WO2005014681A2 - Process for preparing polyethylene - Google Patents

Process for preparing polyethylene Download PDF

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Publication number
WO2005014681A2
WO2005014681A2 PCT/US2004/022225 US2004022225W WO2005014681A2 WO 2005014681 A2 WO2005014681 A2 WO 2005014681A2 US 2004022225 W US2004022225 W US 2004022225W WO 2005014681 A2 WO2005014681 A2 WO 2005014681A2
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Prior art keywords
reactor
settling
catalyst
solids
polymer
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PCT/US2004/022225
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French (fr)
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WO2005014681A3 (en
Inventor
Patrick Noll
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Fina Technology, Inc.
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Publication date
Application filed by Fina Technology, Inc. filed Critical Fina Technology, Inc.
Priority to EP04777975A priority Critical patent/EP1646660A2/en
Priority to MXPA06000832A priority patent/MXPA06000832A/en
Priority to CA002533176A priority patent/CA2533176A1/en
Publication of WO2005014681A2 publication Critical patent/WO2005014681A2/en
Publication of WO2005014681A3 publication Critical patent/WO2005014681A3/en

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    • GPHYSICS
    • G05CONTROLLING; REGULATING
    • G05BCONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
    • G05B17/00Systems involving the use of models or simulators of said systems
    • G05B17/02Systems involving the use of models or simulators of said systems electric
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/2415Tubular reactors
    • B01J19/2435Loop-type reactors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/01Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • GPHYSICS
    • G05CONTROLLING; REGULATING
    • G05BCONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
    • G05B13/00Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion
    • G05B13/02Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion electric
    • G05B13/04Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion electric involving the use of models or simulators
    • G05B13/048Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion electric involving the use of models or simulators using a predictor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00191Control algorithm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00243Mathematical modelling
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00Characteristics for processes of polymerization
    • C08F2400/02Control or adjustment of polymerization parameters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S706/00Data processing: artificial intelligence
    • Y10S706/902Application using ai with detail of the ai system
    • Y10S706/903Control
    • Y10S706/906Process plant

Definitions

  • the present invention relates to a process for preparing polyethylene.
  • the present invention particularly relates to preparing high density polyethylene using a slurry loop reactor.
  • the present invention is a process for producing polyethylene using a slurry loop reactor comprising using a mathematical model to predict a plurality of process control parameters. The prediction is based on the desired product properties, reactor contents mass balance, and reactor characteristics. The slurry loop reactor is controlled using the predicted process control parameters.
  • the present invention is a controller programmed with such a mathematical model for use in controlling a polyethylene slurry loop reactor.
  • the present invention is a process for optimizing the configuration of a polyethylene slurry loop reactor comprising using such a mathematical model to design the reactor.
  • DETAILED DESCRIPTION OF INVENTION the present invention is a process for producing polyethylene using a slurry loop reactor.
  • the polyethylene produced can be high density polyethylene.
  • the slurry loop reactors useful with the process of the present invention include those using settling legs to remove polymer particles from the reactor. These reactors are also sometimes referred to as Phillips Reactors and manufacturing processes using such reactors are sometimes referred to as Phillips Processes. Loop reactors not having such legs can also be used with the method of the present invention.
  • a mathematical model is used.
  • this model uses mass balance of reactor contents, reactor geometry, catalyst kinetics, and settling phenomena in the outlet settling legs to determine relationships between inlet feed rates and reactor geometry on production conditions. The relationship between these can be defined using a series of equations having a plurality of variables.
  • Ch concentration of hydrogen in the reactor liquid
  • N ⁇ number of settling legs
  • Vt terminal velocity of settling polymer
  • P n rate of polymer leaving reactor that is not part of the settling leg solids bed
  • T s rate of slurry leaving reactor that is part of the settling leg solids bed
  • N Ar Archimedes number for polymer settling in settling leg
  • Aip cross sectional area of a settling leg occupied by polymer
  • a ⁇ cross sectional area of a settling leg
  • the ethylene feed into the reactor can be calculated from mass balance of ethylene around the reactor.
  • the catalyst feed to the reactor can be calculated.
  • the solid residence time is calculated as follows:
  • the slurry leaving the settling leg consists of two portions: the settled bed of polymer and liquid in the bottom of the settling leg, which is a larger concentration of solids than the reactor, and the polymer and liquid above this bed, which is the same concentration of solids as in the reactor.
  • the concentration of polymer in the settling bed solids bed is a function of the polymer and liquid densities as well as the polymer bulk density and is calculated as follows:
  • a mass balance of the two portions of polymer leaving in the outlet slurry is:
  • the polymer diameter is expressed as: Assuming the polymer settling in the settling leg to be steady-state and the polymer particles are close to spheres, the settling rate can be described by the following equations.
  • the Archimedes number for the polymer settling through the isobutane liquid is:
  • these equations can be used to solve for numerous combinations of knowns and unknowns. For example, if the number of settling legs is known, then the diameter of the settling legs can be calculated. This is a simple calculation using the same sequence of equations as above. For other variables, the equations above may be used in alternative sequences. An unknown variable, for example the ethylene concentration in the liquid, must first have an estimated value and then the sequence used in an iterative fashion until the ethylene concentration converges on a solution that satisfies all the equations. This type of calculation can be performed using the equations detailed above with an automated I spreadsheet.
  • the present invention is a controller for an industrial high density polyethylene slurry loop reactor. While the present invention can be used in manual or spreadsheet form, it can also be incorporated into the logic circuits of a controller. In one embodiment, the controller is a neural net or other artificial intelligence (Al) controller. When using the model of the present invention with a spreadsheet, it can be desirable to incorporate additional functionality into the spreadsheet using, for example, VISUAL BASIC®, or some other compatible computer program. It is also within the scope of the present invention that the model be incorporated into a computer program such as Fortran or C++. Many operations in a chemical process are routinely controlled using a Proportional Integral Derivitive (PID) controller.
  • PID Proportional Integral Derivitive
  • controllers While very useful in a conventional setting, are not preferred for the present invention. Such controllers are designed and used to monitor a single process variable and perform their control function based upon that single variable.
  • many PID controllers are used in conjunction with a second controller that can receive data from the PID controller and then reprogram the PID controller based upon the total inputs from the reactor sensors and controllers.
  • the present invention is implement using an Al controller capable of accepting multiple inputs and sending multiple outputs.
  • the controller is a neural network model based controller.
  • one such controller is a controller using Process Perfecter® software developed by Pavilion Technologies.
  • the process of the present invention for controlling a reactor can be very useful, particularly when changing polymer grades or production rates.
  • the process of the present invention can be used to optimize and control a loop reactor to produce polyethylene with desirable properties.
  • the model can also be used to design a loop reactor such that settler size, cycle time, reactor volume and energy consumption can all be optimized. While the primary subject of this application is directed to the production of polyethylene, it is well known that loop reactors can be used to produce other types of polymers.
  • polypropylene can also be produced using the method of the present invention and is within the scope of the present invention.
  • Any polymer that can be 5 produced using a loop reactor can be produced using the method of the present invention.
  • EXAMPLES The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated.0 EXAMPLE 1
  • the mathematical model described above is placed into a spreadsheet and automated to allow for quick calculation of solutions.
  • the intended operating range of the reactor is used to form the ranges of the known variables. Within these ranges, the variables are randomized and the spreadsheet used to calculate solutions to several5 different combinations of production conditions.
  • EXAMPLE 3 A computer spread sheet is programmed as in Example 2 except that it is set up to allow for the input of feeds to the reactor to calculate the outlet flow rates and compositions.
  • the interface for this model is displayed in the APPENDIX A as the RX Model Iterative.
  • the formulas are displayed in APPENDIX C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Automation & Control Theory (AREA)
  • Artificial Intelligence (AREA)
  • Computer Vision & Pattern Recognition (AREA)
  • Evolutionary Computation (AREA)
  • Medical Informatics (AREA)
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Abstract

Disclosed is process for producing polyethylene using a slurry loop reactor. The process includes using a mathematical model to predict a plurality of process control parameters based on the desired product properties and reactor characteristics and controlling the process using the predicted process control parameters. Also disclosed is a process controller programmed with the model and a method for optimizing the configuration of a loop reactor using the model.

Description

Process For Preparing Polyethylene
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a process for preparing polyethylene. The present invention particularly relates to preparing high density polyethylene using a slurry loop reactor.
