Method for in-situ bridging packaging of heteropoly acid ionic liquid by Zr-based MOFs

A technology of ionic liquids and heteropolyacids, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, hydrocarbon oil treatment, etc. Catalytic activity and other issues, to achieve the effect of good effect, excellent catalytic performance and reusable performance

Active Publication Date: 2020-02-28
FUZHOU UNIV
View PDF3 Cites 6 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Heteropolyacids are a class of oxygen-containing polyacids composed of heteroatoms and polyatoms in a certain structure through the coordination bridge of oxygen atoms. They have high catalytic activity and are commonly used as solid acid catalysts. However, they are relatively Low specific surface area, easily soluble in organic solvents and difficult to recover have always affected its application prospects in oxidative desulfurization
However, the catalytic activity of the composites prepared by this method is not significantly improved compared with heteropolyacids, and the reusability is poor, mainly because heteropolyacids are not uniformly dispersed in the pores of MOFs and are easy to push, thereby blocking the pores. affect its catalytic activity
In addition, heteropolyacids immobilized on MOFs by physical adsorption are easy to leach out when encountering organic solvents, which is the main reason for their poor reusability.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for in-situ bridging packaging of heteropoly acid ionic liquid by Zr-based MOFs
  • Method for in-situ bridging packaging of heteropoly acid ionic liquid by Zr-based MOFs
  • Method for in-situ bridging packaging of heteropoly acid ionic liquid by Zr-based MOFs

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] (1) [mim(CH 2 ) 3 COOH] 3 Preparation of PWs

[0026] Accurately weigh 0.01 mol of methyl 4-bromobutyrate in a 25 mL round bottom flask, add 0.01 mol of 1-methylimidazole (molar ratio 1:1) dropwise under magnetic stirring, and reflux at 80 °C After 48 h, a light yellow viscous substance was obtained, which was cooled to room temperature, washed with ether (10 mL×3), and dried in vacuo. The resulting product was added dropwise with 0.01 mol HCl (40% aqueous solution) under magnetic stirring. Acidify, reflux at 80°C for 30 min, cool to room temperature, wash with ether (10 mL×3), and dry in vacuo to obtain 1-carboxypropyl-3-methylimidazolium chloride ([mim(CH 2 ) 3 COOH]Cl). [mim(CH 2 ) 3 Dissolve COOH]Cl in 50 mL deionized water to make solution A, then weigh 0.002 mol of phosphotungstic acid (HPW) and dissolve it in 40 mL deionized water to make solution B, add solution A to solution B dropwise , stirred at room temperature for 12 h, filtered and washed, the res...

Embodiment 2

[0034] Taking dibenzothiophene as the target sulfide, it was dissolved in n-octane to prepare simulated gasoline with a concentration of 1000 ppmS. Take 5 mL of the above simulated gasoline, 0.04 g [mim(CH 2 ) 3 COOH] 3 PW@UiO-66 and 5 mL of acetonitrile were added to a 25 mL round bottom flask, stirred at room temperature for 10 min, and then 0.106 g of H 2 o 2 (30% aqueous solution), reacted at 60 °C for 2 h, cooled to room temperature, and analyzed the upper oil phase by gas chromatography to detect the content of dibenzothiophene. It was determined that under the above reaction conditions, [mim(CH 2 ) 3 COOH] 3 The oxidation removal rate of PW@UiO-66 for dibenzothiophene can reach 100%.

Embodiment 3

[0036] Taking benzothiophene as the target sulfide, it was dissolved in n-octane to prepare simulated gasoline with a concentration of 1000 ppmS. Take 5 mL of the above simulated gasoline, 0.04 g [mim(CH 2 ) 3 COOH] 3 PW@UiO-66 and 5 mL of acetonitrile were added to a 25 mL round bottom flask, stirred at room temperature for 10 min, and then 0.106 g of H 2 o 2 (30% aqueous solution), reacted at 60 °C for 2 h, cooled to room temperature, and analyzed the upper oil phase by gas chromatography to detect the content of benzothiophene. It was determined that under the above reaction conditions, [mim(CH 2 ) 3 COOH] 3 The oxidation removal rate of PW@UiO-66 for thiophene can reach 95.3%.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention provides a method for in-situ bridging packaging of heteropolyacid ionic liquid by Zr-based MOFs, and belongs to the technical field of composite materials. According to the method, heteropolyacid is immobilized into pore channels of the Zr-based MOFs in an in-situ synthesis manner by utilizing a bridging effect of carboxyl functionalized ionic liquid (positive ions of the ionic liquid can be combined with deprotonated heteropolyacid to form new ionic liquid, and carboxyl groups of the ionic liquid can be coordinated and combined with metal clusters of the MOFs). According to thenovel heteropolyacid immobilization method, the problem that the immobilized heteropolyacid is easy to leach out can be well solved. Moreover, the immobilization method has very strong universality and can be suitable for various heteropolyacids and MOFs taking carboxyl as a coordination group. A Zr-based MOFs in-situ bridging encapsulated heteropolyacid solid catalyst prepared by the invention shows excellent catalytic performance and reusability in a reaction of oxidative removal of thiophene compounds in simulated gasoline.

Description

technical field [0001] The invention belongs to the technical field of composite material synthesis, and in particular relates to a preparation method of a Zr-based MOFs in-situ bridging and encapsulating heteropolyacid ionic liquid composite catalyst. Background technique [0002] Realizing the effective removal of sulfur compounds in oil has always been the focus of research in the field of petroleum refining and chemical industry, and is the key to improving the quality of oil products. At present, the removal of sulfur-containing compounds in oil refining and fuels mainly relies on hydrodesulfurization, but this method has obvious disadvantages that it cannot effectively remove thiophene sulfur-containing compounds and their derivatives, and requires relatively harsh reaction conditions. In addition, hydrodesulfurization can also hydrosaturate high-octane olefins, resulting in lower octane in the finished gasoline. Therefore, exploring the method of efficiently removin...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J31/02B01J27/188C10G27/12
CPCB01J27/188B01J31/0284B01J31/1691B01J2531/48C10G27/12C10G2300/202C10G2400/02
Inventor 叶长燊齐兆洋邱挺黄智贤王清莲李玲王晓达林小城
Owner FUZHOU UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap