Title of Invention	“METHOD FOR PREPARING LINEAR ALPHA-OLEFINS WITH REMOVAL OF AROMATIC BY-PRODUCTS"
Abstract	The present invention relates to a method for preparing linear alpha-olefins by oligomerization of ethylene in the presence of an organic solvent and an oligomerization catalyst, wherein a product fraction of C10+ alpha-olefins contaminated with aromatic C9+ compounds is separated from a product main stream and transferred into a conversion reactor, where C10+ alpha-olefins and aromatic C9+ components are reacted in the presence of a • Friedel-Crafts alkylation catalyst to produce aromatic C19+ compounds; and to a reactor system therefore.

Title of Invention

“METHOD FOR PREPARING LINEAR ALPHA-OLEFINS WITH REMOVAL OF AROMATIC BY-PRODUCTS"

Abstract

The present invention relates to a method for preparing linear alpha-olefins by oligomerization of ethylene in the presence of an organic solvent and an oligomerization catalyst, wherein a product fraction of C10+ alpha-olefins contaminated with aromatic C9+ compounds is separated from a product main stream and transferred into a conversion reactor, where C10+ alpha-olefins and aromatic C9+ components are reacted in the presence of a • Friedel-Crafts alkylation catalyst to produce aromatic C19+ compounds; and to a reactor system therefore.

