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a r t i c l e i n f o a b s t r a c t
Article history: A comprehensive steady-state population balance model is developed for the particle size distribution
Received 31 July 2008 (PSD) of the polypropylene produced in tubular loop reactors. The model considers the ow type, the
Received in revised form 23 October 2008 polymer particle dynamics, the particle growth and the attrition. Moreover, an empirical single particle
Accepted 26 October 2008
model is used to describe the particle growth under internal and external heat and mass transfer limita-
tions totally. The predicted PSD data obtained under steady-state polymerization conditions agree well
Keywords:
with the actual data collected from industrial scale plant. The model are also used to predict the effects
Polypropylene
of some operational parameters on the polymer PSD produced under steady-state conditions. The results
Tubular loop reactor
PSD
show that the polymer PSD are greatly affected by the feed catalyst size, the feed catalyst PSD, and the
Population balance polymerization temperature.
Steady state 2008 Elsevier B.V. All rights reserved.
1. Introduction predicted the effects of the feed catalyst PSD on the polyolen
PSD produced in a FBR. Soares et al. [14] developed a mathe-
Polypropylene can be produced in various types of reactors, such matical model to analyze the effects of the ideal and non-ideal
as autoclave, continuous stirred tank, uidized-bed reactor (FBR) or reactor residence time distributions on the polymer PSD. Zacca et
tubular loop reactor. The last one is certainly the most important at al. [2] presented a population balance approach modeling of multi-
present [1]. In the tubular loop reactor, small catalyst particles (e.g. stage olen polymerization processes using the catalyst residence
20100 m) react with monomers to form polymer particles in a time as main coordinate. Their work allowed the consideration of
size range of 1005000 m in a liquid phase and the polymer parti- particle size selection effects within the process in a FBR. Khang
cles are produced as a solid suspension in the liquid stream [28]. In et al. [3] developed a population balance approach to model the
addition, the polymerization rate, the cost of post-treatment after effect of non-ideal mixing behavior of solid particles on the poly-
polymeric process and the polymer properties are inuenced by olen PSD in a FBR. Hatzantonis et al. [4] developed a generalized
the polymer particle size distribution (PSD) [68]. Therefore, the steady-state population balance model rigorously accounting for
polymer PSD modeling may be useful for the understanding of the the combined effects of particle growth, attrition, elutriation and
propylene polymerization in tubular loop reactors. Furthermore, a agglomeration in a gas-phase FBR. Yiannoulakis et al. [5] employed
mathematical model is necessary in order to predict the effects of a polymeric ow model to describe the growth rate of a sin-
operation parameters, especially the feed catalyst on the product gle particle under internal and external heat and mass transfer
PSD in tubular loop reactors. limitations in a FBR and this single particle model was solved
In propylene polymerization eld, most of papers published together with a steady-state population balance model to pre-
were concerned with the modeling of heat and mass transfer inside dict polymer PSD. Mattos et al. [15] developed and implemented
the polymer particles and of the reaction mechanism [912]. The a mathematical model for steady-state slurry and bulk propy-
overall polymerization process combined with the polymer PSD in lene polymerization process. The model was capable of predicting
the reactor was usually neglected. the polymer molecular structure and morphology, including PSD.
Choi et al. [13] put forward a population balance model for Using a mixing cell approach and detailed polymerization kinet-
a continuous gas-phase olen polymerization reactor. The model ics combined with population balance equation, Harshe et al. [6]
developed a comprehensive model for propylene polymerization in
a FBR. The need for coupling the reaction-engineering model with
Corresponding author. Tel.: +86 592 2187190; fax: +86 592 2187231. the population balance equation was also demonstrated in their
E-mail address: luozh@xmu.edu.cn (Z.-H. Luo). work.
