k2 C C n H2nþ2 ðnparaffinÞ  k18 C C n H2n ðolefin2ðnÞÞ C H2 þ k3 C C n H2n ðolefin1Þ  k19 C C n H2n2 ðndienÞ C H2
dt
þ k21 C C n H2n ðolefin2ðnÞÞ þ k4 C C n H2nþ2 ðisoparaffinÞ  k22 C C n H2n2 ðndienÞ C H2 þ k5 C C n H2n ðisoolefinÞ  k20 C C n H2n2 ðisodienÞ C H2 þ k6 C C n H2nþ2 ðP paraffinÞ
þ 3k9 C C n H2n ðP olefinÞ þ 4k7 C C n H2nþ2 ðP paraffinÞ þ 3k8 C C n H2n ðcycloparaffinÞ þ 2k10 C C n H2n2 ðP dienÞ

were in a very good agreement with each set of experimental data We compared the calculated values of the output stream with
taken at the industrial unit for the whole period considered the analogous experimental values to test the validity of the model.
(9 years). The results of the rate constants estimation are given in The values correspond to beginning of the catalyst lifetime, when
Table 3. its deactivation by coke is minimal.
134 E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139

Table 3
Values of the main kinetic parameters of C9–C14 alkanes dehydrogenation process.

Reaction Kinetic parameter of the reaction


Ea (kJ/mol) k0 k
N-alkane ? Alkene-1 + H2 110 7.45  107 s1 0.5698 s1
N-alkane ? Alkene-2(n) + H2 118 8.03  107 s1 0.5235 s1
Alkene-1 + H2 ? N-alkane 60 3.92  103 l s1 mol1 0.2682 l s1 mol1
Alkene-2(n)+H2 ? N-alkane 85 5.45  103 l s1 mol1 0.007 l s1 mol1
Alkene-1 ? N-diene + H2 190 2.65  1011 s1 2.1079 s1
Alkene-2(n) ? N-diene + H2 190 2.65  1011 s1 2.1079 s1
N-diene + H2 ? Alkene-1 160 5.55  109 l s1 mol1 0.0436 l s1 mol1
N-diene + H2 ? Alkene-2(n) 160 4.1843  109 l s1 mol1 0.0329 l s1 mol1
Isoalkane ? Isoalkene + H2 170 2.1  1011 s1 0.2178 s1
Isoalkene ? Izo-diene + H2 150 8.30  108 s1 1.7688 s1
Izo-diene + H2 ? Isoalkene 115 3.28  106 l s1 mol1 0.0342 l s1 mol1
Alkane ? Cycloalkane + H2 200 5.2  1010 s1 0.0004 s1
Alkane ? Arene + 4H2 140 1.1  108 s1 0.0149 s1
Alkene ? Arene + 3H2 135 1.4  108 s1 0.0426 s1
N-diene ? Arene + 2H2 135 2.0  108 s1 0.0608 s1
Cycloalkane ? Arene + 3H2 160 9.0  1010 s1 0.4733 s1
Alkane ? Cracking product 200 1.0  1010 s1 0.0001 s1
Alkene ? Cracking product 200 1.0  1010 s1 0.0001 s1
N-diene ? Cracking product 200 1.0  1010 s1 0.0001 s1
Arene ? Coke formation product 220 5.5  1010 s1 0.000017 s1
Alkene ? Coke formation product 220 4.8  1010 s1 0.000006 s1
N-diene ? Coke formation product 220 5.0  1010 s1 0.000015 s1

Table 4
Calculated and experimental values of product concentration comparison for dehydrogenation process.

Component Input component concentration (mass%) Output component concentration (mass%) Deviation of calculation (%)
Calculation Experiment
Alkanes 97.14 86.94 86.93 0.01
Alkenes 0.0 9.28 9.27 0.11
Dienes 0.0 0.49 0.5 2.00
Isoalkanes 2.98 2.71 2.69 0.74
Isoalkenes 0.0 0.28 0.29 3.45
Isodienes 0.0 0.02 0.02 0.00
Arenes 0.98 0.28 0.29 3.45
Coke formation products 0.0 55.72  10–3 55.94  10–3 0.40
Cracking products 5.46 6.17 5.94 3.77
Hydrogen 94.54 93.83 94.06 0.25