Full Text	METHOD FOR PREPARING LINEAR ALPHA-OLEFINS WITH REMOVAL OF AROMATIC BY-PRODUCTS AND REACTOR SYSTEM THEREFOR The present invention relates to a method for preparing linear alpha-olefins by oligomerization of ethylene in the presence of an organic solvent and a catalyst. Methods for the production of linear alpha-olefins by oligomerization of ethylene are widely known in the art. Usually, a catalyst is utilized in that process comprising a zirconium compo¬nent and an organoaluminum component which acts as an activator. For example, DE 43 38 414 Cl discloses a process for the production of linear alpha-olefins, wherein one reactor is utilized into which a catalyst solution and ethylene are introduced. That process results in a product distribution of linear alpha-olefins having C4-C28 carbon atoms, wherein the fraction of C20+ usually contains waxy, polymeric substances. The product stream containing alpha-olefins with C4-C28 carbon atoms may be separated into fractions, e.g. by distillation or extraction. One main fraction obtained is a fraction containing C10+ alpha-olefins, preferably C10-C18. This fraction may be often contaminated by aromatic components, preferably C9+ aromatic components which are formed during oligomerization. Of course, these by-products are not desired, as a less valuable fraction C10+ is provided. In the prior art, the aromatic components have been so far removed by repeated extraction and/or distillation, e.g. five distillation columns have been used so far to remove the aromatic components from the C10+ alpha olefin fraction. It is therefore an object of the present invention to provide a method for preparing linear alpha-olefins which overcomes the drawbacks of the prior art. Especially, a method shall be provided wherein aromatic by-products, commonly present in the C10+ alpha-olefin fraction, can be easily removed with low costs, in order to improve the value of the C10+ alpha-olefin fraction. This object is achieved in that a product fraction of C10+- alpha-olefins contaminated with aro¬matic C9+ compounds is separated from a product main stream and transferred into a conversion reactor, where C10+ alpha-olefins and aromatic 9+- components are reacted in the presence of a Friedel-Crafts alkylation catalyst to produce aromatic C19+ components. Preferably, the Friedel-Crafts-alkylation catalyst is selected from any material with sufficient acidity to catalyze the alkylation. More preferably, the Friedel-Crafts-alkylation catalyst is selected from clay, zeolites, Lewis ac¬ids and protonic acids. In one preferred embodiment, the Friedel-Crafts-alkylation catalyst is selected from clay, zeolite, H2SO4, P4O10, H3PO4, AlCl3, FeCl3, SbCl5, SnCL,, BF3, TiCl4, and ZnCl2. The aromatic C19+ compounds prepared may be preferably separated from unreacted C10+ alpha-olefins in or downwards the conversion reactor, preferably by distillation. Moreover, it is preferred that the separated C19+ compounds are combined with C20+ residue ob-tained during the oligomerization. The aromatic C19+ compounds may be transferred to a further device for thermal use thereof, preferably combustion. In one preferred embodiment, the conversion in the conversion reactor is conducted at ambient temperature. Further preferred, additional solvent is added to the fraction of C10+ alpha-olefins prior to intro-duction into the conversion reactor. Most preferably, the C10- alpha-olefin fraction is a C10-C18 fraction. The invention further provides a reactor system for oligomerization of ethylene to form linear alpha-olefins, preferably utilizing a method according to the invention, comprising an oligomeri¬zation reactor and a conversion reactor, wherein a Friedel-Crafts-alkylation catalyst is present in that conversion reactor. Surprisingly, it was found that the aromatic by-products contained in the C10+- linear alpha-olefin fraction can be easily converted (removed) by reacting the C10+ alpha-olefins with aromatic components, obtained in the oligomerization process, in the presence of a Friedel-Crafts alkyla-tion catalyst in a separate conversion reactor to produce aromatic components having at least C19+. These C19+ aromatic components can be easily separated from the C10- alpha-olefin fraction and can be further processed, for example, combusted. Thus, the separation of the aromatic by¬products is achieved in a very simple method step and safes five distillation columns which have been used so far to separate the aromatic by-products from the alpha-olefins fraction. Therefore, investment and operation costs are decreased, and a value added product (alpha-olefin fraction without by-products) is obtained. As is obvious for someone skilled in the art, the concept of the present invention may be also adapted to any hydrocarbon streams containing aromatic impurities or by-products. For example, in case of paraffinic streams, olefins have to be added into the paraffinic stream to allow the conversion to heavy aromatic compounds which may be easily separated. In general, the conversion of linear alpha-olefins (C10+) with aromatic components (C9+) is ac-cording to the following scheme: (Formula Removed) wherein R' is any alkyl group having two or more carbon atoms and R is any alkyl group having at least eight carbon atoms, preferably eight to sixteen carbon atoms. Additional advantages and features of the inventive method and reactor system are further illus¬trated with reference to the accompanying drawing, wherein Fig. 1 illustrates a schematic dia¬gram of the reactor system for carrying out the method according to the present invention. In Fig. 1 a reactor 1 for the oligomerization of ethylene to prepare linear alpha-olefins is pro¬vided. In the reactor 1 ethylene is oligomerized in the presence of a solvent, preferably toluene, and a suitable catalyst, preferably at a temperature of about 60-100°C. After oligomerization (the reactor is preferably operated continuously), a product stream is removed from the reactor via a discharge line 2. The product stream comprises the solvent, catalyst, liquid linear alpha-olefms and high molecular weight oligomers as well as unreacted dissolved ethylene. The constituents of the product stream may be separated, e.g. in a separation unit 3. For example, the liquid linear alpha-olefms may be separated into several fractions by distillation to obtain fractions of C4-C8, C10-C18 and C20+-. Usually, the fraction of C10-C18 (C10+) comprises aromatic by-products. This fraction may be transferred from the separation unit 3 via line 4 into a conversion reactor 5, op¬tional additional solvent may be provided, wherein the C10+ fraction and the aromatic by-products are reacted in the presence of a Friedel-Crafts-alkylation catalyst. The discharge stream of the conversion reactor 5 may be then further processed, e.g. the aromatic by-products (now C19+) can be separated from the alpha-olefins by distillation and transferred to a further device, e.g. for combustion. The purified C10+ fraction may be utilized for any desired purpose and has added value. The features disclosed in the foregoing description, in the drawing or in the claims may, both separately and in any combination thereof, be material for realizing the invention in diverse forms thereof. We Claim: 1. Method for preparing linear alpha-olefins by oligomerization of ethylene in the presence of an organic solvent and an oligomerization catalyst, characterized in that a product frac¬tion of C10+ alpha-olefins contaminated with aromatic C9+ compounds is separated from a product main stream and transferred into a conversion reactor, where C10+ alpha-olefins and aromatic C9+ components are reacted in the presence of a Friedel-Crafts alkylation catalyst to produce aromatic C19+ compounds. 2. Method according to claim 1, wherein the Friedel-Crafts alkylation catalyst is selected from any material with sufficient acidity to catalyze the alkylation. 3. Method according to claim 2, wherein the Friedel-Crafts alkylation catalyst is selected from clay, zeolites, Lewis acids and protonic acids. 4. Method according to claim 3, wherein the Friedel-Crafts alkylation catalyst is selected from clay, zeolite, H2SO4, P4O10, H3PO4, A1C13, FeCl3, SbCl5, SnCl4, BF3, TiCl4 and ZnCl2. 5. Method according to any of the preceding claims, wherein the aromatic C19+ compounds prepared are separated from unreacted C10+ alpha-olefins in or downwards the conversion reactor. 6. Method according to claim 5, wherein the aromatic C19+ compounds are separated by dis-tillation. 7. Method according to claim 5 or 6, wherein the separated C19+ compounds are combined with C20+ residue obtained during the oligomerization. 8. Method according to any of the claims 5 to 7, wherein the aromatic C19+ compounds are transferred to a further device for thermal use thereof, preferably combustion. 9. Method according to any of the preceding claims, wherein the conversion in the conver¬ sion reactor is conducted at ambient temperature. 10. Method according to any of the preceding claims, wherein additional solvent is added to the fraction of C10+ alpha-olefins prior to introduction into the conversion reactor. 11. Method according to any of the preceding claims, wherein the C10+ alpha-olefin fraction is a C10-C18 fraction.