1385-8947/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2008.10.023
Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476 467
polymer lm in R200 are transported into R201 and react with polymerization. Thus, Eq. (5) can possibly be improved and modi-
the incoming monomers. Simultaneously, the particles may either ed empirically as shown below:
grow in size due to the polymerization reaction or rupture into n
small ones caused by mechanical or rheological attrition. There- Dcat
rp (t) = ekd t rp,0 (6)
fore, the polymer particle is inuenced by the original size of the Dpp
catalyst particle, the polymerization rate, the attrition rate, and
wherein Dcat and Dpp are the catalyst and the polymer particle diam-
the residence time [15]. Moreover, due to the original catalyst PSD
eter, respectively; represents the efciency factor, which is a liner
and residence time distribution (RTD) inside the reactors, the nal
function of Dcat shown in Eq. (7), describing the specic surface
product PSD can be very broad. Accordingly, the population bal-
and the active sites buried in the support material of different size.
ance model should take into account of the following three basic
Notice that Dpp is also a function of the residence time and the
aspects, namely, the propylene polymerization kinetics, the particle
catalyst particle diameter Dcat , which is described in Eq. (8):
dynamics and the residence time distribution.
In the present study, attention is specially paid to the particle = ke Dcat + 1 (7)
size of the solid phase. For the sake of simplicity, the polymer par-
ticle is assumed to be of spherical shape with constant density. Dpp = Dpp (t, Dcat ) (8)
According to Refs. [4,23], the polymer PSD in the reactors (R200
and R201) can be described via the statistical density function, P(D), 3.3. Particle dynamics
which can be formulated with the following equation:
Dmax According to Refs. [2,3,5,6,13,15], the following assumptions for
P(D) dD = 1 (1) particle dynamics are made in this paper:
Dmin
(1) all catalyst active sites have been activated simultaneously,
where P(D) dD is the mass fraction of the polymer particles in the
(2) there are no radial concentration gradients within the particles,
size range of (D, D + dD). Note that due to the well-mixed assump-
(3) the temperature gradients in the particles are ignored.
tion for the particles in the reactors, the particle density function
in the product steam is identical to that in the reactors.
Assuming a polymer particle formed base on a catalyst particle,
then the following mass balance equation can be obtained:
3.2. Polymerization kinetics
t
3 3 3
To describe the propylene polymerization kinetics over a D cat rp (t) dt = (D Dcat )pp (9)
6 cat 0
6 pp
ZieglerNatta catalyst, a simple kinetic model is employed [6,24].
The polymerization kinetic scheme comprises a series of ele- In addition, Eq. (10) can be obtained via derivation of Eq. (9):
mentary reactions, namely, site activation, propagation, site 2
3pp Dpp dDpp
deactivation, site transformation and chain transfer reactions. rp (t) = (10)
3
cat Dcat dt
Among them, the propagation reaction and the site deactivation
play an important role in the particle growth rate [6,22]. Based on
Based on the constant value of Dcat for a single polymer particle,
the above discussion and the pseudo-kinetic rate constant method,
the correlation of Dpp and t can also be obtained and shown in Eq.
the following kinetic equations are suggested and adopted:
(11) by incorporating Eq. (6) into Eq. (10):
Propagation rate:
n 2
Dcat 3pp Dpp dDpp
ekd t rp,0 = (11)
Dpp 3
cat Dcat dt
rp = kp Mc Mm (2)
Site deactivation rate: Accordingly, Eqs. (12) and (13) can be obtained by integrating
Eq. (11):
rd = kd c (3)
Dpp = Dpp (t, Dcat )
Combination of Eqs. (2) and (3) leads to 1/(3+n)
(3 + n) rp,0 cat Dcat
(3+n)
(1 ekd t )
dc rp =
(3+n)
+ Dcat
rd = = kd (4) 3 pp kd
dt kp M Mm
(12)
Integrate rp with the isothermal condition and rp as a function
of time, t, thus Eq. (5) can be obtained:
3+n 3+n
1 3(Dpp Dcat ) pp kd
rp = rp,0 ekd t (5) t = t(Dpp , Dcat ) = ln 1 (13)
kd 3+n
(3 + n) rp,0 cat Dcat
where it is important to point out that the feed impurity can lead
to the catalyst deactivation. Besides, the catalyst can also deacti- From the viewpoint of statistical methodology, it is obvious that
vate spontaneously [3]. Therefore, kd is supposed to represent the a polymer particle with diameter of Dpp in the size range of (Di , Di+1 )
above two deactivation routes totally, which are independent and has the following possibility:
dependent, respectively. Di+1 Dcat,max j
t
i+1
When referring to the polymer particles, the inter- and
Ppp (Dpp ) dDpp = Epp (t) dt Pcat (Dcat ) dDcat
intra-particle heat and mass transfer limitations do affect the poly- Di Dcat,min t
j
i
merization rate. Though slow reaction rate considered in Ref. [25], (14)
some aspects of polymer particles growth are similar, thus we
assume that the polymerization rate are more likely to be affected where Pcat (Dcat ) is the catalyst PSD density function; Epp (t) is the
by the amount of the polymer produced on the surface of the cata- residence time distribution based on the polymer particles for each
j j
lyst particle compared with the residence time in the early stage of diameter of catalyst particles; ti and ti+1 are both functions of Dpp
Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476 469
and Dcat as discussed in Eq. (13). In addition, as for the discrete per particle mass due to the attrition can be described in Eq. (18):
situation, Eq. (14) can be rewritten as Eq. (15):
(dmpp (Dpp )/dt) 3Ra (Dpp )
= (18)
ncat j
t
i+1
mpp (Dpp ) Dpp
Wpp,i = mcat,j Epp (t) dt (15)
j
t
j=1 i 3.4.2. Formulation of population balance equation
Following the population balance method described in Fig. 2
where ncat represents the number of catalyst particle diameter size
[4], the steady-state mass balance equation for particles in the size
cuts; mcat,j represents the mass fraction of catalyst particles in each
range of (D, D + D) is given by Eq. (19):
(19)
0 Dpp = Dcat
tribution to the overall polymerization rate [4]. Denoting Ra (D) as Ppp (D) = (22)
Ppp (D0 ) Dpp = D0
the particle attrition rate, the average rate of particle mass change
470 Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476
Fig. 2. Schematic representation of particle size variation with respect to particle growth and attrition mechanism.
where D0 is an arbitrary value close to Dcat , but not exactly equals to introducing Eq. (13) and (24):
Dcat . For the case of size distributed catalyst feed, the particle den-
t
sity function will be given by the weighted integral of the particle d Ppp [Dpp (t, Dcat )] (dDpp /dt) dt
dFpp (t) 0
size distributions resulting from the various discrete uniform size Epp (t) = = (24)
catalyst fractions: dt dt
Dcat,max
Because of the catalysts short residence time in R200 and its
mild reaction conditions, there is only a little effect of the R200
Ppp (Dpp ) = Ppp (Dpp , Dcat )Pcat (Dcat ) dDcat (23)
Dcat,min
on the total polymer PSD, thus, in the estimation procedure, only
R201 is taken into account. With the residence time distribu-
tion of the polymer particles in the tubular loop reactors and the
3.5. Solution methodology plant data including PSDs of the polymer and catalyst, the kinetic
parameters of kd , ke and n can be tted iteratively through the
The present study has considered R200 and R201 as shown in procedure discussed in Section 3.3. On the one hand, the esti-
Fig. 1. The corresponding solution methodology is introduced as mation procedure is necessary when lots of parameters are to
follows. be conrmed or sorts of parameters are available; on the other
First, the input is read through the Read Input module. The input hand; we also emphasize that the catalyst, especially, its sup-
is validated and the initialization of the model variables is done. port material have important effects on the catalyst fragmentation
The overall reactors (R200, R201) simulation is calculated in the and the intra-particle mass and heat limitations. Papers published
external Reactors Module (not discussed in this paper). This exter- on the polymer particles and catalyst fragmentations have clearly
nal module is incorporated to supply the total particle mass, W; shown the importance of the support material of the catalyst [25].
the polymer particles output rate, F1 and F2 , in the tubular loop Therefore, it is necessary to describe an empirical single polymer
reactors as expressed in Eq. (21), besides, the polymer properties particle model as accurate as possible through parameter estima-
including the molecular weight distribution and melt index. For tion.
more information, readers are encouraged to refer Refs. [1,12,28].
According to the external module, we can easily predict both the 4. Results and discussion
polymer PSD and properties, and discuss the effects of the oper-
ational parameters on the polymer PSD. Then the program goes 4.1. Parameters estimation
to the next modules solving the population balance equations for
R200 and R201, in sequence. To solve these steady-state population The catalyst used in the plant is an advanced fourth generation
balance equations, shown in Eq. (21), the whole range of varia- of the ZieglerNatta catalyst (TiCl4 /MgCl2 + PEEB + AlR3 ), and was
tion of particle diameter is divided into a suite of equally spaced sampled and characterized by means of microscope to obtain the
diameters. Subsequently, the differential Eq. (21) is approximated particle accumulation curve, and then the particle density curve
by a system of linear recursive algebraic equations written at dis- was also obtained by derivation. Both the corresponding curves are
crete diameters, and then this system of linear algebraic equations shown in Fig. 3. The polymer powder obtained from the plant was
is recursively solved for each catalyst diameter cuts starting from analyzed by using a sizer and was also numerically tackled, the
each catalyst size, to calculate the PSD in the reactors in sequence same as the catalyst, and the result is given in Fig. 4.