The errors of calculating the primary components concentra- developed integrated criterion for estimating the service state of
tions do not exceed 4% (Table 4), confirming the high accuracy of catalysts for the dehydrogenation of higher n-alkanes. This makes
process kinetic parameters determined using the model. it possible to predict the real service life of catalysts, subject to pro-
cess conditions and the composition of feedstock.
The patent search reveals that the data in [18–20] on the prac-
4. The optimal technological parameters
tical use of the dehydration process, its laws, the properties of used
catalysts, and the methods used to study the causes of their deac-
The realization of the potential of the catalysts depends on the
tivation does not allow us to solve the problem mentioned.
hydrodynamic modes in the reactors and the technological condi-
The properties of the dehydrogenation Pt-catalysts vary consid-
tions. In addition, the real (current) and the steady-state (optimum)
erably during the service life: the effective specific surface area
activities of various commercial catalysts vary widely. The steady-
changes as a result of heat treatment and the accumulation of coke
state activity is regarded as the value that is established upon equal-
(accompanied by a change in its porous structure and a decrease in
ization of the rates of deactivation and self-regeneration of contact
the number of active sites), and the catalyst is poisoned by harmful
[17–19]. The deviation between the current activity and the opti-
impurities [21].
mum must be a quantitative criterion of determining the efficiency
Studies of the deactivation of catalysts by means of mathemat-
of the catalysts in terms of practical realization of their potential.
ical simulation confirm the existence of the optimum region for the
The current activity of the catalysts as the relative value of
occurrence of the self-regeneration reaction on Pt sites. Under con-
which is determined by the ratio between the coke-free surface
ditions of the thermodynamic equilibrium of the reaction system,
and the total surface :
the rates of formation and hydrogenation of intermediate conden-
SðtÞ sation products are equal. A decrease in the specific surface area
aðtÞ ¼ ; ð3Þ due to coke formation is thus reversible, because the catalyst oper-
Sðt0 Þ
ates at high temperatures in a hydrogen bearing environment. This
where S(t) – catalysis surface free of coke; S(t0) – total catalysis means it is possible to perform the process in an optimum region
surface. that corresponds to the thermodynamic equilibrium of the reac-
The optimum technological parameters for improving the tions of the formation and hydrogenation of coke forming
conversion of n-alkanes in the reactors can be found using the structures.
E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139 135