Full Text

METHOD FOR PREPARING LINEAR ALPHA-OLEFINS WITH REMOVAL OF AROMATIC BY-PRODUCTS AND REACTOR SYSTEM THEREFOR
The present invention relates to a method for preparing linear alpha-olefins by oligomerization of ethylene in the presence of an organic solvent and a catalyst.
Methods for the production of linear alpha-olefins by oligomerization of ethylene are widely known in the art. Usually, a catalyst is utilized in that process comprising a zirconium compo¬nent and an organoaluminum component which acts as an activator.
For example, DE 43 38 414 Cl discloses a process for the production of linear alpha-olefins, wherein one reactor is utilized into which a catalyst solution and ethylene are introduced. That process results in a product distribution of linear alpha-olefins having C4-C28 carbon atoms, wherein the fraction of C20+ usually contains waxy, polymeric substances.
The product stream containing alpha-olefins with C4-C28 carbon atoms may be separated into fractions, e.g. by distillation or extraction. One main fraction obtained is a fraction containing C10+ alpha-olefins, preferably C10-C18. This fraction may be often contaminated by aromatic components, preferably C9+ aromatic components which are formed during oligomerization. Of course, these by-products are not desired, as a less valuable fraction C10+ is provided. In the prior art, the aromatic components have been so far removed by repeated extraction and/or distillation, e.g. five distillation columns have been used so far to remove the aromatic components from the C10+ alpha olefin fraction.
It is therefore an object of the present invention to provide a method for preparing linear alpha-olefins which overcomes the drawbacks of the prior art. Especially, a method shall be provided wherein aromatic by-products, commonly present in the C10+ alpha-olefin fraction, can be easily removed with low costs, in order to improve the value of the C10+ alpha-olefin fraction.

This object is achieved in that a product fraction of C10+- alpha-olefins contaminated with aro¬matic C9+ compounds is separated from a product main stream and transferred into a conversion reactor, where C10+ alpha-olefins and aromatic 9+- components are reacted in the presence of a Friedel-Crafts alkylation catalyst to produce aromatic C19+ components.
Preferably, the Friedel-Crafts-alkylation catalyst is selected from any material with sufficient acidity to catalyze the alkylation.
More preferably, the Friedel-Crafts-alkylation catalyst is selected from clay, zeolites, Lewis ac¬ids and protonic acids.
In one preferred embodiment, the Friedel-Crafts-alkylation catalyst is selected from clay, zeolite, H2SO4, P4O10, H3PO4, AlCl3, FeCl3, SbCl5, SnCL,, BF3, TiCl4, and ZnCl2.
The aromatic C19+ compounds prepared may be preferably separated from unreacted C10+ alpha-olefins in or downwards the conversion reactor, preferably by distillation.
Moreover, it is preferred that the separated C19+ compounds are combined with C20+ residue ob-tained during the oligomerization.
The aromatic C19+ compounds may be transferred to a further device for thermal use thereof, preferably combustion.
In one preferred embodiment, the conversion in the conversion reactor is conducted at ambient temperature.
Further preferred, additional solvent is added to the fraction of C10+ alpha-olefins prior to intro-duction into the conversion reactor.