2. Background of the Art It is well known in the art of manufacturing chemicals in general and polymers in particular to use a reactor consisting of a pipe containing a flowing stream of reactants. One such pipe reactor is known as the slurry loop reactor. In a slurry loop reactor, reactants are feed into a pipe containing a solvent and a catalyst. The admixture of solvent, reactants, and catalyst are continuously recycled through the pipe, hence the term "loop," with the reaction product being continuously removed. In the manufacture of high density polyethylene, particles of polyethylene can be removed from the reactor by means of a settling leg. U. S. Patent No. 3.293,000 to Marwil discloses the use of settling legs in a loop reactor for manufacturing an ethylene butane copolymer. In this reference, the settling leg functions to allow a portion of the polymer slurry to escape from the loop into outlets that allow the particles to be gravimetrically removed.
[0004] While technology for preparing polymers has changed with respect to catalysts and reactants, the same general loop reactor technology employed in the 1960s is still in use. For example, U.S. Patent No. 4,613,484 to Ayres, et al., discloses an improvement to settling legs, also referred to as accumulator legs, is disclosed. This technology is still generally current and in present use, particularly for the production high density polyethylene. Despite loop reactors having been used for a long time, the process of starting a running a loop reactor is not without problems. U. S. Patent No. 6,303,825 to Gerlich, et al. discloses a method of starting up a loop reactor system. This reference suggests using a microprocessor to automate starting up and running a loop reactor. One suggested algorithm recognizes the end of the startup of the reactor and then controls the reactor at steady state. SUMMARY OF THE INVENTION In one aspect, the present invention is a process for producing polyethylene using a slurry loop reactor comprising using a mathematical model to predict a plurality of process control parameters. The prediction is based on the desired product properties, reactor contents mass balance, and reactor characteristics. The slurry loop reactor is controlled using the predicted process control parameters. In another aspect, the present invention is a controller programmed with such a mathematical model for use in controlling a polyethylene slurry loop reactor. In still another aspect, the present invention is a process for optimizing the configuration of a polyethylene slurry loop reactor comprising using such a mathematical model to design the reactor. DETAILED DESCRIPTION OF INVENTION In one embodiment, the present invention is a process for producing polyethylene using a slurry loop reactor. The polyethylene produced can be high density polyethylene. The slurry loop reactors useful with the process of the present invention include those using settling legs to remove polymer particles from the reactor. These reactors are also sometimes referred to as Phillips Reactors and manufacturing processes using such reactors are sometimes referred to as Phillips Processes. Loop reactors not having such legs can also be used with the method of the present invention. [0010] In the practice of the method of the present invention, a mathematical model is used. In one embodiment, this model uses mass balance of reactor contents, reactor geometry, catalyst kinetics, and settling phenomena in the outlet settling legs to determine relationships between inlet feed rates and reactor geometry on production conditions. The relationship between these can be defined using a series of equations having a plurality of variables. The variables that can be employed in a process of the present invention include: Et = ethylene flow into reactor E0 = ethylene flow out of reactor // = isobutane flow into reactor ι0 = isobutane flow out of reactor Hi = hexene flow into reactor H0 = hexene flow out of reactor Hc = hexene conversion in reactor hi = hydrogen flow into reactor h0 = hydrogen flow out of reactor hc = hydrogen conversion in reactor
P0 = polymer flow out of reactor
L0 = liquid flow out of reactor TiW = total mass flow into reactor
Tow = total mass flow out of reactor
Tov = total volume flow out of reactor
Cj = catalyst flow into reactor c0 = catalyst flow out of reactor CE = concentration of ethylene in the reactor liquid
C = concentration of hexene in the reactor liquid
Ch = concentration of hydrogen in the reactor liquid
T = temperature of reactor
P = pressure of reactor Sw = weight concentration of solids in the reactor slurry
Sv = volume concentration of solids in the reactor slurry
Sws = weight concentration of solids in the settling leg solids bed
Nι = number of settling legs
V = reactor volume dι = settling leg diameter hi = settling leg height xb = bulk density of reactor polymer xp = density'of reactor polymer η = density of reactor liquid rs = density of reactor slurry ts = residence time of reactor solids k = catalyst activity p = catalyst productivity dc = catalyst diameter fc = catalyst feed factor kc = catalyst activity factor
Vt = terminal velocity of settling polymer
Ps = polymer settling rate
Pn = rate of polymer leaving reactor that is not part of the settling leg solids bed
Ts = rate of slurry leaving reactor that is part of the settling leg solids bed
Tn = rate of slurry leaving reactor that is not part of the settling leg solids bed m, = viscosity of reactor liquid rc = density of catalyst dp = polymer diameter
NAr = Archimedes number for polymer settling in settling leg
NRe = Reynolds number for polymer settling in settling leg g = acceleration due to gravity
Aip = cross sectional area of a settling leg occupied by polymer
Aι = cross sectional area of a settling leg The mathematical model of the present invention is developed based upon these variables. For example, a given slurry loop reactor can have the following known values:
Po -= 58034 Ib/h Lo = 52966 Ib/h CE = 5.0537 wt% C = 0.54695 wt% ch = 0.0075519 wt% He = 71 .03 % He = 50 % T = 210 F = 98.9 C P = 600 psig = 41 .8 atm w = 37.668 wt% V = 100 m3 di = 10 in hi = 15 ft ■~b = 0.45 g/cc
Figure imgf000005_0001
do = 100 m rc = 2.2 g/cc 9 = 9.80 m/s2 Relationships between the variables can be calculated as follows.