According to the theory of active sites, the surface of a catalyst The optimal catalyst operation mode corresponds to the main-
at the stage of formation in preparation and operation (regenera- tenance of the catalyst activity at its optimal level by varying the
tion and feedstock cycle) is an open system (the reaction mixture independent process parameters: catalyst type, temperature, raw
affects the formation of an active surface); its formation is gov- material flow rate, pressure, hydrogen-containing gas, circulation
erned by the technological conditions, the composition of feed- ratio, raw material quality.
stock, and the concentration of the promoters. The rate of the temperature increase at the reactor inlet, as well
In this regard, the deactivation of a catalyst is an unsteady, non- as the hydrogen-containing gas flow rate must provide the equilib-
equilibrium process of the formation of coke forming structures on rium conditions for coking and hydrogenation of intermediate con-
its surface [22]. The functioning of the catalyst surface is due to densation products. In this case, the maximal yield of the target
quasistationary states that correspond to the optimum (steady- product will correspond to the maximally possible lifetime of a
state) catalyst activity in the feedstock cycle. In this case, the ther- Pt-catalyst.
modynamic equilibrium between the reactions of coke formation In order to estimate the influence of the raw material composi-
and the hydrogenation of intermediate condensation products is tion on the yield of target n-alkenes used further in the alkylation,
established in the nonequilibrium process of deactivation. The the contribution of each of C9–C14 components to the quantitative
long-term maintenance of the stationary state in the reactions un- characteristics of the products (yield of target LABs) was deter-
der nonequilibrium conditions of deactivation can be performed by mined. The range of hydrocarbon concentrations at the inlet of
controlling the temperature and the contact time [17]. dehydrogenation reactor was chosen in accordance with the inter-
For the nonequilibrium process of the formation of an active val of their variation in the real raw materials. The calculation re-
surface of catalysts, it is generally necessary and sufficient to meet sults are shown in Fig. 4.
the following conditions [23]: From the dependences given it is clear that the yield of alkenes
grows with an increase in the C10–C13 hydrocarbons concentra-
(i) the nonlinearity of the reaction system (i.e., the degree of tions, whereas the increase in the concentration of C14 hydrocar-
impact on the reaction process) is not proportional to a bons hardly influences the yield of the target product. It should
change in the parameters under control (contact time, tem- be noted that the changes in the concentrations of C12 and C13
perature, and flow rate of promoters); hydrocarbons have the most profound effect corresponding to a
(ii) the nonequilibrium of the reaction system and quasistation- sharper ascent of the curves. The greatest contribution of these
ary states; hydrocarbons to the yield of the target products can be explained
(iii) the reversibility of chemical reactions. by the fact that the concentrations of C9 and C14 hydrocarbons in
the raw material is two orders less than that of C10–C13 hydrocar-
In industrial catalysis, the natural criterion of stability is the bons. Thus, the latter make the major contribution to the formation
catalyst lifetime. However, the estimation of this criterion is very of alkenes.
time-consuming under laboratorial conditions. Moreover, the con- The calculations were performed for the different catalysts
ditions of laboratorial experiments must be maximally close to the loaded into the dehydrogenation reactor of an industrial unit dur-
industrial ones, and this also causes additional expenses. ing different periods of its operation. Obviously, the application of
Therefore, the following indirect parameters are applied: (1) the the mathematical model of this process provides the choice of the
rate of temperature growth compensating the activity decrease, (2) optimal catalyst type taking into account the composition of raw
the level of steady-state (optimal) activity, and (3) the number of materials.
regenerations endured by a catalyst. Dehydrogenation catalysts differ in content of the base
All these criteria allow us to estimate a catalyst under steady- metal–platinum (KD1 – 1.06 wt.%, KD2 – 0.99 wt.%, and
state operational conditions. To solve any multi-criterion problem, KD3 – 0.92 wt.%), Supported catalysts KD2 and KD3 apply the
it is necessary to define a generalized efficiency criterion reflecting cordierite-Al2O3, the catalyst support KD1 – c-Al2O3. Moreover,
the influences of technological conditions, volume and composi- the KD3 catalyst comprises structure-promoting additives
tion of processed raw materials. (potassium), thereby increasing its stability.
The definition of the steady-state catalyst activity is given in Different reaction abilities of C9–C14 alkanes in the reactions of
[24]: it settles when the rates of catalyst deactivation and dehydrogenation determine the optimal dehydrogenation catalyst
self-regeneration become equal. Determining the equilibrium activity corresponding to the equilibrium conditions between the
conditions for the coke formation and the dehydrogenation of reactions of coking and the hydrogenation of intermediate conden-
intermediate condensation products, it is possible to calculate sation products. In this paper, the main optimization criterion im-
the catalyst operational mode corresponding to its maximally pos- plies that the least coke is formed while the desired alkene
sible lifetime at a specified yield of the target product [25,26]. production level is maintained by getting advantage of different
In the dehydrogenation process, the criterion of the technolog- raw alkanes reactivity.
ical mode optimality is either the maximal yield of the target prod- Fig. 5 illustrates the generalized scheme reflecting the intercon-
uct per unit of time regardless the stability of a catalyst or, on the nections between the target reaction and the side reactions pro-
contrary, the time of catalyst operation at a fixed yield of the target ducing the condensation monomer, i.e., the coke forming
product. The maximal economic benefits can be reached by regu- component.
lating the process operational mode (temperature, pressure, or The scheme includes the possibility of the formation of target
flow rate of hydrogen-containing gas) for a certain catalyst type n-alkenes directly from initial n-alkanes by splitting hydrogen
and raw material composition [27,28]. from them. According to this scheme, the condensation monomer
In the process of dehydrogenation, the pressure is nearly con- can be formed from dienes and aromatic hydrocarbons. In this
stant, the hydrogen/raw materials molar ratio, and the tempera- case, in the synthesis of n-alkenes, we deal with competitive reac-
ture are chosen so as to provide a specified yield and quality of tions in which the target product (n-alkene) and the condensation
the target product. In this case, the most important LAB quality monomer (aromatic hydrocarbon) are formed from the same initial
characteristic is its biodegradability determined by the concentra- components (n-alkanes) in the course of dehydrogenation and
tion of alkenes in the product and also by the branching index of dehydrocyclization through the formation of intermediate prod-
hydrocarbons coming to the alkylation stage. ucts (dienes).
136 E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139

Fig. 4. Alkene yield depending on the concentration of (a) C10, (b) C11, (c) C12, (d) C13, and (e) C14 hydrocarbons in the raw materials.

