\\ J, Saudi Chem,Soc,; Vol. 8, No. 1; pp. 97-104 (2004) ‘THE EFFECT OF DESIGN PARAMETERS ON INDUSTRIAL UNIPOL POLYETHYLENE FLUIDIZED BED POLYMERIZATION PROCESS, Nayef M. Ghasem!, Waheed A. AL-Masry”,, Fahad S. Al-Mubaddel’ and Yousef S. A-Zeghayer” "Department of Chemical Engineering, University of Malaya, Kuala Lumpur 59100, Malaysia (Received 25" May 2003; Accepted 27" Dec. 2003) Ha sgt le Lance daeey gel Lets ates eal gle eal All obs ote cht sone a2 Gail ge Sol Lets JOE ye CUAL ST 5pals Cae Soll BLA Sy ell mathe as eld asta g5UA) goal Q cabal oh C18 "Upsig” Ue has ook cht abs # hall OH abe de ia aly Dyer ak gl teat) UL JE GS Jecely (gees Geld Jolie UU iy jibe ny cr pial Sees BLN le fell CU ON Ly Jel ga UT doe et ee dag gh dat) ad Cath Dye oy IS ot Aaya mee LS CY Jers pd IL le Le ft ub of Ce He ce tnely NE hy (anes EM gy yl itm Stl antly (1A OT Polyethylene is the largest synthetic commodity polymer in terms of its annual production rate, and it is ‘widely used through out the world due to its versatile physical and chemical properties. The polymerization of olefins occurs through their interaction with active sites on catalyst solid surfaces. A mathematical model describing the UNIPOL process for the production of polyethylene in the gas phase using Ziegler-Natta catalyst in a bubbling fluidized bed is developed and used to analyze the major processes determining the behavior and performance of these industrially important units. The effects of the reactor volume and its height to diameter ratio on the dynamic behavior of the reactor were studied. It has been found that they have considerable influence on the system performance and production rat, Also, the investigation showed that both static bifurcation (multiplicity of the steady states) as well as ‘dynamic bifurcation (stable/unstable periodic attractors) behavior cover wide regions of the design and ‘operating parameters damain, Keywords: Polyethelyen, polymerization, fluidized bed, UNIPOL, Ziegler-Natta, reactor stability 7 *Department of Chemical Engineering, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia. INTRODUCTION In recent years, polyethylene achieved its permenant position in thermoplastics industries due to a remarkable catalyst and gas-solid fluidized bed tectinology [1-4]. In addition, by ‘employing the Ziegler-Natta catalyst, the process can operate at relatively low pressure and temperature (20 atm and 100 °C) compared to the conventional process (2000 atm and 200 °C). However, improper control of the process parameters, especially the catalyst feed rate, ‘gas feed temperature and gas superficial velocity may lead to temperature runaway and clusters formation in the reactor. Subsequently, the plant hhas to be shut down for cleaning purpose. In addition, the situation becomes worse when the reactor bed temperature exceeds the polyethylene softening point (127 °C), where the solid particles tend to agglomerate and may form huge chunks in the reactor. Union Carbide’s process technology, known as "UNIPOL" to produce polyethylene, is charac- terized by mild operating conditions, and is less energy intensive than the traditional high pressure process (2000-3000 atm). In the UNIPOL process, “To whom all correspondence should be addressed. email walmasry@ksu.edu.sa98 NaygfM. Ghasem, Waheed A. Al-Masry, Fahd S, ArMubaddel and Yousef'S. Al-Zyegheyr high purity ethylene and catalyst are continuously fed into the fluidized-bed reactor, where ethylene and co-monomers such as Butene-1 or Hexene-1 are polymerized together under a pressure of 20- 30 atm and a narrow temperature range. In gas phase ethylene polymerization reactors, tight temperature control is the most important factor to ensure that the temperature in the reaction zone is kept above the dew point of the reactants, yet below the melting point of the polymer to prevent melting and consequent agglomeration of the product particles [5]. Therefore, the most commercial gas phase fluidized bed polyethylene reactors are operated in a relatively narrow temperature range between 80-127 °C [6]. Even within this temperature range, temperature excursions must be avoided because they can result in low catalyst productivity and significant changes in product properties. In the present work, the effect of reactor height to diameter ratio for reactor volume of 29.5 m’ {2} was investigated as 1 function of catalyst feed rate and compared to the literature values. The aim of the present work ‘was to determine the stable operating zones for gas fluidized bed process and plant design, and to find the criteria for running the process safely with high reactor productivity. PROCESS DESCRIPTION A simple flowsheet of the UNIPOL process is shown in Figure 1. The feed to the reactor consists of ethylene, co-monomer (I-butene or I-hexene), hydrogen, inert (nitrogen) and catalyst (Ziegler- Natta). The uncreated gases stream from the top of the reactor is cooled by passing it through a heat exchanger. The heat exchanger is assumed to cool the recycle gas instantaneously to the desired feed temperature as the case considered by Choi and Ray (2). The temperature in the reaction zone can be adjusted by manipulating the flow rate of the cooling water in the extemal heat exchanger [5] ‘The temperature in the reaction zone can also be adjusted by manipulating the coolant temperature at the reactor walls. The height of the bed is held constant by adjusting the polymer withdrawal rate. The pressure drop across the fluidized bed is a good measure of the bed height when the fluidizing gas velocity is kept constant. J, Saudi Chem. Soc.; Vol. 8, No. 1 REACTOR MODEL. Mass balances on hydrogen and co-monomers are not considered in the system model, because hydrogen and co-monomer have only mild effects fon the reactor dynamics [3]. In modeling the process, the two-phase model (bubble and dense phase) is used. Considering a freely bubbling fluidized bed composed of dense phase and bubble phase for polyethylene polymerization, as well as the same assumptions and physical parameters used by Ghasem [1] and Choi and Ray [2], the following model equations are obtained! Material balance Bubble phase (ethylene): X, =X, +(1- Xe *8 & a) ‘The average value of Xyacross the bed height: = I-e**) @) KB } : y Emulsion phase (ethylene): = a(1-X,)+PI(1-X,)(1-e"**) -G XX, eS) @) © xpx, tom ~ @+x, Emulsion phase (catalyst) & a dt AH(I-8°)1- ene )P, 4) cuxyett ~~ 8EX, Energy balance Bub ps yee Xy= X + (er X) HN R65) The evcrag vale oF Xs as the bed ght R= Ixae =%s |x KHIR, “ae Ree) Dense phase (ethylene): (6)‘The Effect of Design Parameters on Industrial Unipol Polyethylene Fluidized Bed Polymerization... 99 (x1) ax oy (YeeX (ale) = [inet RT sor [oe aR Se) pWXK re _ OX Xe OG —D H+X, @+X; Rae] a” Correlations used to predict the bubble fraction in the bed, the void fraction of the emulsion phase, gas velocities of bubble phase and emulsion phase, mass and heat interchange coefficient can be found elsewhere [2,3]. The physical constants used in the bifurcation analysis are shown in Table 1 A Etrytee aa Hyarogen ion, Toetylene stone tank * Figure 1: schematic diagram of the UNIPOL process. 1: Reactor, 2: Heat exchanger, 3: Compressor, 4:Degassing unit, 5: Catalyst feeder Table 1: Physical constants and parameters. Parameter J. Saudi Chem, Soe.; Vol. 8, No. 1 Value Dimension 0.456 eal gC" 0.44 cal g' Kt 0.95 gem? 237 gom” 0.029 gon” 7.6x10° calem' 5" K! 4.167x10° em’ g" car! s" 9000 cal mol" 1.16x10* gems" 916 cal g” 60x10" om? s 250 em 600 em,100 Nayef M. Ghasem, Waheed A. Al-Masry, Fahd S. Al-Mubaddel and Yousef S. Al-Zyegheyr RESULTS AND DISCUSSION To construct the static and dynamic bifurcation characteristics of industrial fluidized bed polyethylene reactor, the above model equations were solved using the AUTO software [9] for solving a set