IP Library Granted Patent US 7,786,227
Granted Patent B2
US 7,786,227 · App. 11/890,726 · Granted Aug 31, 2010

Monomer concentration prediction and control in a polymerization process

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Quick Facts
Patent No.
US 7,786,227
App. No.
11/890,726
Granted
Aug 31, 2010
Kind
B2
Abstract

A method for the control of a polymerization process, which method employs the combination of a densitometer measurement of the polymerization reaction mixture and a quadratic computer model.

Claims (150)

1. In an ethylene monomer slurry polymerization process for forming solid high density polyethylene polymer particles in a reaction mixture of ethylene monomer, ethylene polymerization catalyst, and hydrogen in liquid solvent and controlling the physical properties of said polyethylene polymer particles utilizing at least one process measurement taken from said polymerization process, said polymerization process employing a densitometer to obtain the density of said polymerization reaction mixture containing said ethylene monomer, the improvement comprising:

(a) measuring at least one pressure and at least one temperature in said reaction mixture, calculating the average concentration of solids in said reaction mixture, measuring the density of said reaction mixture with said densitometer, measuring said ethylene monomer concentration, each of said measurements providing an analog signal output, and converting said analog signals to digital signals;

(b) providing a digital computer with a data base that includes said digital signals obtained from step (a);

(c) programming said digital computer according to a densitometer quadratic concentration model having constants and a real root for determining the ethylene monomer concentration in said reaction mixture, said densitometer quadratic concentration model comprising

(1) a reference temperature calculated according to the equation

TRX=measured temperature T minus 200

(2) a reference pressure is calculated according to the equation

PRX=measured pressure P minus 585.3

(3) a composition term using ethylene in mole % and hydrogen in mole % calculated using the equation,

AX

=

C

2

=

2

+

H

2

28.57

100

(4) reaction mixture liquid density polynomial terms a calculated using the equation,

DENLIQ 1= a 1 +a 2 TRX+a 3 AX+a 4 PRX+a 5 TRX*AX+a 6 TRX*PRX*AX+a 7 TRX 2

DENLIQ 2 =DENLIQ 1 +b 1 AX 2 +b 2 TRX*AX 2 +b 3 AX 2 PRX DENLIQ 3 =DENLIQ 2 +c 1 TRX 3

(5) a polyethylene polymer particle density term calculated using the equation,

DENPOL=d 1 +d 2 TRX

(6) a reaction mixture liquid density term calculated using the equation,

DENLIQ

=

100

*

slurrydensity

*

DENPOL

-

FSOLIDS

*

slurrydensity

*

DENPOL

100

*

DENPOL

-

FSOLIDS

*

slurrydensity

(7) a reaction mixture polyethylene polymer particle solids concentration term calculated using the equation,

QSOLIDS

=

100

*

DENPOL

*

(

slurrydensity

-

DENLIQ

3

)

Slurrydensity

*

(

DENPOL

-

DENLIQ

3

)

(8) said constants in said quadratic concentration model calculated are calculated according to the equations,

Q CONSTANTS= e 1 +e 2 TRX+e 3 PRX+e 4 TRX 2 +e 5 TRX 3

QA=f 1 +f 2 TRX+f 3 PRX

QB=g 1 +g 2 TRX+g 3 TRX*PRX

QC=Q CONSTANTS− DENLIQ

(9) said real root in said quadratic concentration model for the determination of the ethylene monomer concentration in said reaction mixture is calculated using the equations,

QA *( X 2 )+ QB*X+QC= 0

X

=

-

QB

-

(

QB

)

2

-

4

*

QA

*

QC

2

*

QA

and

(10) the concentration of ethylene monomer in said reaction mixture is calculated using the equation,