Fig. 5. Formation of the condensation monomer in the synthesis of n-alkenes.


E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139 137

E1 E2
The constants of target and side reactions of the process of 0 0
C apoM  k1  eb1 ck  eRT ¼ C k  C H2  k2  eb2 Ck  eRT ;
dehydrogenation relate as in the following equation: 0 E3
0 E4
C apoM  k3  eb3 ck  eRT ¼ C k  C H2  k4  eb4 Ck  eRT :
0 0 0 0
km ¼ k  Fm; kk ¼ k  Fk; ð4Þ
where Fm and Fk are the deactivation functions for the metal and Hence, the steady-state catalyst activity is determined by the
acidic sites respectively. Here, total amount of coke on the catalyst surface, the raw material com-
position, and the hydrogen concentration.
F m ¼ Am  ebm C k ; F k ¼ Ak  ebk C k ; ð5Þ
where bm and bk are the poisoning coefficients for the metal and 5. Solving the technological problems with the mathematical
acidic sites of the catalyst respectively, Am  Ak  1, model
1
T1
 T12 The model calculations allow us to conclude that the real oper-
bm ¼ ; DT ¼ T 2  T 1 ; ð6Þ
C k2  C k1 ational mode of the KD3 catalyst did not correspond to optimal
mode for the catalysts of this type (Fig. 6a–c). As for the calculated
mode, the catalyst lifetime is being chosen as an optimization
T2 is the compensation temperature, and Ck2 and Ck1 are the
parameter; i.e., the coke formation on the catalyst is minimized,
fractions of coke on a catalyst.
while the yield of the target product remains fixed at the desired
Therefore the rate of chemical reactions on metal sites of a cat-
level. Again, this is possible due to different reactivities of alkanes
alyst can be determined as follows:
in raw stock, which contents are continuously changed.
Eij
0
W ij ¼ C i  kij  ebm Ck  eRT ; ð7Þ At the same yield of the target product, it is possible to decrease
the process temperature profile by 10–15 °C and, accordingly, reduce
where Wij is the ith hydrocarbon conversion rate in the jth reac- the concentration of byproducts (dienes) to 0.2–0.3% instead of 0.4–
tion; Ci is the ith hydrocarbon concentration in the mixture; k is 1.0 wt%, and the concentration of coke on the catalyst to 1.5–2.0 wt%.
the constant of the jth chemical reaction for the ith hydrocarbon; The optimization was also carried out for the KD1 catalyst
and Eij is the ith hydrocarbon activation energy in the jth reaction. (Fig. 6a_1–c_1), also showing a considerable potential for increas-
Under the equilibrium conditions of the coking and the hydroge- ing the cost-effectiveness of the catalysts along with their opera-
nation of intermediate condensation products, if their main tional lifetime. The KD1 and KD2 catalysts are out of date but the
sources are aromatic hydrocarbons and dienes, the following equa- model calculations show that their optimal operational modes
tions are true: can also be found.

Fig. 6. Changes in the (a), (a_1) inlet temperature of dehydrogenation reactor, (b), (b_1) coke concentration and (c), (c_1) diene concentration on the catalysts (a)–(c) KD3 and
(a_1)–(c_1) KD1 in their (1) optimal and (2) current operational modes, having the least coke formation as the criterion of optimization.
138 E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139

exception. Therefore, it is expected that the catalyst would provide


maximum output of the high-quality product.
The developed computer modeling system allows testing differ-
ent catalysts to choose the optimum for given technological
parameters and raw stock composition [29]. In this paper three
catalysts were compared – KD1, KD2, and KD3.
The desired product yield determines the LAB output in the
end; side product yield determines the quality LAB (the less the
amount of side product the better).
It is shown in Fig. 8 that KD3 is most appropriate under the gi-
ven conditions as it secures highest yield of quality desired prod-
uct. At the same time, the price of this catalyst is about the same
as its predecessor, which makes it the best choice.