of ordinary differential equations. ‘AUTO code uses a continuation method in which the computation begins at a known solution point and continues to points along a specific branch of solutions. AUTO can be used to trace the steady state solution branches, to detect bifurcation points (multiple steady state solutions), and to ‘compute the bifurcation branches. It also locates Hopf bifurcation points and traces periodic solution branches. The most important reactor variable is the reaction temperature, as it must be below the softening temperature of polymer, ‘otherwise, partial melting of polymer particles and particle agglomeration may occur, and local hot spots may form in the reaction zone making operation difficult or impossible. Figure 2 shows the loci of the static limit points (SLPs) (dashed line) and Hopf bifurcation (HB) points (solid line) on two parameter continuation diagram for the height to diameter ratio (H/D) versus catalyst feed rate (q,) at fixed values of other parameters ‘The diagram can be used to predict the behavior of the resulting one parameter bifurcation diagram with catalyst feed rate (q.) as the bifurcation parameter at constant values of H/D as shown by the horizontal lines (H/D = 2.3, 3, 4) and other parameters (U/tige = 6, Co = 0.025 glem’, Yr = 1.1, Yw = 1.2). A cusp point (c) is formed on the static limit points loci curve. Above the cusp point up to the top of the HB loci curve the multiplicity of the system disappear and two HB points appear. The multiple steady state regions with two static limit points and two HB points dominate the region below the cusp point. Above the top of the beak of the HB loci curve (ie. H/D > 5.6) no HB neither static limit points (SLP) appears and the system behaves as a stable steady state. The two parameter continuation diagram is useful to predict the behaviors of the system prior to ‘operation ols ae 9 wo Catalyst feed rate (100 g/h) Figure 2: Two parameter continuation diagram for H/D versus q.. J. Saudi Chem. Soe,; Vol. 8, No. 1The Effect of Design Parameters on Industrial Unipol Polyethylene Fluidized Bed Polymerization .. 101 ‘The one-parameter bifurcation diagram (Figure 3) shows the effect of the catalyst feed rate as the bifurcation parameter for three selected values of H/D. The diagram shows the effect of catalyst feed rate and H/D on dimensionless dense phase monomer concentration (X,). The increase in catalyst feed rate is directly proportional to the rate of reaction, which means more consumption of monomer (ie. decrease in X,) takes place, by contrast, at fixed values of catalyst feed rate (for example 900 g/h) the increase in H/D increases X, Which means less conversion and more un-reacted monomer exits the reactor. Figure 4 shows catalyst feed rate effect on the dimensionless reactor dense phase temperature (%) at fixed values of H/D. It can be seen that at fixed values of catalyst feed rate the increase in HID decreases reactor temperature due to increase in the rate of heat removal. With the increase in e.ca a.7a4 a.ca4 a.sa Xi 8.404 0.304 8.204 000000m00000000000 gt eeeeccccccceeeee a 1 2 3 4 Catalyst feed rate (100 g/h) H/D, the range of catalyst feed rate at which stable steady state exist increases, as shown from the shift of HB points t the right with increase in H/D. Great care should be taken to avoid conditions that lead to formation of chunks or sheets or, in worse case, an unstable fluidized bed, which collapses, or causes polymer particles to fuse together. The control of a fluidized bed therefore has to be exercised to reduce chunking and sheeting and to prevent bed collapse or a need to terminate the reaction and shut down the reactor. This is the reason why commercial scale reactors are designed to operate well within proven stable operating zones, and why the reactors are used in a carefully circumscribed fashion Steady state _ stable <7 unstable Period