Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base

一种TS-1、无机碱的技术，应用在化学仪器和方法、分子筛和碱交换化合物、无机化学等方向，能够解决扩散阻力大、钛物种向外扩散路径长等问题，达到提高催化性能、普遍适用性、降低成本的效果

Inactive Publication Date: 2012-06-20
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These factors lead to a long outward diffusion path of the internally dissolved titanium species during the modification process and a large diffusion resistance.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] In the first step, the large-grain cheap TS-1 synthesized according to the published document Appl.Catal.A, 185, (1999) 11 was calcined at 540° C. for 6 hours in an air atmosphere to remove the template.

[0044] In the second step, the ratio of cheap TS-1, tetrapropylammonium bromide, sodium hydroxide and water is TS-1 (g): salt (mol): alkali (g): water (g)=50: The ratio of 0.035:1.4:500 was evenly mixed. Modified at 170°C for 24 hours in a static kettle.

[0045] In the third step, the obtained TS-1 was suction-filtered, washed to pH = 7, dried at 110°C for 12 hours, and finally calcined at 390°C for 6 hours.

[0046] The TS-1 samples before and after modification were subjected to gas-phase epoxidation of propylene according to the reaction conditions described in the published literature (Acta Catalytica Sinica, 31(2010) 1195-1199). Reaction condition is: hydrogen, oxygen, propylene gas velocity are respectively 170ml / min, 8ml / min and 18ml / min (H 2 / O 2 / C 3 =1...

Embodiment 2

[0048] Repeat Example 1, but the modified sample is TS-1 synthesized by the classical system (patent USP4410501). The results of the epoxidation reaction were: the C3H6 conversion and PO selectivity of TS-1 before modification were 4.4% and 91.2%; 3 h 6 Conversion and PO selectivity were 8.8% and 99.6%.

Embodiment 3

[0050] Repeat Example 1, carry out liquid-phase epoxidation of propylene under the following reaction conditions: in 400ml stainless steel high-pressure batch reactor, add 0.2g catalyst A, 30ml methanol, 2ml30% hydrogen peroxide, feed propylene under stirring, propylene pressure 0.4 MPa, the reaction temperature is 50°C, and the reaction time is 60 minutes, the sample is taken, and the conversion rate of hydrogen peroxide is measured by iodometric method. The selectivity of propylene oxide and the effective utilization of hydrogen peroxide were analyzed by gas chromatography. The hydrogen peroxide conversion rate of TS-1 before modification was 72.7%, the selectivity of propylene oxide was 73.4%, and the effective utilization rate of hydrogen peroxide was 68.8%; after modification, the conversion rate of TS-1 hydrogen peroxide was 87.4%, and the ring The selectivity of oxypropane is 92.6%, and the effective utilization rate of hydrogen peroxide is 92.7%.

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Abstract

The invention belongs to the technical field of inorganic chemicals synthesis and relates to a method for modifying titanium silicalite. The method is characterized by comprising the following steps: preprocessing the TS (titanium silicalite)-1; modifying the preprocessed TS-1 by mixed liquor containing quaternary ammonium salt and inorganic base, wherein the quaternary ammonium salt refers to tetrapropyl ammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide and a mixture of tetrapropyl ammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide and tetrapropylammonium iodide, and the inorganic base refers to lithium hydroxide, sodium hydroxide, potassium hydroxide and a mixture of lithium hydroxide, sodium hydroxide and potassium hydroxide; and postprocessing the modified TS-1. The method for modifying the titanium silicalite has general applicability, and is suitable for TS-1 molecular sieves synthesized by various methods, in particular the TS-1 molecular sieves synthesized by inexpensive systems; and the catalytic performance of epoxidation of gas phase and liquid phase propylenes of the TS-1 molecular sieves can be simultaneously improved.

Description

technical field [0001] The invention belongs to the technical field of inorganic chemical synthesis, and relates to a modification method of titanium silicon molecular sieve (TS-1). Background technique [0002] Titanium-silicon molecular sieve (TS-1) is obtained by introducing transition metal titanium into the molecular sieve framework with MFI structure during the synthesis process. It has excellent selective oxidation performance and specific shape-selective performance. The green catalytic system composed of TS-1 and low-concentration hydrogen peroxide can be widely used in the selective oxidation of alcohols, phenols, olefins, ethers and other organic substances, among which phenol hydroxylation, cyclohexanone amine oxidation and propylene epoxidation have been Realize industrial production. [0003] Macro Taramasso et al first disclosed the synthesis method of TS-1 in 1981 (GB2071071A, USP4410501). Over the past 30 years, after continuous development and enrichment,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/08
CPCC01B39/08C07D301/03C07D305/06C01B37/005B01J29/035C07D303/04B01J29/89C01B39/085B01J2229/34B01J2229/183B01J2229/38B01J29/041
Inventor 郭洪臣苏际刘光红
Owner DALIAN UNIV OF TECH
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