Most preferably, the C10- alpha-olefin fraction is a C10-C18 fraction.
The invention further provides a reactor system for oligomerization of ethylene to form linear alpha-olefins, preferably utilizing a method according to the invention, comprising an oligomeri¬zation reactor and a conversion reactor, wherein a Friedel-Crafts-alkylation catalyst is present in that conversion reactor.
Surprisingly, it was found that the aromatic by-products contained in the C10+- linear alpha-olefin fraction can be easily converted (removed) by reacting the C10+ alpha-olefins with aromatic components, obtained in the oligomerization process, in the presence of a Friedel-Crafts alkyla-tion catalyst in a separate conversion reactor to produce aromatic components having at least C19+. These C19+ aromatic components can be easily separated from the C10- alpha-olefin fraction and can be further processed, for example, combusted. Thus, the separation of the aromatic by¬products is achieved in a very simple method step and safes five distillation columns which have been used so far to separate the aromatic by-products from the alpha-olefins fraction. Therefore, investment and operation costs are decreased, and a value added product (alpha-olefin fraction without by-products) is obtained.
As is obvious for someone skilled in the art, the concept of the present invention may be also adapted to any hydrocarbon streams containing aromatic impurities or by-products. For example, in case of paraffinic streams, olefins have to be added into the paraffinic stream to allow the conversion to heavy aromatic compounds which may be easily separated.
In general, the conversion of linear alpha-olefins (C10+) with aromatic components (C9+) is ac-cording to the following scheme:

(Formula Removed)
wherein R' is any alkyl group having two or more carbon atoms and R is any alkyl group having at least eight carbon atoms, preferably eight to sixteen carbon atoms.
Additional advantages and features of the inventive method and reactor system are further illus¬trated with reference to the accompanying drawing, wherein Fig. 1 illustrates a schematic dia¬gram of the reactor system for carrying out the method according to the present invention.
In Fig. 1 a reactor 1 for the oligomerization of ethylene to prepare linear alpha-olefins is pro¬vided. In the reactor 1 ethylene is oligomerized in the presence of a solvent, preferably toluene, and a suitable catalyst, preferably at a temperature of about 60-100°C. After oligomerization (the reactor is preferably operated continuously), a product stream is removed from the reactor via a discharge line 2. The product stream comprises the solvent, catalyst, liquid linear alpha-olefms and high molecular weight oligomers as well as unreacted dissolved ethylene. The constituents of the product stream may be separated, e.g. in a separation unit 3. For example, the liquid linear alpha-olefms may be separated into several fractions by distillation to obtain fractions of C4-C8, C10-C18 and C20+-. Usually, the fraction of C10-C18 (C10+) comprises aromatic by-products. This fraction may be transferred from the separation unit 3 via line 4 into a conversion reactor 5, op¬tional additional solvent may be provided, wherein the C10+ fraction and the aromatic by-products are reacted in the presence of a Friedel-Crafts-alkylation catalyst. The discharge stream of the conversion reactor 5 may be then further processed, e.g. the aromatic by-products (now C19+) can be separated from the alpha-olefins by distillation and transferred to a further device, e.g. for combustion. The purified C10+ fraction may be utilized for any desired purpose and has added value.

The features disclosed in the foregoing description, in the drawing or in the claims may, both separately and in any combination thereof, be material for realizing the invention in diverse forms thereof.

