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Application of Nickel Metal Organic Framework Catalyst in Dimerization of Ethylene to Produce 1-Butene

A technology of metal-organic frameworks and catalysts, applied in the direction of organic compound/hydride/coordination complex catalysts, organic chemistry, physical/chemical process catalysts, etc., can solve the problem of high pressure requirements for ethylene, and achieve cheap raw materials and advanced technology Simple, easy-to-composite effects

Active Publication Date: 2022-07-29
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the catalyst uses a large amount of cocatalyst, and the pressure requirement for the reactant ethylene is also high

Method used

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  • Application of Nickel Metal Organic Framework Catalyst in Dimerization of Ethylene to Produce 1-Butene
  • Application of Nickel Metal Organic Framework Catalyst in Dimerization of Ethylene to Produce 1-Butene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 11D

[0044] Example 1 Synthesis and use of 1D Ni-MIL-77 catalyst

[0045] (1) The synthesis method of 1D Ni-MIL-77 material is as follows: 0.004mol Ni(NO 3 ) 2 ·6H 2 O, 0.006mol glutaric acid and 0.008mol KOH were dissolved in 44ml of mixed solvent with a volume ratio of ethanol and water of 1:1. After fully stirring, the mixed solution was dispersed in 0.4mol / L lye solution, and the stirring was continued for 30min. Transfer to a hydrothermal kettle, react at 180°C and autogenous pressure for 48 hours, then take out the reactor and cool to room temperature naturally, the obtained product is collected by centrifugation, washed repeatedly with ethanol and deionized water, and dried at room temperature to obtain 1DNi-MIL-77.

[0046] (2) The catalyst solution was prepared as follows: the obtained 1D Ni-MIL-77 was put into a mortar and ground into powder, 0.03 g was weighed and put into a Shrek bottle, vacuum-N 2 Replace three times and save for future use. At the same time, put 3...

Embodiment 2

[0048] Example 2 Synthesis and use of 3D Ni-MIL-77 catalyst

[0049] (1) The synthesis method of 3DNi-MIL-77 material is as follows: 0.03mol glutaric acid, 0.02mol NiCl 2 ·6H 2 O and 0.04mol KOH were dissolved in 22ml of a mixed solvent with a volume ratio of ethanol and water of 1:1 (the molar ratio of each reactant was 1.5:1:2:60), fully stirred to dissolve, and the mixed solution was transferred to water The reaction was carried out at 180 °C and autogenous pressure for 48 hours in a hot kettle, and then the reaction kettle was taken out and cooled to room temperature naturally. The obtained product was collected by centrifugation, washed with deionized water until neutral, and dried at room temperature to obtain 3DNi-MIL-77.

[0050] (2) The catalyst solution was prepared as follows: the obtained 3D Ni-MIL-77 was put into a mortar and ground into powder, 0.03 g was weighed and put into a Shrek bottle, activated under vacuum at 150°C for 12 h, taken out and vacuum-N 2 Rep...

Embodiment 3

[0052] Example 3 Influence of the amount of cocatalyst on the effect of 1D Ni-MIL-77 catalyzed by ethylene oligomerization

[0053] The difference between this example and Example 1 is that when 1D Ni-MIL-77 catalyst is used in the ethylene oligomerization reaction, the amount of cocatalyst MAO is changed, that is, 3400 μl MAO solution ( Al:Ni=100). The reaction results are shown in Table 1.

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Abstract

The invention relates to the application of a nickel metal organic framework catalyst in the production of 1-butene by ethylene dimerization. Among them, nickel metal organic framework catalysts include 1D Ni‑MIL‑77 and 3D Ni‑MIL‑77, which can be obtained by one-step hydrothermal synthesis with low cost. The hydrothermally synthesized 1D Ni-MIL-77 and 3D Ni-MIL-77 do not need post-modification and can be directly used as catalysts to catalyze ethylene oligomerization under the action of co-catalysts to obtain higher ethylene oligomers. Polymerization activity and 1-butene selectivity. The catalyst of the present invention can be recycled and reused. Butene selectivity above 99% and 1‑C 4 The selectivities are all above 85.0%, and in the range of normal reactivity, 1‑C 4 The highest selectivity can reach 99.0%.

Description

technical field [0001] The invention belongs to the field of petrochemical industry, and relates to the application of a nickel metal organic framework catalyst in the oligomerization of ethylene to produce alpha-olefin. Background technique [0002] Ethylene is one of the most produced chemicals in the world today. A variety of industrial synthesis reactions can be carried out with ethylene as a raw material, and many important chemical products can be obtained. Among them, the production process of preparing linear α-olefins by oligomerization has received extensive attention. Nickel-based catalysts are widely used in ethylene oligomerization because of their relatively cheap and readily available raw materials and relatively mild reaction conditions, such as the application of nickel-based catalysts in SHOP process (Mason R.F., 1972, US3676523). The SHOP process is a non-selective oligomerization process, and the α-olefin product conforms to the S-F distribution (C 4 -...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C2/42C07C11/08B01J31/22
CPCC07C2/42B01J31/1691B01J31/223B01J2531/847C07C11/08
Inventor 李钢王聪郭洪臣
Owner DALIAN UNIV OF TECH
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