Assuming mass balance around the reactor,
T.w = Lo +P0 = 52966 lb/h + 58034 lb/h = 111000 lb h
The component mass flows in the outlet liquid can be calculated based on known outlet concentrations. Hydrogen flow is negligible portion of total liquid flow. E =-^- = (5??66 Xl-«7) = 26771bΛ ° 100 100 H ___ L0CH = (52966 lb/h)(0.54695) _ ^ 100 100 ' h - - = (52966 lb/h)(0.0075519) _ 0 100 100 L +EXH = L fo=L0-E0-H0= 52966 lb/h - 2677 lb/h - 290 lb/h = 50000 lb/h I Assuming mass balance of isobutane around the reactor, /,-Jo=0 It=Jo =50000 lb/h Assuming constant conversion of hexene and hydrogen into polymer across the intended operating region, the hexene and hydrogen feeds into the reactor can be calculated: H,(100~CH) H„ = 100 IQQg. = (100X290 lbh) = lo001b/h ' 100-C„ 100-71.03 b,.(ιoo-cΛ) 100 100/zo _(l00)(41b/h) h, = = 8 lb/h 100 -C,, 100-50
Assuming that HDPE was produced from only the monomers ethylene and hexene, the ethylene feed into the reactor can be calculated from mass balance of ethylene around the reactor.
Figure imgf000006_0001
Using the catalyst productivity and catalyst mass balance around the reactor, the catalyst feed to the reactor can be calculated.
Figure imgf000006_0002
58034 Ib/h 35.715 M, p 1624.9 lb/lb c,-c„ =0 c. =c0= 35.715 lb/h
An empirical correlation of isobutane liquid density, developed by Lewalle can be use with the process of the present invention. This correlation expresses liquid density (g/cc) as a function of liquid compositions (wt%), temperature (C), and pressure (atm) in the reactor:
Figure imgf000007_0001
08P /4.943e- 06 + 5.33e-06R -C„ (7.718e-04 + 2.362e-06R) -1.714e-07P2 +1.307e-09P3
Figure imgf000007_0002
-72(7.646e-06-6.735e-08P)+r2C£
Figure imgf000007_0003
Figure imgf000007_0004
0 The liquid density, upon substitution of variables, simplifies to p, =0.431 g/cc
Using the calculated liquid density, the assumed polymer density, and the solids concentration, the slurry density can be calculated:5 100/7 /7, (l00)(0.89g/cc)(0.431g/cc) P, 100pp+Slv{p,-pp) (100)(0.89 g/cc) + (37.668Xθ.431 g/cc - 0.89 g/cc) p. =0.535 g/cc
o The volumetric flow rate of slurry out of the reactor can be calculated from the mass flow rate and density of each component: 58034 lb/h 52966 lb/h Y 453.6 gY gal > 1ov + = 376gpm Pn Pi 0.89 g/cc 0.431 g/cc J lb 3785 cc 60min The volumetric solids concentration in the reactor is: S <?„ = oo 100 = 229.Λ64zl vo 1l0%/
Figure imgf000008_0001
The solid residence time is calculated as follows:
_ Vpβw = (l00 m3)(0.535 g/ccX37.668) le06 cc lb 60 min _ . ' ~ 100Po ~ (l 00X58034 lb/h) ' m3 453.6 g ' h ~ ■ mm
Assuming HDPE production kinetics as being first-order for ethylene concentration in the liquid and catalyst flow rate, the kinetic rate can be expressed as: P0 = kc0CEτs
Substituting the catalyst productivity and rearranging the kinetic rate equation, the catalyst activity is calculated as follows: P p = — c„ k = ^_ = 1624 9 Mb = 7_00 1Mb/min/wto/o τsCE (45.9 in)(5.0537 wt%)
The catalyst feed factor is a function of other measured reactor variables that makes it independent of catalyst type or catalyst activity. It is expressed as: e = fc.