We Claim:
1. Method for preparing linear alpha-olefins by oligomerization of ethylene in the presence of an organic solvent and an oligomerization catalyst, characterized in that a product frac¬tion of C10+ alpha-olefins contaminated with aromatic C9+ compounds is separated from a product main stream and transferred into a conversion reactor, where C10+ alpha-olefins and aromatic C9+ components are reacted in the presence of a Friedel-Crafts alkylation catalyst to produce aromatic C19+ compounds.
2. Method according to claim 1, wherein the Friedel-Crafts alkylation catalyst is selected from any material with sufficient acidity to catalyze the alkylation.
3. Method according to claim 2, wherein the Friedel-Crafts alkylation catalyst is selected from clay, zeolites, Lewis acids and protonic acids.
4. Method according to claim 3, wherein the Friedel-Crafts alkylation catalyst is selected from clay, zeolite, H2SO4, P4O10, H3PO4, A1C13, FeCl3, SbCl5, SnCl4, BF3, TiCl4 and ZnCl2.
5. Method according to any of the preceding claims, wherein the aromatic C19+ compounds prepared are separated from unreacted C10+ alpha-olefins in or downwards the conversion reactor.
6. Method according to claim 5, wherein the aromatic C19+ compounds are separated by dis-tillation.
7. Method according to claim 5 or 6, wherein the separated C19+ compounds are combined with C20+ residue obtained during the oligomerization.

8. Method according to any of the claims 5 to 7, wherein the aromatic C19+ compounds are
transferred to a further device for thermal use thereof, preferably combustion.
9. Method according to any of the preceding claims, wherein the conversion in the conver¬
sion reactor is conducted at ambient temperature.
10. Method according to any of the preceding claims, wherein additional solvent is added to
the fraction of C10+ alpha-olefins prior to introduction into the conversion reactor.
11. Method according to any of the preceding claims, wherein the C10+ alpha-olefin fraction is a C10-C18 fraction.

Documents:

7701-delnp-2008-Abstract-(27-05-2014).pdf

7701-delnp-2008-Abstract.pdf

7701-delnp-2008-Assignment-(12-09-2013).pdf

7701-delnp-2008-Claims-(29-08-2013).pdf

7701-delnp-2008-Claims.pdf

7701-delnp-2008-Correspondance Others-(04-09-2013).pdf

7701-delnp-2008-Correspondence Others-(11-09-2013).pdf

7701-delnp-2008-Correspondence Others-(12-09-2013).pdf

7701-delnp-2008-Correspondence Others-(27-05-2014).pdf

7701-DELNP-2008-Correspondence-Others-(02-04-2009).pdf

7701-delnp-2008-Correspondence-Others-(29-08-2013).pdf

7701-delnp-2008-Description (Complete).pdf

7701-delnp-2008-Drawings.pdf

7701-delnp-2008-Form-1-(12-09-2013).pdf

7701-DELNP-2008-Form-18 (02-04-2009).pdf

7701-delnp-2008-Form-2-(12-09-2013).pdf

7701-delnp-2008-Form-2-(27-05-2014).pdf

7701-delnp-2008-Form-2-(29-08-2013).pdf

7701-delnp-2008-Form-5-(04-09-2013).pdf

7701-delnp-2008-Form-5-(29-08-2013).pdf

7701-delnp-2008-GPA-(12-09-2013).pdf

7701-delnp-2008-GPA.pdf

7701-delnp-2008-Petition-137-(29-08-2013).pdf

Form-1.pdf

Form-3.pdf

Form-5.pdf

« Previous Patent

Next Patent »

Patent Number

261166

Indian Patent Application Number

7701/DELNP/2008

PG Journal Number

24/2014

Publication Date

13-Jun-2014

Grant Date

09-Jun-2014

Date of Filing

11-Sep-2008

Name of Patentee

SAUDI BASIC INDUSTRIES CORPORATION

Applicant Address

P.O. Box 5101  11422 Riyadh  Saudi Arabia

Inventors:

#	Inventor's Name	Inventor's Address
1	FRITZ, Peter, M.	Truderinger Strasse 21 82008 Unterhaching Germany
2	MÜLLER, Wolfgang	Jasperallee 35 81245 München Garmany
3	WINKLER, Florian	Ziebland Strasse 10 80799 München Garmany
4	BÖLT, Heinz	Schiessstättstrasse 12b 82515 Wolfratshausen Garmany

PCT International Classification Number

C07C 2/08 (2006.01), C07C 7/148 (2006.01

PCT International Application Number

PCT/EP2007/000812

PCT International Filing date

2007-01-31

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	06005686.8	2006-03-21	EPO