Ethylene oligomerization catalyst and preparation method

An ethylene oligomerization and catalyst technology, applied in the field of ethylene oligomerization catalyst and preparation, can solve the problems of excessive C activity, decrease, and low carbon olefins, etc., and achieve the effects of high oligomerization reaction activity, high yield and low content

Active Publication Date: 2010-09-01
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

USP4886933 uses two kinds of alkylaluminum compounds as cocatalysts to carry out ethylene oligomerization to prepare α-olefins. USP4783573 adds a third component on this basis to carry out ethylene oligomerization. The third component is one or more Lewis bases, such as Thiophene, methyl disulfide, thiourea, triphenylphosphine or trioctylphosphine to achieve the purpose of improving the thermal stability of the catalyst itself and improving product distribution, but there are still many deficiencies, such as low carbon olefins in the product Many, most notably C 4 Excessive or decreased activity, etc.

Method used

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preparation example Construction

[0027] The preparation method of the catalyst provided by the present invention comprises the steps of stirring evenly in zirconium tetrachloride suspension aromatic hydrocarbon, adding butanol to fully react, cooling down to -5-5°C and adding SiCl x R 4-x Fully reacted silicon-containing compounds, SiCl x R 4-x In, R is C 1 ~C 4 Alkyl or C 6 ~C 8 The aryl group, x is an integer of 1-4.

[0028] The butanol described in the above method is preferably n-butanol.

[0029] The molar ratio of butanol and zirconium tetrachloride added in catalyst preparation is 3-9:1, preferably 3-6:1, and the reaction temperature of zirconium tetrachloride and butanol is 60-120°C, preferably 70-100°C .

[0030] After the reaction of zirconium tetrachloride and alcohol, SiCl added during silicon modification x R 4-x The molar ratio with zirconium tetrachloride is 0.1~18:1, preferably 6~12:1, SiCl x R 4-x The reaction temperature with butanol is -5 to 5°C, preferably 0 to 5°C.

[0031] ...

example 1

[0038] Preparation of the oligomerization catalysts described in the present invention.

[0039] Suspend 10mmol of zirconium tetrachloride in 26g of toluene, stir at 70°C for 1 hour, add 30mmol of n-butanol, reflux at 85°C for 4 hours, cool down to 0°C, add 80mmol of silicon tetrachloride for 4.0 hours, add 7.0 g of toluene to obtain the oligomerization catalyst solution A that the zirconium concentration is 0.2 mol / liter, by quantitatively analyzing the HCl generated, the mol ratio of each component is recorded as follows:

[0040] Zr(On-Bu)Cl 3 : 2.0 SiCl 3 (On-Bu): 6.0SiCl 4

example 2

[0042] Preparation of the oligomerization catalysts described in the present invention.

[0043] Suspend 2.33g (10mmol) of zirconium tetrachloride in 34.6g of toluene, stir at 70°C for 1 hour, add 40mmol of n-butanol, reflux at 100°C for 4 hours, cool to 0°C, add 0.8mmol of tetrachloride Silicon was reacted for 3.0 hours, and 5.45 g of toluene was added to obtain an oligomerization catalyst solution B with a zirconium concentration of 0.2 mol / liter. By quantitatively analyzing the generated HCl, the molar ratio of each component was recorded as follows:

[0044] Zr(On-Bu)Cl 3 : 0.8SiCl 3 (On-Bu): 2.2 (n-BuOH)

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Abstract

The invention provides an ethylene oligomerization catalyst, which comprises Zr(OBu)Cl3, SiClx-1R4-x(OBu), BuOH and SiClxR4-x in a mole ratio of 1:(0.5-5.0):(0-5.0):(0-20), wherein Bu is butyl; R is alkyl of C1 to C4 or aryl of C6 to C8; and x is an integer from 1 to 4. The catalyst has high reaction activity in an ethylene oligomerization reaction, a plurality of long chain hydrocarbons of C12 to C20 exist in an oligomerization product and the yield of alpha-olefin is high.

Description

technical field [0001] The invention relates to an ethylene oligomerization catalyst and a preparation method thereof, in particular to a halogenated alkoxy zirconium catalyst and a preparation method thereof. Background technique [0002] Olefin oligomerization is an important part of olefin polymerization. With the expansion of demand for specific products in modern production and life, the rise of oligomerization is triggered. In particular ethylene oligomerization is used to prepare higher chain olefins. [0003] Traditional and well-known ethylene oligomerization processes, such as Gulf, Ethyl, SHOP, etc., have been widely imitated and learned. However, these traditional processes have problems such as harsh operating conditions, low single-pass catalyst activity, wide carbon number distribution of products, difficult separation of products and raw materials, and difficult disposal of waste liquid. In particular, the operating pressure is too high, reaching about 20 MP...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/12B01J31/02C07C2/26
Inventor 倪静荣峻峰景振华宗明生
Owner CHINA PETROLEUM & CHEM CORP
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