Using mass balance of catalyst around the reactor and rearranging the kinetic rate equation yields the following equation for catalyst feed factor: f = kic. = ktcn = — P — - 7 5803i4 lb/h r = 2 ™50 l1b//h/mι •n/ /w +t0%/ ° τsCE (45.9 minX5.0537 wt%)
The catalyst activity factor quantifies the reactivity of the specific catalyst with respect to its size. It is expressed as: _ ΛΛ 11 Λ , . . Λ, , 3 = 7.00 lb/MMlb/mιn wt%/
Figure imgf000008_0002
The slurry leaving the settling leg consists of two portions: the settled bed of polymer and liquid in the bottom of the settling leg, which is a larger concentration of solids than the reactor, and the polymer and liquid above this bed, which is the same concentration of solids as in the reactor. The concentration of polymer in the settling bed solids bed is a function of the polymer and liquid densities as well as the polymer bulk density and is calculated as follows:
Figure imgf000009_0001
A mass balance of the two portions of the outlet slurry is: T ow = T s + T * n A mass balance of the two portions of polymer leaving in the outlet slurry is:
Using the known polymer concentrations of these two portions and solving the set of simultaneous equations, the amount of polymer leaving the settling leg from the settled bed of polymer can be calculated. This flow rate also indicates the polymer settling rate in the settling leg: 100P T. =
100P„ P. = lOOP. 100P„ 71 = S„
_ 100P. r„. -+ , 100(Po -P,) ow 111000 lb/h 58034 lb/h 100 100 37.7 P. = = 36460 lb/h 1 67.9 37.7
The viscosity of isobutane liquid as a function of temperature is: -7-3891 μ, (c?)
Figure imgf000010_0001
= Q 071 1 CP
An equation offered by Mignon to describe the relation between the size of the growing polymer particle, the catalyst particle size, and the catalyst productivity can be used with present invention. The polymer diameter is expressed as:
Figure imgf000010_0002
Assuming the polymer settling in the settling leg to be steady-state and the polymer particles are close to spheres, the settling rate can be described by the following equations. The Archimedes number for the polymer settling through the isobutane liquid is:
Figure imgf000010_0003
(666 μf (0.431 g/cc)(9.80 m/s2 ](θ.89 g/cc - 0.431 g/cc) NAr = (0.071 l cP)2
Figure imgf000010_0004
100 cm V l m )
N, = 1.13e05 An equation by Dallavalle expresses the drag coefficient for this type of flow up to
Reynolds number of 2e05. This equation can be used to calculate the Reynolds number from the Archimedes number:
Nie = ( 14-42 + 827V^ "3-798 ) = ( Vl4.42 + 1.827Vl.l3e05 -3.798
NRe = 453 The Reynolds number confirms that the above equation is valid for this flow regime. The velocity of the settling polymer can now be calculated using the Reynolds number:
Figure imgf000011_0001
_ N eμ, _ (453)(θ.0711 cP) g/m/s le06 μ f m V 3.28 ft v, = = 0.369 ft/s d p, (666 Xθ.431 g/cc) cP m 100 cm m
The expression relating the mass flow of settling solids to the velocity of those solids
Ps = N,A ϊ.pvv ttpp The area of the settling leg occupied by polymer is:
'" 100 400 ' v Substituting this area into the mass flow of settling solids equation yields: p s = X 4()0-N /d .2 S v Xpp
Rearranging this equation, the number of settling legs required for this reactor geometry and these production conditions is: 400P N, = πd, Svv,pp (400)(364601b/h) _ 453.6 g l ft ft ( ( in = 4 (lOin)2(22.6)(θ.369 fl/sXθ.89 g/cc) lb 3600 s 12 in 2.54 cm
In the practice of the process of the present invention, these equations can be used to solve for numerous combinations of knowns and unknowns. For example, if the number of settling legs is known, then the diameter of the settling legs can be calculated. This is a simple calculation using the same sequence of equations as above. For other variables, the equations above may be used in alternative sequences. An unknown variable, for example the ethylene concentration in the liquid, must first have an estimated value and then the sequence used in an iterative fashion until the ethylene concentration converges on a solution that satisfies all the equations. This type of calculation can be performed using the equations detailed above with an automated I spreadsheet.