[4]. It is important to point out that in present study, Ppp (D0 ) is The estimation of kinetic parameters was accomplished as dis-
rearranged to make Eqs. (1) and (23) satised. This procedure is cussed in Section 3.5 using the above plant data. Accordingly, the
different from Refs. [4,8], wherein the value of the product out- values of kd , ke and n were obtained successfully. Moreover, accord-
ow rate is rearranged to make Eqs. (1) and (23) satised given the ing to the value of kd , the value of kd,0 is also updated via the
case of the constant bed weight in the FBR. Herein, the two PSDs Arrhenius law. It can be seen from Fig. 5 that the predicted data
of the two reactors have been calculated; moreover, if plant data is in good agreement with the plant data. Hence, the single particle
are available, it is interesting that the selective route of parame- model was available as accurate as possible with updated kinetic
ters estimating can be chosen to estimate kd , ke and n introduced parameters through estimation procedure. Parts of parameters esti-
previously. Besides, there is a RTD for polymer module wherein mated or used here are tabulated in Table 1. The following shows
the polymer particles residence time distribution is obtained by the employment of this single particle model.
Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476 471
Fig. 6. Polymerization rate decays with time at the initial stage of polymerization.
Table 1
Simulated parameters in the study.
Fig. 5. Comparison of the particle weight fraction between the predicted data and
the plant data. Fig. 7. Polymerization rate decays with particle growth.
472 Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476
Fig. 8. Particle size distribution predicted for R200: T200 = 15.5; T201 = 70;
Fig. 10. Residence time distribution for the catalyst and polymer particles.
FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14;
Fprop,200 = 1500.03.
Eq. (12) into Eq. (25), the residence time distribution for the catalyst
4.2. Comparison between the plant data and the simulated data particles can be obtained and shown in Eq. (26):
3
F E (t) dt
The polymer PSD data predicted by the population balance W Ppp (Dpp ) dDpp = 3
Dpp pp D cat
cat cat
model are compared with the plant data. Because the R200 reactor 6 6 cat 3
(/6)Dcat cat
is relatively small in volume and the corresponding polymerization (25)
rate is also small with its mild conditions. In addition, the polymer
particles in R200 are difcult to sample. Therefore, only the poly-
3
W Dcat
mer particles in R201 were sampled and their PSD data are used in cat dDpp
Ecat (t) = 3 3
Ppp (Dpp ) (26)
present study, but both of the PSDs predicted of the two reactors (Dpp pp Dcat cat )Fcat dt
are shown in Figs. 8 and 9.
Based on the population balance equations for uniform-size cat-
Fig. 9 shows that there is a very good agreement between the
alyst feed, residence time distributions for some of the catalyst cuts
predicted data and the plant data. Therefore, the present work can
are shown in Fig. 10. In addition, the residence time distributions
be applied to predict the polymer PSD in the steady-state tubular
of the polymer particles discussed previously are also shown in
loop reactors; though Fig. 9 shows that the predicted data has more
Fig. 10, which are all identical for each of the catalyst cuts. Fig. 10
ne powder and less large particles than the plant data. The rea-
shows that the residence time distributions of the polymer and the
sons for these differences may be the neglects of the agglomeration
catalyst are different even though they are both suspending in the
effect during the polymerization and the electrostatic effect during
liquid phase and dragged through the tubular loop reactors with
the experimental analysis of the polymer samples, which may alter
the liquid phase. The reason for this difference is that the polymer
the shape of the PSD more or less. Whats more, the assumption
particles grow with the increase of the residence time but the cat-
of well mixed in tubular loop reactor also affects on the predicted
alyst particles remains constant in mass with the polymerization
results.
continuing. Therefore, the residence time distribution of the cata-
For polymer particles with diameter of Dpp in a size cut of dDpp ,
lyst seems to the same as that of the liquid phase, which assumed
their total mass can be expressed in Eq. (25), where Ecat (t) is the
as the perfect mixed.
residence time distribution based on the catalyst. By incorporating
In addition, Fig. 10 also shows that catalyst particle with differ-
ent size has different residence time distribution, and the above
difference is caused by Eq. (21), wherein, for each single-size cat-
alyst feed, the weight of the total solid in the reactor, W, resulting
from the external module, remains constant, but each catalyst par-
ticle is different in polymerization rate. Thus, to reach the same W,
the residence time for larger catalyst particles have to be extended
according to Eq. (7).
