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

in tubular loop reactors

Zheng-Hong Luo , Pei-Lin Su, Xiao-Zi You, De-Pan Shi, Jin-Cheng Wu

Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Shiming Street 422,

Xiamen 361005, Peoples Republic of China

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

Nomenclature parameters estimation and the population balance equation, the

model takes into account the ow type, the particle dynamics and

A parameter for the ne powders size distribution the particle growth, as well as, the attrition. Particular attention is

C* concentration of activate site (mol/kg) paid to the effects of the operational parameters on the polymer

D particle diameter (m) PSD and to the comparison of PSD between the predicted and the

E(t) residence time density function (h1 ) actual data.

F owrate (kg/h)

F(t) residence time accumulation function

G(D) particle diameter growth rate (m/h) 2. Process for propylene polymerization in tubular loop

k reaction kinetic constant reactors

m particle mass (kg)

M monomer concentration (mol/m3 ) In the present study, Himont Spheripol Loop technology with

Mm monomer molecular weight (kg/mol) the continuous tubular loop reactors as its heart is studied. To illus-

n parameter for single particle model trate the concepts discussed in this paper, a typical schematic ow

P(D) mass density function (m1 ) sheet is given in Fig. 1.

r reaction rate There are many papers concerning the loop technology [2,16,17].

Ra particle diameter attrition rate (m/h) Comprehensive reviews have also been reported [18,19]. Some

t residence time (h) points related to this work are listed in the following contents.

T reaction temperature ( C) First, the loop reactors, including the prepolymerization reactor

w weight fraction of solid phase in the reactor (R200, 0.46 m3 ) and the main polymerization reactor (R201, 56 m3 ),

W total particles mass in tubular loop reactor (kg) are of most importance in the Himont Spheripol Loop technol-

ogy. Secondly, R201 consists of three tubular reactors connected

Greek letters and symbols in sequence with each other, in practice, the tubular loop reactor

efciency is a closed tube as a whole, wherein the reacting slurry driven by

mathematical constant a recycling pump circulates with high-recycle rates, as depictured

particle density (kg/m3 ) in Fig. 1. Under these conditions, it is possible and reasonable to

standard deviation assume the tubular loop reactor as a continuous stirred-tank reac-

tor (CSTR) with constant volume [2,15,20,21], but slurry density.

Subscripts and superscripts The reacting slurry is supposed to be a mixture of liquid phase

cat catalyst property (monomer and hydrogen) and a solid phase (polymer and cat-

d deactivation reaction alyst). Finally, the catalyst is assumed to undergo the common

DONOR electronic donor for ZieglerNatta catalyst activationpolymerizationdecay pathway.

e efciency

f polymer ne powders 3. Mathematical model

H2 hydrogen

max maximum size 3.1. Introduction

min minimum size

p propagation reaction During the solid-catalyzed liquid-phase propylene polymeriza-

pp polypropylene tion in the tubular loop reactors, the small catalyst particles are

prop propylene continuously fed into R200 at a constant rate. The catalyst frag-

TEAL triethyl aluminum ments into a large number of small particles or layers under mild

0 initial stage reaction conditions in R200 [22], accordingly, the polymerization

1 inlet stream reaction is initiated, and the catalyst particles are well lmed to

2 outlet stream prevent the fragments from separating from the catalyst parti-

200 prepolymerization reactor R200 cles. Subsequently, the small catalyst particles coated with the thin

201 main polymerization reactor R201

eling efforts in this eld are made to account for the detailed aspect

of the population balance model and the particle residence time

in reactors separately. In practice, the two are coupled with each

other. It is also clear that the PSD models established before mainly

focused on the FBR. Though there is no difference between them

when both FBR and tubular loop reactor are treated as a continu-

ous stirred tank reactor (CSTR) in simulation, they are still different

in plant operation and solution methodology of the population

balance equation. Moreover, it is important that most of the PSD

models proposed are not validated with any actual industrial data.

Nevertheless, they are still helpful as reference when dealing with

the PSD model of the polypropylene produced in tubular loop reac- Fig. 1. Himont Spheripol Loop process (Fujian Petrochemical Company of SINOPEC):

Acatalyst; Bpropylene; Chydrogen; Dcoolant in; Ecoolant out; 18control

tors.

sites; 9E201, heat exchanger; 10E203, heat exchanger; 11P200, pump;

In the present work, a comprehensive steady-state population 12P201, pump; 13Z203, mixer; 14R200, prepolymerization reactor; 15R201,

balance model is developed for the prediction of the polypropylene main polymerization reactor; 16D202, buffer tank.

468 Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476

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)

size cuts; Wpp,i represents the mass fraction of polymer particles

feed, the rst term in Eq. (19) represents the particle inow in the

with the diameter lying between Di and Di+1 .

size range of (D, D + D), which is the case of R201 when the out-

For the sake of estimation for kinetic parameters from plant data,

ow of R200 enters into with size-distributed polymer particles.

a chi-square merit function is dened and used to determine best-

On the other hand, for a uniform-size catalyst feed as in R200, this

t parameters by its minimization:

term is only taken into account for the rst particle cut. Substitute

npp

(D)pp,i

W (D)pp,i W

each of the related terms in Eq. (19) for mathematical expression

2 = (16) using the particle density function, particle growth rate and attri-

(D)i

i=1 tion rate, as well as the corresponding mass ow rate, then we

obtain:

where npp is the number of plant data points and (D) is the stan- F F

dard deviation of the plant data points [26]. 1 2

P1 (Di ) D P2 (Di ) D + P2 (Di1 )G(Di1 )

W W

3.4. Steady-state population balance model 3G(Di )

+ P2 (Di+1 )Ra (Di+1 ) + P2 (Di ) D P2 (Di )(G(Di )

