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Catalyst for preparing nonene and dodecene by propylene oligomerization, preparation method and application

A catalyst, dodecene technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of low propylene conversion rate, short catalyst life, selectivity low problems, to achieve the effect of high propylene conversion, uniform distribution of active components, and high selectivity

Active Publication Date: 2019-06-04
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The purpose of the present invention is to develop a catalyst with a long service life in order to overcome the shortcomings of the prior art, such as short catalyst life, easy sliming, low conversion rate of propylene, and low selectivity of nonene and dodecene in the product. High strength, good catalytic activity and high selectivity catalyst for propylene oligomerization to prepare nonene and dodecene

Method used

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  • Catalyst for preparing nonene and dodecene by propylene oligomerization, preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] According to the molar ratio of ethyl orthosilicate to water and ethanol as 1:1:1, take 3.6g of water and 9.2g of ethanol into the beaker, add 41.7g of ethyl orthosilicate dropwise at room temperature, and stir for 2 hours; The atomic ratio is 1:8. Take 8.5g of butyl titanate and put it into the above beaker, stir for 20min, and let it stand for 2 days after the end. The prepared Ti-Si glue was stirred at 60° C. for 2 h. by SiO 2 : Water: Ethanol: The molar ratio of ethylene glycol is 1:5:2:0.4, take 18g water, 18.4g ethanol, 5g ethylene glycol, 3.0g phosphotungstomolybdenum heteropoly acid H 3 PW 6 Mo 6 o 40 , after stirring for 2 hours, add it into the Ti-Si glue, continue stirring for 1 hour, pour it into a shallow dish, dry it, and bake it at 550°C for 4 hours. Grinding into powder, adding molding aids, drying at 105°C for 12 hours, and then calcining at 550°C for 4 hours to obtain the desired catalyst. Put the catalyst into the tubular reactor, at a reaction ...

Embodiment 2

[0030] According to the molar ratio of ethyl orthosilicate to water and ethanol as 1:2:2, take 7.2g of water and 18.4g of ethanol into the beaker, add 41.7g of ethyl orthosilicate dropwise at room temperature, and stir for 3h; The atomic ratio is 1:4. Take 17g of butyl titanate and put it into the above beaker, stir for 30min, and let it stand for 1 day after the end. The prepared Ti-Si glue was stirred at 50° C. for 2 h. by SiO 2 : Water: Ethanol: The molar ratio of ethylene glycol is 1:5:2:0.6, take 18g water, 18.4g ethanol, 7.44g ethylene glycol, 2.5g phosphotungstomolybdenum heteropoly acid H 3 PW 6 Mo 6 o 40 , after stirring for 2 hours, add it into the Ti-Si glue, continue stirring for 1 hour, pour it into a shallow dish, dry it, and bake it at 500°C for 3 hours. Grind into powder, add molding aids to shape, dry at 95°C for 12 hours, and then bake at 550°C for 3.5 hours to obtain the desired catalyst. Put the catalyst into the tubular reactor, at a reaction tempera...

Embodiment 3

[0032] According to the molar ratio of ethyl orthosilicate to water and ethanol as 1:2:1, take 7.2g of water and 9.2g of ethanol into the beaker, add 41.7g of ethyl orthosilicate dropwise at room temperature, and stir for 2h; The atomic ratio is 1:6. Take 11.3g of butyl titanate and put it into the above beaker, stir for 1 hour, and let it stand for 2 days after the end. The prepared Ti-Si glue was stirred at 60° C. for 2 h. by SiO 2 : Water: Ethanol: The molar ratio of ethylene glycol is 1:6:3:0.6, take 21.6g water, 27.6g ethanol, 7.44g ethylene glycol, 2.0g phosphotungstomolybdenum heteropoly acid H 6 P 2 W 9 Mo 9 o 62 and 1.5g phosphotungstomolybdenum heteropolyacid H 3 PW 6 Mo 6 o 40 After stirring for 2 hours, add it into the Ti-Si glue, continue to stir for 50 minutes, pour it into a shallow dish, dry it, and bake it at 550°C for 4 hours. Grind into powder, add molding aids to shape, dry at a constant temperature at 105°C for 8 hours, and then calcinate at 550°...

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Abstract

The invention relates to a catalyst for preparing nonene and dodecene through propylene oligomerization and a purpose thereof. The catalyst is characterized in that phosphorus tungsten molybdenum oxide active ingredients are loaded on a TiO2 / SiO2 carrier by an in-situ sol-gel method. The catalyst is used for preparing the nonene and dodecene through propylene oligomerization. Under the conditions that the reaction temperature is 200 to 300 DEG C, the reaction pressure is 1.5 to 3.5MPa, the feeding air speed is 2000 to 5500 h<-1> and the activated water mass percentage is 0.8 percent to 1.2 percent, the conversion rate of propylene is greater than or equal to 90 percent; the selectivity of nonene is greater than or equal to 64 percent; the selectivity of the dodecene is greater than or equal to 23 percent. The catalyst provided by the invention is used for the propylene oligomerization, and has the advantages of high catalysis activity, low reaction temperature and low pressure. Experiments prove that the service life of the catalyst is more than three years; the requirements of long period operation of industry can be met; the total selectivity is high.

Description

technical field [0001] The invention belongs to the field of olefin oligomerization technology and catalyst preparation. Background technique [0002] The production of nonene and dodecene is a typical example of olefin oligomerization to prepare trimers and tetramers. Most of them use propylene as a raw material, and use acidic catalysts for oligomerization reactions to obtain propylene oligomerization products. It is characterized by relatively simple process and mature technology. The main difference between various propylene oligomerization processes lies in the different catalysts used. According to relevant literature reports, so far, most of the industrial catalysts for preparing trimers and tetramers from propylene still use phosphoric acid series catalysts. [0003] The biggest advantage of the solid phosphoric acid catalyst is that phosphoric acid can be relatively firmly adsorbed on the surface of diatomite, and the acid is not easy to lose. The catalyst is used...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/19B01J31/38C07C2/18C07C11/02
CPCY02P20/52
Inventor 李为民吴海成孙佳华金天
Owner CHANGZHOU UNIV