Its interesting that the population balance model proposed here
and the models proposed by Zacca et al. [2] concerning the loop
reactor both characterize the catalysts residence time distribution
as the type of CSTR.
Fig. 11. Effects of the catalyst size on the polymer PSD in R200: T200 = 15.5; Fig. 14. Effects of the attrition rate constant on the polymer PSD in R201: T200 = 15.5;
T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14; T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14;
Fprop,200 = 1500.03. Fprop,200 = 1500.03.
Fig. 13. Effects of the catalyst deactivation constant on the polymer PSD in Fig. 15. Fine powders produced with the increase of the attrition rate: T200 = 15.5;
R201: T200 = 15.5; T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14;
Fprop = 24616.14; Fprop,200 = 1500.03. Fprop,200 = 1500.03.
474 Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476
Fig. 18. Effects of the propylene feed rate on the polymer PSD in R201: T200 = 15.5;
Fig. 16. Effects of the reaction temperature on the polymer PSD in R201: T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop,200 = 1500.03.
T200 = 15.5; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14;
Fprop,200 = 1500.03.
particles with the increase of the polymerization temperature. The
observed shift of the PSD curve to large particles is due to the
are improved by following a conic function other than a delta func- increase of the polymerization rate at high temperature.
tion: Figs. 17 and 18 show the effects of the catalyst feed rate and the
Df max
np propylene feed rate on the polymer PSD in R201, respectively.
3Ra (Dpp,i )
F2 Ppp (Df ) dDf = W Ppp (Dpp ) dDpp (28) With the increase of the catalyst feed rate, the total polymeriza-
Dpp,i
Df min
i=1 tion rate increases. Hence, the content of the solid in the reactor
increases, leading the increase of the density of the mixture in
Ppp (Df ) = A(Df Dfmin )(Df Df max ) (29) R201, thus, increase the particle residence time, though, this slightly
affects the product PSD, as shown in Fig. 17. With the increase of
Df min Df Df max (30) the propylene feed rate, as can be seen from Fig. 18 the catalyst
average residence time in R201 decreases greatly, which leads to
With the attrition rate constant increases, the polymer PSD the decrease of the average polymer particle size.
becomes narrower and the weight fraction of the larger particles The effect of the polymer PSD in R200 on the polymer PSD in
decreases slightly as showed in Fig. 14, though the ne powders R201 is showed in Figs. 19 and 20. There is nearly the same polymer
increase evidently in Fig. 15. PSD in R201 showed in Fig. 20 even though three case of polymer
particles feed with different PSD from R200 into R200. It proves
4.3.3. Effects of the operational parameters on the polymer PSD that the effect of the polymer PSD in R200 on the polymer PSD in
For propylene polymerization in industry, the polymer PSD is R201 is weak.
inuenced by the polymerization temperature, the catalyst feed
rate, and the propylene feed rate generally. These inuences are 4.4. Multi-size catalyst feed
predicted in our work.
Fig. 16 illustrates the effect of the liquid-phase polymerization Based on the single-size catalyst feed model and Eq. (23), the
temperature on the polymer PSD in R201. As can be seen from effect of the catalyst PSD on the polymer PSD in R201 can also be
Fig. 16, the distribution width of the polymer PSD increases with obtained via the above model. In present study, the initial catalyst
the increase of the polymerization temperature in R201. Simulta- PSD is divided into a number of size cuts and the overall PSD in
neously, there is a great shift in the PSD curve to larger polymer R201 is obtained as a sum of PSDs resulted from the individual
Fig. 17. Effects of the catalyst feed rate on the polymer PSD in R201: T200 = 15.5; Fig. 19. Effects of the propylene feed rate on the polymer PSD in R200: T200 = 15.5;
T201 = 70; FTEAL = 3.37; FDONOR = 0.33; FH2 = 0.7; Fprop = 24616.14; Fprop,200 = 1500.03. T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14.
Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476 475
Fig. 20. Effects of the prepolymerization in R200 on main polymerization of Fig. 23. Effects of the catalyst particle size multi-distribution on the polymer PSD
R201: T200 = 15.5; T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; in R201: T200 = 15.5; T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7;
Fprop = 24616.14. Fprop = 24616.14; Fprop,200 = 1500.03.
in Fig. 22:
2
1 (ln Dcat ln Dcat )
Pcat (Dcat ) = exp (31)
2Dcat 2 2
Fig. 21 shows that the three catalysts fed with the same Dcat
of 60 m are different in of 0.3, 0.4 and 0.5 based on Eq. (31).
Moreover, the three corresponding polymer PSDs are also obtained
via our model and illustrated in Fig. 22. In addition, Fig. 23 illus-
trates that the bimodal polymer PSD can be obtained by using a
catalyst feed consisting of two types of catalyst particles with dis-
tinct diameter, and the shape of the overall polymer PSD directly
depends on the diameter and mass fraction of the two catalysts.
With the increase of the fraction of the large catalyst particles, the
area of the large polymer particles increases in the outlet polymer
Fig. 21. Catalyst size distribution with different standard deviations.: T200 = 15.5; PSD. Therefore, it is possible to produce special polymer particles
T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14;
with certain PSD type by varying the feed catalyst PSD.
Fprop,200 = 1500.03.
5. Conclusions
catalyst cuts. Hatzantonis et al. [4] assumed that the feed catalyst
PSD has a log-normal distribution and is shown in Eq. (31). Accord-
A comprehensive steady-state population balance model is
ingly, the feed catalyst size distribution is illustrated in Fig. 21,
developed for the prediction of the polypropylene PSD produced
and the corresponding predicted polymer PSD is also shown
in tubular loop reactors. The model takes into account the ow
type, the polymer particle dynamics and the particle growth. Some
actual data of the steady-state polymerization collected from a local
plant are supplied to verify the model. The predicted polymer PSD
produced under steady-state polymerization condition is found to
agree well with the plant data.
The effects of the kinetic and operational parameters on the
polymer PSD are also investigated. The simulated results show that
the average diameter of the polymer particles increases and there
is a shift to a broader PSD with the increase of the diameter of the
catalyst particles when the single-size catalyst feeds. Moreover, as
to the single-size catalyst applied, the polymer PSD becomes nar-
rower with the increases of both the deactivation rate constant
and the attrition rate, but becomes broader with the increase of
the polymerization temperature. Simultaneously, we also nd that
the average diameter of the polymer particles decreases with the
increase of the propylene feed rate. Furthermore, the simulated
results show that a bimodal PSD can be obtained by using a cat-
Fig. 22. Effects of catalyst size distribution on the PSD in R201: T200 = 15.5; alyst feed consisting of two catalysts with distinct diameter, the
T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14; shape of the overall polymer PSD directly depends on the diameter
Fprop,200 = 1500.03. and the mass fraction of this two catalysts.
476 Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476
Acknowledgments [14] J.B.P. Soares, A.E. Hamielec, Effect of residence time distribution on the size
distribution of polymer particles made with heterogeneous ZieglerNatta and
supported metallocene catalysts. A generic mathematical model, Macromol.
The authors thank National Natural Science Foundation of China Theor. Simul. 4 (1995) 10851104.
(no. 20406016) for nancial support and Fujian Petrochemical [15] A.G. Mattos Neto, J.C. Pinto, Steady-state modeling of slurry and bulk propylene
Company of SINOPEC for plant data and permission to publish it. polymerizations, Chem. Eng. Sci. 56 (2001) 40434057.
[16] Pdero Henrique Hermes Araujo, Jose Carlos de la Cal, Jose Maria Asua, Jose
Authors also thank the anonymous referees for comments on this Carlos Pinto, Modeling particle size distritbution (PSD) in emulsion copoly-
manuscript. merization reactions in a continuous loop reactor, Macromol. Theor. Simul. 10
(2001) 769779.
[17] Z.H. Luo, Z.K. Cao, N.J. Zhu, an analysis on model of a loop reactor for polypropy-
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