branch @ stable 00 unstable 5 6 7 8 93 Figure 3: Effect of catalyst feed rate on X; at fixed values of H/D J, Saudi Chem. Soc.; Vol. 8, No. 1102 Nayef M. Ghasem, Waheed A. Al-Masry, Fahd S. AlbMubaddel and Yousef. Al-Zyegheyr a g Fip=23 aa} 5 8 Xs 8 al : won130 tae et 5 6 7 8 9 w Catalyst feed rate (100 g/h) Figure 4: Effect of catalyst feed rate on X3 at fixed values H/D. CONCLUDING REMARKS, ‘The reactor height to diameter ratio is an important design parameter in polyethylene fluidized bed reactors. The increase in height to diameter ratio increases the rate of heat removal, and reduces the risk of melting and agglomeration of the polymer inside the reactor. By contrast, higher values of height to diameter ratio, decreases polyethylene production rate and. the rate of the un-reacted ethylene leaving the reactor due to the low residence time, Itis clear that the static and dynamic bifurcation behaviors dominate the operation of fluidized bed catalytic reactors for the production of polyethylene (UNIPOL process) and have important implications on safe operating temperature and polyethylene production rate. An increase in catalyst feed rates increases reaction rate monotonically thus increasing polyethylene production rate. It also increases the rate of heat generation which can cause temperature runaway and polymer melting, J. Saudi Chem. Soe,; Vol. 8, No. 1 NOMENCLATURE Ca» monomer concentration in the bubble phase (gem*) Coe monomer concentration in the dense phase (gem*) Cy reference gas concentration (g cm’) Cig heat capacity of gas (cal ¢” K"!) Cys heat capacity of polymer (cal g" K"!) D” bed diameter (em) D,_ particle diameter (cm) E, activation energy for propagation (cal mol") H_ bed height (em) AH, heat of reaction (cal g"') ‘hy wall heat transfer coefficient (cal cm” " K"') Kp =Kye Ap/Gp KH = HHye(CouyCy)" Kyo reaction rate constant at reference temperature (em? g's) qe catalyst injection rate (gh!) R__ gas constant (cal mol" K"!) Ty. bubble phase temperature (K) T,_ emulsion phase temperature (K) Ty temperature of the feed gas (K) T,._ wall temperature (K)The Effect of Design Parameters on Industral Unipol Polyethylene Fluidized Bed Polymerization ... 103 Ther reference temperature (300 K) reference time (1.08X10" s) tu, velocity of bubble rising through the bed (ems") ue upward velocity of gas through the emulsion phase (ems") Us inlet gas velocity (em s") Uge minimum fluidization velocity (em s") Xex catalyst concentration (g catalyst/g polymer) Xi = CneCo" dimensionless monomer concen- tration in the dense phase X,_ dimensionless catalyst concentration Tr! dimensionless reactor temperature CyuCy" dimensionless monomer concen- tration in the bubble phase Xs = TyTmc! dimensionless bubble phase temperature Yu = TyTai! dimensionless wall coolant temperature variable fluidized bed height (em) Greek symbols a = (uae B (fo)(Head ros 81-6 6B = E(RT ad" B= (uy Un a polymer void fraction nr Void fraction e Prot Ems)(Co Ba) (1-6) PpiCpe(CoC ag" J, Saudi Chem. Soc.; Vol. 8, No. 1 Y= CAHMCyp Tre Pea density of catalyst (g em”) P; density of gas (g em") pot density of polymer (g em?) tata(CoCppn* REFERENCES [1] NM. Ghasem, Chem. Eng, Techno, 22, 777 (1999). (2] K-Y. Choi and W.H. Ray, Chem. Eng. Sei. 40, 2261 (1985), 13] KB. McAuley, DM. Macdonald and PJ McLellan, AIChE 1,41, 868 (1995), [4] KB. McAuley, J.P” Talbot and T.J. Hariss, Chem. Eng. Sci, 49, 2035 (1994) [5] S.A. Dadebo, MLL. Bell, P.J. MeLellan and K.B. McAuley, J Proc. Con. 7, 83 (1997). [6] T. Xie, KB. MeAuley, J.C.C. Hsu and D.W. Bacon, Ind, Eng. Chem. Res, 33, 449 (1994). [7] KB. McAuley and J.F, MacGregor, AICHE J, 37, 825 (1991). [8] K.B. McAuley and J.F. MacGregor, AICHE J, 39 855 (1993). 9] EJ. Doedel, AUTO Software, California Institute of Technology, Pasadena, CA (1986).104 NayefM. Ghasem, Waheed A. Al-Masty, Fahd S. Al-Mubaddel and Yousef S. Al-Zyegheyr J, Saudi Chem, Soe,; Vol. 8, No. 1