6.2. Water supply into the dehydrogenation reactor

A survey of the scientific literature and patent databases


showed that many works deal with the problem of increasing the
on-stream time of dehydrogenation catalysts and enhancing the
selectivity of the process by metering the amount of water sup-
plied to the reactor. Certain modes of water feed to the dehydroge-
nation reactor were described so as to maintain the optimum
moisture content in the system, which in turn must be determined
by the degree of catalyst deactivation by coke-generating com-
Fig. 7. Changes in the (a) inlet temperature of reactor and (b) diene concentration
in the (1) optimal and (2) current operational modes of the KD3 catalyst, having the
pounds, the feedstock composition, and process conditions.
least diene formation as the criterion of optimization. For example, the effect of water admixture on the dehydrogena-
tion of alkanes having a carbon number of 7–20 (mainly n-dode-
cane) on a platinum catalyst is studied in [18–20]. A favorable
The model calculations performed for the currently used KD3 effect of the introduction of water into the reaction medium was
catalyst show that its operational temperature mode maintained revealed. It was recommended to supply water in an amount of
in the reactor is close to the optimal one, and this is testified by 400–3000 ppm. Bloch et al. [19] reported the results of study of
a sufficiently long cycle of its operation (up to 8 months instead the effect of water on the dehydrogenation of alkanes with a higher
of the average of 5–6 months). But at this duration of catalyst oper- carbon number of 10–18 (dehydrogenation of n-dodecane inclu-
ation the dienes concentration becomes too high, so the catalyst sive). Investigation of the effect of different concentrations of water
mode in this process should be optimized in the direction of in the reactor (0, 400, 1400, and 3000 ppm) showed that water re-
decreasing the byproduct concentrations (Fig. 7). duces the initial catalyst activity, but the selectivity successively
One of the optimization options implies that the desired alkene increases from 86.5% to 93.1%. It was argued that the stability of
yield is specified based on the chromatographic data taken at spe- the catalyst increases in this case. The necessity of increasing the
cific times. The optimal temperature, coke concentration on the concentration of feed water with the increasing process tempera-
catalyst, and the outlet byproduct concentrations are fitted so as ture and the lowering activity of the catalyst for dehydrogenation
to provide the required yield of the target alkenes. of higher alkanes having a carbon number of 5–18 was substanti-
The model calculations show that at the same specified values ated in [20]. The optimal flow rate depends on the catalyst compo-
for the yield of the target product, maintaining the optimal tem- sition, feedstock nature, and hydrogen-rich gas flow rate.
perature reduces (up to 40 rel.% by the end of the working cycle) Important feature of catalysts (besides the high cost) is its life-
the dienes output, which generally determines the quality of fur- time which is a characteristic of each certain catalyst and can be up
ther synthesized alkyl benzene. A twofold decrease in the concen- to 10 or 11 months in case of modern catalyst types. In the end of
tration of the coke-forming components on the catalyst surface is its lifetime the catalyst loses its characteristics due to deactivation,
also achieved, prolonging the catalyst lifetime. so it is necessary to change it.
The capabilities of the developed software package are the The way to extend the life time of the dehydrogenation catalyst
following: is supplying increasing amounts of water into the reactor. We have
developed the method of quantitative computing the amount of
- Monitoring the plant operation, computing different param- water supply and realized it in the software [30,31].
eters of LAB production including products output, tempera- Initially water supply into dehydrogenation was at low constant
tures, and catalyst operation characteristics. level (Fig. 9). It was later determined that increasing the water sup-
- The system takes raw stock composition into account. ply is effective in terms of prolonging the life time of the catalyst
- The ability to test the performance of different catalysts. and lowering the operating temperature while keeping the desired
- The forecasting feature. conversion level. The special software module allows calculating
- Automatic computing of different reconstruction options. the amount of water to supply. The input parameters for the mod-
- Control and technical support for the plant. ule include the operational conditions and the production targets.
Coke is a product of the polymerization reactions of hydrocar-
6. Impact on the technology bons (Fig. 2). The amount of water depends on its concentration
on the surface of a catalyst, which is determined by solving the sys-
6.1. Testing different catalysts tem of equations of the model.
Changing the oxidation reaction conversion of amorphous coke
Nowadays, the great part of every petrochemical plant’s inputs by means of water allowing to calculate the optimal supply of
is purchasing costly catalysts. The LAB production is not an water in the reactor depending on the temperature and degree of
E.V. Frantsina et al. / Chemical Engineering Journal 238 (2014) 129–139 139

Fig. 8. Yields of the desired and side products with different catalysts loaded.

optimize the process of C9–C14 n-alkane dehydrogenation on a Pt-


catalyst.
Software package developed by our group is integrated into the
industrial control system of the target plant, allowing the engi-
neering staff to monitor the plant operation real-time. The recom-
mendations concerning the water supply are implemented at the
industrial plant; the corresponding methods are protected by the
appropriate legal documents.

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