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Ethylene oligomerization catalyst, preparation method and application thereof

An ethylene oligomerization and catalyst technology is applied in the field of homogeneous zirconium catalyst and its preparation, which can solve the problems of clogging pipelines and affecting industrial production, and achieve the effects of avoiding the formation of high polymers, rational distribution and high yield

Active Publication Date: 2019-01-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the aforementioned documents have improved the zirconium-based ethylene oligomerization catalysts, there is still room for improvement in terms of the yield of C6-C20 and the yield of α-olefins
[0005] In addition, zirconium-based ethylene oligomerization catalysts generally lead to the formation of high polymers—high polymers will block pipelines during the oligomerization process and seriously affect industrial production—the aforementioned literature does not mention this aspect

Method used

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  • Ethylene oligomerization catalyst, preparation method and application thereof

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preparation example Construction

[0036] The present invention provides a preferred preparation method of the ethylene oligomerization catalyst, the method comprising:

[0037] (1) In an inert solvent, ZrX 4 reacting with 1,3-dichloro-2-propanol to prepare a solution; and

[0038] (2) the solution obtained in step (1) and the general formula are SiCl n R 4-n The silicon compound reaction, thus makes the step of described catalyst;

[0039] Wherein, X is Cl, Br, or I, n is 0, 1, 2, 3 or 4, and R is a hydrocarbon group.

[0040] In the present invention, the inert solvent refers to a solvent that is harmless to the catalytic performance of the ethylene oligomerization catalyst and the ethylene oligomerization reaction.

[0041] According to the present invention, in step (1), the inert solvent is preferably benzene, toluene, xylene, trimethylbenzene, n-hexane or cyclohexane, and any mixture thereof.

[0042] In the preparation method, the raw materials used and their mutual ratios are the same as the corres...

Embodiment 1

[0059] This example illustrates the preparation method of the ethylene oligomerization catalyst of the present invention.

[0060] 2.33g (10mmol) ZrCl 4 Place in a three-necked flask, add 30 mL of toluene, heat to 70°C, reflux and stir for 1 hour, add 2.85 mL (30 mmol) of 1,3-dichloro-2-propanol dropwise, continue to reflux for 4 hours, cool down, and place in an ice-water bath 3.82mL (30mmol) trimethylchlorosilane was added dropwise under the condition, reacted for 4 hours, and toluene was added until the solution was 50mL to obtain an oligomerization catalyst solution A with a zirconium concentration of 0.2 mol / liter.

Embodiment 2

[0068] This example illustrates the preparation method of the ethylene oligomerization catalyst of the present invention.

[0069] The same method as in Example 1 was adopted, except that the amount of 1,3-dichloro-2-propanol was 8.7 mL (90 mmol) to prepare catalyst solution D.

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Abstract

The invention relates to an ethylene oligomerization catalyst, a preparation method and application thereof. Specifically, the catalyst is prepared by reaction of ZrX4, 1, 3-dichloro-2-propanol and asilicon compound with a general formula of SiClnR4-n. The catalyst provided by the invention can improve the product distribution of oligomerization product and increase the yield of alpha-olefin.

Description

technical field [0001] The invention relates to an ethylene oligomerization catalyst as well as its preparation method and application. Specifically, the present invention relates to a homogeneous zirconium catalyst for ethylene oligomerization to produce linear α-olefins, its preparation method and application. Background technique [0002] It is customary in the industry to refer to terminal olefins above C4 (double bonds at the end of the molecular chain) as α-olefins. As an industrial product, α-olefins have a wide range of carbon numbers (C4-C40), and straight-chain α-olefins with carbon numbers ranging from C6 to C20 are widely used. [0003] Olefin oligomerization is the main way to produce α-olefins. At present, the relatively mature processes include Gulf method, Ethyl method and SHOP method. The catalysts used in these three processes are alkyl aluminum or nickel compounds. The reaction conditions are relatively harsh, and the pressure can generally be up to tens...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/00C07F7/12B01J31/12B01J31/14C07C2/26C07C11/02C07C11/08C07C11/107
CPCB01J31/12B01J31/128B01J31/143B01J2231/20C07C2/26C07F7/121C07C11/02C07C11/08C07C11/107Y02P20/52
Inventor 荣峻峰宗明生
Owner CHINA PETROLEUM & CHEM CORP