[0043] In one embodiment, the present invention is a controller for an industrial high density polyethylene slurry loop reactor. While the present invention can be used in manual or spreadsheet form, it can also be incorporated into the logic circuits of a controller. In one embodiment, the controller is a neural net or other artificial intelligence (Al) controller. When using the model of the present invention with a spreadsheet, it can be desirable to incorporate additional functionality into the spreadsheet using, for example, VISUAL BASIC®, or some other compatible computer program. It is also within the scope of the present invention that the model be incorporated into a computer program such as Fortran or C++. Many operations in a chemical process are routinely controlled using a Proportional Integral Derivitive (PID) controller. These controllers, while very useful in a conventional setting, are not preferred for the present invention. Such controllers are designed and used to monitor a single process variable and perform their control function based upon that single variable. In an embodiment of the present invention, many PID controllers, are used in conjunction with a second controller that can receive data from the PID controller and then reprogram the PID controller based upon the total inputs from the reactor sensors and controllers. in another embodiment, the present invention is implement using an Al controller capable of accepting multiple inputs and sending multiple outputs. Preferably, the controller is a neural network model based controller. For example, one such controller is a controller using Process Perfecter® software developed by Pavilion Technologies. While the automated controllers can be desirable for their quick response, in effect controlling the reactor in real time, the use of the present invention manually should not be discounted. When incorporated into a spreadsheet, the process of the present invention for controlling a reactor can be very useful, particularly when changing polymer grades or production rates. In either case, the process of the present invention can be used to optimize and control a loop reactor to produce polyethylene with desirable properties. In an alternative embodiment, the model can also be used to design a loop reactor such that settler size, cycle time, reactor volume and energy consumption can all be optimized. While the primary subject of this application is directed to the production of polyethylene, it is well known that loop reactors can be used to produce other types of polymers. For example, polypropylene can also be produced using the method of the present invention and is within the scope of the present invention. Any polymer that can be 5 produced using a loop reactor can be produced using the method of the present invention. EXAMPLES The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated.0 EXAMPLE 1 The mathematical model described above is placed into a spreadsheet and automated to allow for quick calculation of solutions. The intended operating range of the reactor is used to form the ranges of the known variables. Within these ranges, the variables are randomized and the spreadsheet used to calculate solutions to several5 different combinations of production conditions. These results are placed into a large dataset and fed into the control software for the building of a neural network control model. The resulting neural network control model then possesses all of the inherent .relationships between variables of the original equation-based model. The accuracy of the equation-based model is proven when the control model is 0 placed online for closed loop control of key reactor compositions and rates ethylene concentration, percent solids, hexene concentration, hydrogen concentration, hexene/ethylene concentration ratio, hydrogen/ethylene concentration ratio and production rate. With the model-built controller, the variability of these control variables is decreased by 70% in comparison to conventional PID controllers replaced by the controller of the5 present invention. The robustness of the model is demonstrated by the ability of the controller to perform successfully at from about full reactor capacity down to about half capacity and across a large range of compositions. The generic nature of the model with respect to catalyst using catalyst feed factor and catalyst activity factor to describe catalyst instead of o catalyst feed flow, catalyst activity, and catalyst size is been shown by its ability to be used for Chromium, Ziegler-Natta, and Metallocene catalysts successfully with the same controller. EXAMPLE 2 A loop reactor is modeled according to the method shown above, with relationships established between the variables. Assumptions are made and then confirmed upon experimental observation. A computer spreadsheet is programmed with the model. The interface for this model is displayed in APPENDIX A as the RX Model. The formulas are displayed in APPENDIX B. EXAMPLE 3 A computer spread sheet is programmed as in Example 2 except that it is set up to allow for the input of feeds to the reactor to calculate the outlet flow rates and compositions. The interface for this model is displayed in the APPENDIX A as the RX Model Iterative. The formulas are displayed in APPENDIX C.