C

2

=

=

2

[

100

*

X

-

H

2

28.57

]

wherein “*” indicates a multiplication function, and the parameters a i , b i , c i , d i , e i , f i , g i are constants in each one of the equations shown above and their numerical values are

a

b

C

d

0.4633

−0.68998

−0.0000002

0.927

−0.0008884

−0.0300355

0.000307

−0.36508

0.0033084

0.0000462

−0.0036994

0.0000238

−0.0000082

E

f

g

0.4633

−0.68998

−0.36508

−0.0008884

−0.030055

−0.0036994

0.0000462

0.0033084

0.0000239

−0.0000082

−0.0000002

(d) calculating the physical properties comprising polyethylene polymer particle density, reaction mixture density, polyethylene solids concentration, and ethylene monomer concentration using the model of step (c) together with the database of step (b);

(e) using said calculated physical properties of step (d) as a predictor of at least one physical property of said polyethylene polymer particles produced by said polymerization process; and

(f) controlling said polymerization process based on said calculated physical properties.

2. The method of claim 1 where said predicted physical property is at least one of density and melt index.

Assignments (18)
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032112/0786 →
APPOINTMENT OF SUCCESSOR ADMINISTRATIVE AGENT Recorded Jan 22, 2014
From: UBS AG, STAMFORD BRANCH
To: BANK OF AMERICA, N.A.
Reel/Frame 032112/0863 →
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: CITIBANK, N.A.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032113/0644 →
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: DEUTSCHE BANK TRUST COMPANY AMERICAS
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032113/0684 →
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: BANK OF AMERICA, N.A.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032113/0730 →
SECURITY AGREEMENT Recorded May 19, 2010
From: EQUISTAR CHEMICALS, LP
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 024402/0655 →
SECURITY AGREEMENT Recorded May 18, 2010
From: EQUISTAR CHEMICALS, LP
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 024397/0861 →
SECURITY AGREEMENT Recorded May 7, 2010
From: EQUISTAR CHEMICALS. LP
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 024351/0001 →
SECURITY AGREEMENT Recorded May 6, 2010
From: EQUISTAR CHEMICALS, LP
To: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERAL AGENT
Reel/Frame 024342/0443 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.; EQUISTAR CHEMICALS, LP
Reel/Frame 024337/0705 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
To: EQUISTAR CHEMICALS, LP
Reel/Frame 024337/0186 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.; EQUISTAR CHEMICALS, LP
Reel/Frame 024337/0856 →
RELEASE OF SECURITY INTEREST Recorded May 4, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: EQUISTAR CHEMICALS, LP
Reel/Frame 024329/0535 →
SECURITY AGREEMENT Recorded Oct 30, 2009
From: EQUISTAR CHEMICALS, LP
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 023449/0687 →
SECURITY AGREEMENT Recorded Apr 9, 2009
From: EQUISTAR CHEMICALS, LP
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT
Reel/Frame 022678/0860 →
SECURITY AGREEMENT Recorded Aug 4, 2008
From: BASELL POLYOLEFINE GMBH; ARCO CHEMICAL TECHNOLOGY L.P.; ARCO CHEMICAL TECHNOLOGY, INC.; ATLANTIC RICHFIELD COMPANY; BASELL NORTH AMERICA, INC.; BASELL POLYOLEFIN GMBH; LYONDELL CHEMICAL COMPANY; EQUISTAR CHEMICALS, L.P.
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 021354/0708 →
GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AND PATENT APPLICATIONS Recorded Mar 26, 2008
From: BASELL POLYOLEFINE GMBH; ARCO CHEMICAL TECHNOLOGY L.P.; ARCO CHEMICAL TECHNOLOGY, INC.; ATLANTIC RICHFIELD COMPANY; BASELL NORTH AMERICA, INC.; EQUISTAR CHEMICALS. LP.; LYONDELL CHEMICAL COMPANY; LYONDELL CHEMICAL TECHNOLOGY, L.P.; LYONDELL PETROCHEMICAL COMPANY; NATIONAL DISTILLERS AND CHEMICAL CORPORATION; OCCIDENTAL CHEMICAL CORPORATION; OLIN CORPORATION; QUANTUM CHEMICAL CORPORATION; BASELL POLYOLEFIN GMBH
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 020704/0562 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 7, 2007
From: BUCHELLI, ALBERTO; HAYNIE, STEVEN P.; WICKER JR., BRUCE A.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 019729/0167 →