IP Library Granted Patent US 7,396,892
Granted Patent B2
US 7,396,892 · App. 11/145,260 · Granted Jul 8, 2008

Process for removal of intermediate hydrogen from cascaded polyolefin slurry reactors

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Quick Facts
Patent No.
US 7,396,892
App. No.
11/145,260
Granted
Jul 8, 2008
Kind
B2
Abstract

Multimodal polyolefin polymers may be prepared in series-connected polymerization reactors where a prior reactor is a slurry reactor employing light solvent as the slurry medium and hydrogen to limit polymer molecular weight, the polymer product from the prior reactor being substantially freed of hydrogen prior to entry into a subsequent polymerization reactor operating at low hydrogen pressure to produce a high molecular weight olefin. The economics and operating performance of such a series slurry reactor polyethylene process can be significantly improved through the use of an intermediate slurry transfer system and hydrogen removal apparatus that employs flash drums in series in conjunction with a warm recycle solvent slurry diluent.

Claims (14)

1. An interstitially mixed, multimodal polyethylene copolymer containing a low molecular weight portion comprising a copolymer of ethylene and at least one other copolymerizable olefin monomer, and a higher molecular weight portion comprising a polyethylene homo- or copolymer, prepared by the process of

a) polymerizing at least two olefin monomers in the presence of hydrogen in a prior slurry reactor employing light solvent as a slurry medium to form a first polyolefin polymer of a first molecular weight; and

b) removing said first polyolefin polymer from said prior slurry reactor as a hydrogen-containing polymer slurry in light solvent and introducing said hydrogen-containing polymer slurry into a subsequent slurry reactor containing ethylene and optionally one or more olefin monomers other than ethylene, and employing a low concentration of hydrogen, polymerizing to form an ethylene homo- or copolymer, and recovering a polyolefin polymer therefrom,

wherein the hydrogen concentration in the hydrogen-containing polymer slurry is lower than the hydrogen concentration in said prior slurry reactor, the hydrogen mass flow from the hydrogen-containing polymer slurry fed to the subsequent reactor is less than a fresh hydrogen mass flow feed to the subsequent reactor by a factor of at least 10, and wherein a rapidly hydrogen-consuming catalyst is not employed in said subsequent slurry reactor.

2. The copolymer of claim 1 , wherein the olefin comonomer present in said prior slurry reactor is selected from the group consisting of propene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.

3. The copolymer of claim 1 , wherein no comonomer is fed to said subsequent slurry reactor other than residual comonomer contained in said polymer slurry from said prior slurry reactor.

4. The copolymer of claim 1 , wherein an olefin comonomer is fed to said subsequent slurry reactor, selected from the group consisting of propene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.

5. The copolymer of claim 1 , wherein both said low molecular weight portion and said higher molecular weight portion are prepared by copolymerizing ethylene and at least one second comonomer selected from the group consisting of propene, 1-butene, 1-hexene, and 1-octene.

6. The copolymer of claim 1 , wherein catalyst is added only to said prior slurry reactor.

7. The copolymer of claim 1 , wherein said catalyst is a supported catalyst having deposited thereon a single catalytic species.

8. The copolymer of claim 1 , wherein said catalyst is a supported catalyst having two different catalytic species deposited thereon.

9. The copolymer of claim 6 , wherein said catalyst is a Ziegler-Natta transition metal catalyst.

10. The copolymer of claim 1 , having a polydispersity of about 25.

11. The copolymer of claim 1 , wherein hydrogen is substantially removed from said polymer slurry from said prior reactor by a cascade of at least two flash drums between said prior and said subsequent reactor.

Assignments (17)
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032112/0786 →
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 →
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 →
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 024337/0856 →
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 024337/0705 →
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 →