Preparation method for 1-heptene

Abstract

The invention relates to a preparation method for 1-heptene. The method comprises a step of contacting ethylene and internal olefin for a cross metathesis reaction in the presence of a catalyst so as to obtain 1-heptene. The catalyst is composed of a compound as shown in a formula (I) and / or a compound as shown in a formula (II). The method has high selectivity and a high conversion rate; with the method, the catalyst shows high activity at a low temperature in a short period of time. The method has the advantages of simpleness, easy operation, controllable reaction conditions and low energy consumption.

Description

technical field

[0001] The invention relates to a method for preparing 1-heptene, in particular to a method for preparing 1-heptene by cross-metathesis reaction between ethylene and internal olefins. Background technique

[0002] α-Olefins are important organic chemical raw materials. Its application fields are very wide, mainly used in chemical products such as synthetic lubricating oil base oils, comonomers, surfactants, plasticizers, fungicides, and emulsifiers. Because α-olefins have great market development potential, some major producers at home and abroad are constantly expanding their production capacity.

[0003] At present, the methods for producing α-olefins mainly include paraffin cracking method, extraction and mixed C4 separation method, ethylene oligomerization method, primary alcohol dehydration method, olefin metathesis method, etc. A method for producing olefins based on a metathesis reaction, such as Chinese patent CN101048356A, discloses a method for th...

Examples

Embodiment 1

[0030] In the glove box under inert atmosphere, according to the molar ratio of 2-octene and ruthenium catalyst is 4500:1, the 2-octene of 4.26ml is dissolved in the toluene of 26ml, 5mg ruthenium catalyst A (catalyst 1 is formula I The catalyst of the structure, wherein R is H, M is metal ruthenium, L 1 is chlorine, L 2 It is tricyclohexylphosphine, m and n are both 2) dissolved in 20ml of toluene, respectively added to two glass syringes, sealed and taken out from the glove box. The reaction device adopts a 100ml autoclave reaction device. Heat the autoclave to 30°C, vacuumize and replace it with ethylene several times, open the vent valve, then quickly add 2-octene into the reaction kettle, and then add the ruthenium catalyst into the reaction kettle. Then close the vent valve, pre-mix and stir for 2 minutes, set the pressure at 0.5 MPa, feed ethylene into it for reaction, and the reaction time is 0.5 h. After the reaction is completed, the liquid phase product is collec...

Embodiment 2

[0032] The experimental method is the same as in Example 1, the reaction temperature is changed to 40°C, and the remaining experimental conditions are unchanged. The test reaction results are as follows: 1-heptene yield: 91.3%, 2-octene conversion rate: 76.5%, selectivity: 80.1 %, catalyst activity: 8.61×10 5 g / mol·Ru·h. Please refer to Table 1 for details.

Embodiment 3

[0034] The experimental method is the same as in Example 1, the reaction time is changed to 10min, and all the other experimental conditions are unchanged. The test reaction results are as follows: 1-heptene yield: 81.7%, 2-octene conversion rate: 44.9%, selectivity: 71.5% , catalyst activity: 4.66×10 5 g / mol·Ru·h. Please refer to Table 1 for details.

technical field

[0001] The invention relates to a method for preparing 1-heptene, in particular to a method for preparing 1-heptene by cross-metathesis reaction between ethylene and internal olefins. Background technique

[0002] α-Olefins are important organic chemical raw materials. Its application fields are very wide, mainly used in chemical products such as synthetic lubricating oil base oils, comonomers, surfactants, plasticizers, fungicides, and emulsifiers. Because α-olefins have great market development potential, some major producers at home and abroad are constantly expanding their production capacity.

[0003] At present, the methods for producing α-olefins mainly include paraffin cracking method, extraction and mixed C4 separation method, ethylene oligomerization method, primary alcohol dehydration method, olefin metathesis method, etc. A method for producing olefins based on a metathesis reaction, such as Chinese patent CN101048356A, discloses a method for th...

Examples

Embodiment 1

[0030] In the glove box under inert atmosphere, according to the molar ratio of 2-octene and ruthenium catalyst is 4500:1, the 2-octene of 4.26ml is dissolved in the toluene of 26ml, 5mg ruthenium catalyst A (catalyst 1 is formula I The catalyst of the structure, wherein R is H, M is metal ruthenium, L 1 is chlorine, L 2 It is tricyclohexylphosphine, m and n are both 2) dissolved in 20ml of toluene, respectively added to two glass syringes, sealed and taken out from the glove box. The reaction device adopts a 100ml autoclave reaction device. Heat the autoclave to 30°C, vacuumize and replace it with ethylene several times, open the vent valve, then quickly add 2-octene into the reaction kettle, and then add the ruthenium catalyst into the reaction kettle. Then close the vent valve, pre-mix and stir for 2 minutes, set the pressure at 0.5 MPa, feed ethylene into it for reaction, and the reaction time is 0.5 h. After the reaction is completed, the liquid phase product is collec...

Embodiment 2

[0032] The experimental method is the same as in Example 1, the reaction temperature is changed to 40°C, and the remaining experimental conditions are unchanged. The test reaction results are as follows: 1-heptene yield: 91.3%, 2-octene conversion rate: 76.5%, selectivity: 80.1 %, catalyst activity: 8.61×10 5 g / mol·Ru·h. Please refer to Table 1 for details.

Embodiment 3

[0034] The experimental method is the same as in Example 1, the reaction time is changed to 10min, and all the other experimental conditions are unchanged. The test reaction results are as follows: 1-heptene yield: 81.7%, 2-octene conversion rate: 44.9%, selectivity: 71.5% , catalyst activity: 4.66×10 5 g / mol·Ru·h. Please refer to Table 1 for details.

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