Claims

WHAT IS CLAIMED: 1. A process for producing polyethylene using a slurry loop reactor comprising using a mathematical model to predict a plurality of process control parameters based on the
5 desired product properties and reactor characteristics and controlling the process using the predicted process control parameters. 2. The process of Claim 1 wherein the variables used to prepare the mathematical model include a plurality of variables selected from the group consisting of: ethylene flow into reactor, ethylene flow out of reactor, isobutane flow into reactor, isobutane flow out of o reactor, hexene flow into reactor, hexene flow out of reactor, hexene conversion in reactor, hydrogen flow into reactor, hydrogen flow out of reactor, hydrogen conversion in reactor, polymer flow out of reactor, liquid flow out of reactor, total mass flow into reactor, total mass flow out of reactor, total volume flow out of reactor, catalyst flow into reactor, catalyst flow out of reactor, concentration of ethylene in the reactor liquid, concentration of hexene in the5 reactor liquid, concentration of hydrogen in the reactor liquid, temperature of reactor, pressure of reactor, weight concentration of solids in the reactor slurry, volume concentration of solids in the reactor slurry, weight concentration of solids in the settling leg solids bed, number of settling legs, reactor volume, settling leg diameter, settling leg height, bulk density of reactor polymer, density of reactor polymer, density of reactor, liquid, density 0 of reactor slurry, residence time of reactor solids, catalyst activity, catalyst productivity, catalyst diameter, catalyst feed factor, catalyst activity factor, terminal velocity of settling polymer, polymer settling rate, rate of polymer leaving reactor that is not part of the settling leg solids bed, rate of slurry leaving reactor that is part of the settling leg solids bed, rate of slurry leaving reactor that is not part of the settling leg solids bed, viscosity of reactor liquid,5 density of catalyst, polymer diameter, Archimedes number for polymer settling in settling leg, Reynolds number for polymer settling in settling leg, acceleration due to gravity, cross sectional area of a settling leg occupied by polymer, and cross sectional area of a settling leg. 3. The process of Claim 2 wherein the variables used to prepare the mathematical o model are: polymer flow out of reactor, liquid flow out of reactor, concentration of ethylene in the reactor liquid, temperature of reactor, pressure of reactor, weight concentration of solids in the reactor slurry, reactor volume, settling leg diameter, settling leg height, bulk density of reactor polymer, density of reactor polymer, density of catalyst. 4. The process of Claim 2 wherein the variables used to prepare the mathematical model are: polymer flow out of reactor, liquid flow out of reactor, concentration of ethylene 5 in the reactor liquid, temperature of reactor, pressure of reactor, weight concentration of solids in the reactor slurry, reactor volume, settling leg diameter, settling leg height, bulk density of reactor polymer, density of reactor polymer, density of catalyst, concentration of hexene in the reactor liquid, concentration of hydrogen in the reactor liquid, hexene conversion in reactor, hydrogen conversion in reactor.0 5. The process of Claim 1 wherein the process is controlled using the mathematical model which has been incorporated into a computer spreadsheet. 6. The process of Claim 1 wherein the process is controlled using the mathematical model which has been incorporated into a controller. 