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Process for producing linear alpha olefins

A straight-chain, metal salt technology, applied in chemical instruments and methods, hydrocarbons, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as no disclosure of straight-chain alpha-olefins

Inactive Publication Date: 2006-08-16
SHELL INT RES MAATSCHAPPIJ BV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

There is no disclosure in this document about the preparation of linear alpha-olefins using a catalyst system in which bis-imine pyridine iron complexes are prepared in situ

Method used

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  • Process for producing linear alpha olefins
  • Process for producing linear alpha olefins
  • Process for producing linear alpha olefins

Examples

Experimental program
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preparation example Construction

[0110] The molar ratio of water to aluminum compound in the preparation of aluminoxane is preferably in the range of 0.01:1 to 2.0:1, more preferably 0.02:1 to 1.2:1, even more preferably 0.4:1 to 1:1, especially 0.5 : 1.

[0111] When preparing the catalyst system here in situ, it is preferred to use cocatalysts and metal salts in amounts such that the Al / Fe or Al / Co atomic ratio is in the range 0.1-106, preferably 10-10 5 , and more preferably 10 2 -10 4 . It is also preferred that the molar ratio of bisaryl imine pyridine ligand / Fe or bis aryl imine pyridine ligand / Co is in the range of 10 -4 -10 4 , preferably 10 -1 -10, more preferably 0.5-2, and especially 1.2.

[0112] Further optional components may be added to the catalyst system herein, such as Lewis acids and bases, such as those described in WO02 / 28805.

[0113] Oligomerization

[0114] The catalyst component is usually used in the oligomerization reaction mixture in such an amount that it contains 10 per m...

Embodiment 1-10

[0164] Oligomerization experiments 1-10 were performed in a 0.5 liter stainless steel reactor. Under an inert atmosphere, the reactor was purged at 70 °C for at least 30 minutes using 0.15 g MMAO and 125 ml anhydrous heptane. After draining the contents, 125 ml of anhydrous heptane and the indicated cocatalyst were added to the reactor, followed by adding the indicated ligand (ligand A) and Fe(2,4-pentanedi keto acid) 3 (Fe added = 0.25 μmol; Ligand / Fe molar ratio = 1.2 + / - 0.1; Al / Fe molar ratio = 700 + / - 50 unless otherwise stated), pressurized to 16 bar with ethylene (a) . Systematic additions (4ml in toluene) to the reactor were made by injection each time, followed by rinsing the system with 2 x 4ml toluene. After 2 additions of catalyst components, the total solvent content in the reactor = about 150 ml heptane / toluene = 8 / 2 (wt / wt). After the initial exotherm, the reactor was brought to 70°C as rapidly as possible while monitoring temperature, pressure and ethylene ...

Embodiment 11-19

[0166] Examples 11-19 were carried out in a 1 liter reactor using isooctane as the reactor solvent, catalyst component solvent, rinse and solvent used to prepare the aluminoxanes. Fe(2,4-Pentedionate) 3 and the amount of solvent used was twice that of the experiments carried out in Examples 1-10 described above. Thus Fe added = 0.5 μmol; total solvent content in the reactor = about 310 ml isooctane after 2 additions of catalyst components. The ligand / Fe molar ratio was the same as in Examples 1-10. Al / Fe molar ratio = 700 + / - 50 unless otherwise stated. In Example 14, the cocatalyst and ligand / Fe(2,4-pentanedione acid) were reversed 3 order of addition.

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Abstract

A process for the production of alpha-olefins comprising reacting ethylene under oligomerisation conditions in the presence of a mixture comprise ng: (a) a metal salt based on Fe (II), Fe (III), Co (II) or Co(III); (b) a pyridine bis-imine ligand; and (c) a co-catalyst which is the reaction product of water with one or more organometallic aluminium compounds, wherein the one or more organometallic aluminium compounds is selected from: (i) ssdelta-branched compounds of Formula (I): Al (CH2,-CR<1>R 2 -CH2,-CR<4>R<5>R<6>) XR<3>YHZ; (ii) ssgamma-branched compounds of Formula (II) Al (CH2-CR<1>R <2> -CR<4>R<5>R<6>) XR<3>YHZ and mixtures thereof; wherein when the metal salt and the bis-arylimine pyridine ligand are mixed together they are soluble in aliphatic or aromatic hydrocarbon solvent.

Description

technical field [0001] The present invention relates to a process for the production of linear alpha-olefins by oligomerization of ethylene and a catalyst system for use in said process. Background technique [0002] Various methods are known for the production of higher linear α-olefins (for example D. Vogt, Oligomerisation of ethylene to higher α-olefins in Applied Homogeneous Catalysis with Organometallic Compounds, Ed.B. Cornils, W.A. Herrmann, 2nd Edition, Vol.1, Ch.2.3.1.3, pp.240-253, Wiley-VCH 2002). These commercial processes provide Poisson or Schulz-Flory type oligomer product distributions. [0003] To obtain a Poisson distribution, no chain termination must occur during oligomerization. But in contrast, in the Schulz-Flory method, chain termination does occur and is independent of chain length. The Ni-catalyzed ethylene oligomerization step of the Shell Higher Olefins Process (SHOP) is a typical example of the Schulz-Flory process. [0004] In the Schulz-Flo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/32C08F10/02C08F4/70B01J31/12B01J31/14B01J31/18C08F10/00
CPCB01J2231/20B01J2531/845C07C2531/14B01J31/143C07C2/32B01J31/1815C08F10/00B01J2531/842C08F4/7042
Inventor E·J·M·德博尔H·范德海登E·克拉格特维基克Q·A·昂J·P·什米特A·范佐恩
Owner SHELL INT RES MAATSCHAPPIJ BV
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