Di

3.4.1. Particle growth and attrition

For the sake of the simplicity and keeping in consistence with 3Ra (Di )

+ Ra (Di )) P2 (Di ) D = 0 (20)

the particle dynamics presented above, a simplication of the mor- Di

phology model is introduced and the growth rate of the polymer

particle diameter is given as follows, which is derived from Eq. (10) All of the terms of Eq. (20) are divided by D and let D

[4,8]: approaches to 0; accordingly, the continuous form of the popula-

3 tion balance equation for the case of uniform-size catalyst feed is

dDpp rp (t) Dcat cat

G(D) = = (17) obtained as given below:

dt 2

3pp Dpp

g F F d d

1 2

P1 (D) P2 (D) [P2 (D)G(D)] + [P2 (D)Ra (D)]

Mattos et al. [15] and Freitas et al. [27] assumed and testi- W W dD dD

ed, respectively, that particle coalescence and breakage were not

3

important for PSD evolution in liquid-phase polymerization reac- + P2 (D) [G(D) Ra (D)] = 0 (21)

D

tors. However, polymer particle attritions may occur under the

conditions of high density and relatively fast circular velocity in the

tubular loop reactors. Then, polymer nes may generate due to the According to Ref. [4], when catalyst particles of size Dcat enter

attrition forces resulting from particle collision in the reactors, and into a loop reactor, once they get contact with the liquid phase

actually, large amount of nes are found in the local plant. Under monomer, polymerization occurs and their sizes increase instan-

the assumption of a continuous size reduction of the polymer par- taneously by at least a very small increment before they exit the

ticles [23], the size of the subtle product can be considered to be reactor. Therefore, the particle size distribution appears to be dis-

innitely small, accordingly, the amount of active sites contained continuous at Dpp = Dcat , or otherwise:

can be ignored. Thus, the subtle product attrited makes little con-

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.

Ed 5.04 104 J/mol [1,28]

kp,0 1.789 108 m3 /(mol h) [1,28]

kd,0 6.313 105 h1 Estimated

ke 3.15 103 m1 Estimated

n 9.1264 102 Estimated

Fig. 4. Polymer PSD from Plant.

C* 25 mol/kg-cat Plant data

pp 910 kg/m3 Plant data

cat 600 kg/m3 Plant data

in the initial stage of polymerization due to the strong decrease

of Dcat /Dpp ratio in the early stage of the polymer/catalyst parti-

monomer concentration between the active site and the bulk uid-

cle formed. For catalyst particles with different efciency factor

phase.

according to Eq. (7), the polymerization rate decays according

Fig. 7 shows the polymerization rate of different catalyst parti-

to the corresponding initial polymerization rate. Pater et al. [25]

cles decays in same trend as a whole. That it is, all polymerization

have put forward an argument that the above result is ascribed

rates rst decay strongly in the small diameter range due to the

to the phase transition in the growing particle. That it is, ini-

mass or heat limitations, and then decrease gently for a short res-

tially, the catalyst forms the continuous phase, within which the

idence time before the polymerization rates decay severely due to

polymer is distributed. Then after the phase transition, the poly-

the active site deactivation in the large diameter range, namely, the

mer forms the continuous phase in which catalyst fragments are

long residence time in the reactors. Besides, it is important to point

distributed. And this change causes a change in monomer con-

out that catalyst particles with different diameters take different

centration at the active sites, resulting in lower reaction rates.

residence time to reach the same diameter.

Besides, Hutchinson et al. [29] also notice the difference of the

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.

The effects of the feed catalyst particle size on the polymer PSD

are shown in Figs. 11 and 12, which show that the average diam-

Fig. 9. Comparison between the predicted data and the plant data: T200 = 15.5; eter of the polymer particles increases and there is a clear shift to

T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14; broader PSD with the increase of the diameter of the catalyst par-

Fprop,200 = 1500.03. ticles. The increase of the reaction rate at larger catalyst leads to

Z.-H. Luo et al. / Chemical Engineering Journal 146 (2009) 466476 473

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.

stant on the polymer PSD in R201. For rst-order site deactivation

kinetics and a given catalyst feed rate, the active site concentra-

tion in the polymer particles decreases greatly with the increase

of the deactivation rate constant. Accordingly, the polymerization

rate decreases with the particles residence time and the polymer

PSD curves become sharp in large particles. Fig. 13 shows that for

faster deactivation constant, the product PSD shifts to lower particle

size.

Figs. 14 and 15 show the effects of the attrition rate constant

on the polymer PSD. Unlike previously published work [4]; the

attrition rate is redened in Eq. (27):

0

Dpp < 1 mm

Fig. 12. Effects of the catalyst size on the polymer PSD in R201: T200 = 15.5; Ra = w 7 (27)

10 Dpp 1 mm

T201 = 70; FTEAL = 3.37; FDONOR = 0.33; Fcat = 0.5775; FH2 = 0.7; Fprop = 24616.14; 0.55

Fprop,200 = 1500.03.

where the attrition rate of polymer particles in the diameter range

the increase of the polymer particles diameter, and its also well of 01 mm is assumed to be 0, and w is the weight fraction of the

explained according to Eq. (17). solid phase in the reactor. It suggests that when the density of the

material within the loop reactor gets higher, the attrition rate will

4.3.2. Effects of the polymerization parameters on the polymer increase, so does the ne powder.

PSD According to Ref. [30], the particle size distribution of the poly-

For propylene polymerization in industry, the polymer PSD is mer nes, given in Eqs. (28)(30) in the reactor and outow streams

affected by the polymerization parameters including the catalyst

deactivation constant and the attrition rate constant.

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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