7. The process of Claim 6 wherein the controller is a neural network model based5 controller. 8. A controller for an industrial slurry loop reactor used to produce high-density polyethylene comprising a controller programmed with an algorithm to control slurry loop reactor using the process of Claim 1. 9. The controller of Claim 9 wherein the controller is a neural network model based o controller. 10. A process for optimizing the configuration of a polyethylene loop reactor comprising using the model of Claim 1 to design the reactor. 11. The process of Claim 10 wherein the reactor is designed such that settler size, cycle time, reactor volume and energy consumption are optimized.5
APPENDIX A
Rx Model
Loop Reactor Worksheet Feeds to Loop Inside Loop Instructions Cat feed factor = *250 S« % Eth in loop = 5-05 wt % in liq MaRacTianges to blue text L . Cat activity factor = " 7 i PE (Heat Bal) = 58034 Ib/h Catalyst/ethylene = "0-59525* Ib/Mlb Temp = 210 F May change. Hexene/ethylene = 16-6667 Ib/Mlb Press = 600 psig Hexene = ""1000 l lb/h % Solids =. 37.6δIΪ0514 jwt% DO NOT make changes to red text. Catalyst = 35-7147 Ib/h *30 s Total ethylene = , 60000 ; Ib/h # of Settling Legs =[ , ""* Click material balance button. Isobutane/ethylene = 0.83333 ratio Loop Volume = * 10*0 m j= Calculated but should be input to control model Total isobutane = "S Bϋ .ib h Settling Leg Diam- = 10 inches Settling Leg Height = 15 ft Flash Tank rPE = 0-89 g/cc % Hβx/%Eth 0.03608 mol/mol BDPE = 0- 5 g/cc % Ethylene = 5.053721 wt% Catalyst Productivity = ϊδ iϊTisr • Ib PE/lb cat % Hexene = 0.54695 ,wt% Temp = 98-9"" C Total Feed = 111000 Ib/h Press = 41-8 atm Liquid (Vapor) = Si s ib/h 0-535 g/cc Isobutane = 50000 Ib/h % Solids = 22-6 vol% Ethylene = 2677 Ib/h % C6 = 0.55 wt% in liq Hexene = 290 Ib/h Solids R-T- = 45.9 min PE = SOOS-f.S Ib/h Liquid R-T- = 83-3 min (catalyst activity) = 7 0 lb PE/lb cat/min/% Eth, 0.431 g/cc Settling Solids = 36460 Ib/h PE from legs = 58034 Ib/h PE from loop = 0 Ib/h Total out = 376 gp
Rx Model Iterative
Loop Reactor Worksheet Feeds to Loop Inside Loop Instructions Cat feed factor =\ "2Sβ " lbPE/h/miπ/%eth % Hft in loop = 5.05 wt% in liq f Slake cϊtangeβto Blue text Cat activity factor=. 7 (micron)Λ3*lbPE/M lbcat/%eth/min PE (Heat Bal) = 58033 Ib/ [jfinctoiii'ng catalyst below) Catalyst/ethylene = 0.S952381 ' Ib/Mlb Temp = 210 F May change- " Hexene/ethylene = J6-666667 Ib/Mlb Press = 600 psig DO NOT make changes to red text- Hexene =r fil 'lb/h % Solids ='. "37.67 * wt% Catalyst =' 35.714286 Ib/h t-y-te = 30 s Total ethylene =., ββfiβø jb/h # of Settling Legs =,< 4 Click material balance button. Isobutane/ethylene = 0.8333333 ratio Loop Volume = 100 m* = In Material Balance Total isobutane = " ~WHW lb/h Settling Leg Diam. = 10 inches 1= Out of Material Balance Settling Leg Height = 15 ft Flash Tank rPE = 0.89 g/cc % Hex/%Eth 0-03608 mol/mol BD = 0-45 g/cc % Ethylene =r~~gM~-- "wt% Catalyst Productivity = 1625 lb PE/lb cat % Hexene = - ιpJS J t% Temp = 98-9 C Total Feed = 111000 Ib/h Press = 41-8 atm Liquid (Vapor) = 52966 ib/h 0-535 g/cc Isobutane = 50000 Ib/h % Solids = 22-6 voI% Ethylene = 2677 Ib/h % C6 = 0.55 wt% in liq Hexene = 290 Ib/h Solids R-T- = 45-9 mm PE = 58034 Ib/h Liquid R.T. = 83-3 min k (catalyst activity) = 7.0 lb PE/lb cat/miπ/% Eth- PE Balance = 1 Ib/h r,„ = 0-431 g/cc Hexene Bal = 0 Ib/h Settling Solids = 36460 Ib/h Settling Solids Bal = 0 Ib/h PE from legs = 58033 Ib/h PEfrom loop = 0 Ib/h Total out = 376 gpm Hydrogen Hydrogen Feed =.~ """" w — " Ib/h Hydrogen Out = 4.00 lb/h % Hydrogen = 0.0076 wt% %Hydrogen = 0-2195 moI% % Hy/% Eth = 0.0210 mol/mol
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