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Three-way catalyst system and application thereof in ethylene oligomerization reaction

A three-way catalyst and catalyst technology, applied in catalytic reactions, catalysts, carbon compound catalysts, etc., can solve the problems of adsorbing catalyst components, affecting air tightness, affecting mass transfer, etc., to reduce the generation of high polymers, improve Wall-hanging slurry, the effect of improving selectivity

Active Publication Date: 2021-06-08
WANHUA CHEM GRP CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Polymer hanging on the wall will not only affect the mass transfer, but also adsorb the catalyst components, which will further cause by-products, produce more polymers, and affect the continuous reaction
Solvent immersion, temperature-rising washing and mechanical cleaning are generally used to clean polymer walls; among them, solvent immersion and temperature-rising washing take a long time, and consume a large amount of solvent, thereby increasing costs; and mechanical cleaning requires dismantling of the reactor, which affects Airtightness, which in turn reduces reactivity, leads to waste of a lot of raw materials and increases costs

Method used

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  • Three-way catalyst system and application thereof in ethylene oligomerization reaction
  • Three-way catalyst system and application thereof in ethylene oligomerization reaction
  • Three-way catalyst system and application thereof in ethylene oligomerization reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0061] The preparation method of phosphine-nitrogen ligand (L1):

[0062] Pyrrole (2.25mol) was dissolved in 180ml (2.80mol) of dichloromethane solution to obtain a reaction solution;

[0063] At -78°C, 1.5 mol of n-butyllithium was added dropwise to the reaction solution under stirring, and the compound (dichlorodimethylsilane 1 mol) and 8 mL (0.11 mol) of trifluoroacetic acid were continuously added to it. , slowly warming up to room temperature and reacting for 50h to obtain reaction solution 1;

[0064] The reaction liquid 1 was filtered, and the compound represented by the structure of formula III (1.25 mol of diphenylphosphine chloride) was added to the obtained filtrate at -78°C, and the reaction liquid was slowly raised to room temperature to obtain the reaction liquid 2;

[0065] The reaction solution 2 was purified by column chromatography (washed with tetrahydrofuran, and the aspect ratio was 2), and then recrystallized at 80° C. to obtain the ligand (L1).

[0066...

Embodiment 2

[0069] The difference between the preparation method of the phosphine-nitrogen ligand (L2) and the phosphine-nitrogen ligand (L1) in Example 1 is that the compound represented by the structure of formula III added is 2-fluorodiphenylphosphine chloride.

[0070]

[0071] The NMR data of the above-mentioned ligand (L2) are as follows: 1H NMR (400MHz, CDCl3): 7.24-7.44 (m, 20H), 6.25-6.34 (m, 4H), 0.14 (s, 6H).

Embodiment 3

[0073] The difference between the preparation method of the phosphine-nitrogen ligand (L3) and the phosphine-nitrogen ligand (L1) in Example 1 is that the compound represented by the structure of formula III added is 3-fluorodiphenylphosphine chloride.

[0074]

[0075] The NMR data of the above-mentioned ligand (L3) are as follows: 1H NMR (400MHz, CDCl3): 7.24-7.44 (m, 20H), 6.25-6.34 (m, 4H), 0.14 (s, 6H).

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Abstract

The invention provides a three-way catalyst system and application thereof in ethylene oligomerization. The three-way catalyst system is obtained by complexing raw materials mainly comprising a phosphine-nitrogen ligand with a structure as shown in a formula I which is described in the specification, a metal precursor taking chromium as a center and a cocatalyst, wherein a molar ratio of the metal precursor to the phosphine-nitrogen ligand as shown in the formula I to the cocatalyst is 1: (0.1-10): (1-1000), preferably 1: (1-1.6): (400-600). When an obtained three-way catalyst system is applied to an ethylene oligomerization reaction, selectivity of alpha-olefin in an ethylene oligomerization reaction process is improved, so the selectivity sum of 1-hexene and 1-octylene in the oligomerization reaction reaches 82% or above.

Description

technical field [0001] The invention belongs to the technical field of ethylene oligomerization, and in particular relates to a three-way catalyst system and its application in the ethylene oligomerization process. Background technique [0002] α-Olefin is an important petrochemical raw material, widely used in synthetic lubricants, emulsifiers, leather treatment agents, rust inhibitors, fabric finishing agents, paper chemicals, etc. Especially 1-hexene and 1-octene have the greatest demand. As a comonomer of ethylene, 1-hexene can significantly improve the impact and tear resistance of polyethylene, and 1-octene can be used to produce polyolefin elastomers . The preparation of α-olefins by ethylene oligomerization is the most commonly used production method in industry. [0003] At present, the biggest problem facing the industrial continuous production of ethylene tetramerization technology is the wall-hanging kettle for polymers. Polymer hanging on the wall will not on...

Claims

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Application Information

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IPC IPC(8): B01J31/18B01J31/22C07C2/32C07C11/02C07C11/107C07F9/572
CPCB01J31/188B01J31/143B01J31/2234C07C2/32C07F9/572B01J2231/20B01J2531/62C07C2531/18C07C11/107C07C11/02Y02P20/52
Inventor 陈冠良刘帮明郭华黄玲燕张田财林小杰王金强张彦雨
Owner WANHUA CHEM GRP CO LTD
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