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High-activity propylene gas-phase epoxidation catalyst and preparation method thereof

A technology for epoxidation and catalysts, applied in the direction of metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of propylene conversion rate less than 2.5%, storage and transportation problems Potential safety hazards, high molybdenum content in catalysts, etc., to improve catalytic activity and stability, reduce cost and environmental pollution, and reduce molybdenum content

Active Publication Date: 2014-11-05
FUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

With TS-1 molecular sieve as catalyst, the reaction conditions are mild and the PO yield is high, but due to TS-1 and H 2 o 2 The cost is higher, and H 2 o 2 There are potential safety hazards in storage and transportation, even if a factory is built nearby, there will be H 2 o 2 The problem of high production energy consumption and high cost limits its industrialization process to a certain extent
M. Haruta et al. (Journal of Catalysis, 1998, 178(2): 566-575) synthesized Au / TiO by deposition-precipitation method for the first time 2 Catalyst, in H 2 with O 2 Under coexistence conditions, a PO selectivity as high as 93% was obtained, but the conversion of propylene was less than 2.5%
The Si / Bi for dear catalytic materials is low, the Bi content is high, carcinogenic organic amines are used in the synthesis method, the cost is high, and the pollution is large
Y. J. Pang et al. (ChemCatChem, 2014, 6(3):876-884) MoO synthesized by simple impregnation method 3 -Bi 2 SiO 5 / SiO 2 Has good propylene gas phase epoxidation activity, but the catalyst Mo content is relatively high, with MoO 3 Calculated as 18.1wt%, and PO selectivity needs to be further improved

Method used

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  • High-activity propylene gas-phase epoxidation catalyst and preparation method thereof

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Experimental program
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Embodiment 1

[0023] Embodiment 1: Catalyst TiO 2 -MoO 3 -Bi 2 SiO 5 / SiO 2 (Si / Bi=50, Mo / Bi=3, Ti / Mo=0.3) preparation. Weigh 25g template agent hexadecyltrimethylammonium bromide and dissolve in 3000mL deionized water, stir in an ice-water bath for 1h, then add 520g tetraethyl orthosilicate to the above template agent solution, stir to form solution A, And continue to stir in the ice-water bath for 1h; Weigh 24g of bismuth nitrate and dissolve it in 100mL of 50% by volume glycerin aqueous solution to form solution B; Add solution B dropwise to solution A to form a mixed solution, continue to mix in the ice-water bath Stir for 1 hour, transfer the obtained white emulsion into a 5000mL autoclave with a PTFE substrate, and conduct a hydrothermal reaction at 80°C for 20 hours; wash the obtained white gel with deionized water, and dry at 110°C After 12 hours, the obtained sample was ground and calcined at 550°C for 8 hours to obtain bismuth silicate (Bi 2 SiO 5 ) SiO 2 Mesoporous materi...

Embodiment 2

[0027] Embodiment 2: As in the catalyst system of embodiment 1, the molybdenum precursor used is ammonium dimolybdate, and the titanium precursor is tetraisopropyl titanate, and the amount of the precursor used is the same as that of embodiment 1, and the carrier is synthesized During the process, after adding solution B to solution A, continue to stir at 0°C for 9 hours, the hydrothermal condition for preparing the carrier is hydrothermal reaction at 50°C autogenous pressure for 48 hours, and the ultrasonic vibration impregnation condition for loading active components is at 4°C After 4 hours, the sample loaded with active metals was dried and ground and then calcined at 450° C. for 8 hours. The other reaction conditions were the same as in Example 1. The results of the epoxidation reaction are shown in Table 1.

Embodiment 3

[0028] Embodiment 3: as the catalyst system of embodiment 1, but be Si / Bi=50 by element molar ratio, Mo / Bi=5, the proportioning ratio preparation catalyst TiO of Ti / Mo=0.3 2 -MoO 3 -Bi 2 SiO 5 / SiO 2 , the titanium precursor is tetraisopropyl titanate, which has the same molar weight as that of butyl titanate in Example 1. When preparing the carrier, it was hydrothermally reacted at 100°C for 48 hours under autogenous pressure, and the ultrasonic vibration impregnation conditions when loading active components 0.2h at 30°C, and the other reaction conditions are the same as in Example 1. The content of each component in the catalyst is by mass percentage, and the carrier Bi 2 SiO 5 / SiO 2 79.5%, MoO 3 17.6%, TiO 2 was 2.9%. The results of the epoxidation reaction are shown in Table 1.

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Abstract

The invention discloses a high-activity propylene gas-phase epoxidation catalyst, TiO2-MoO3-Bi2SiO5 / SiO2, for preparing propylene oxide and a preparation method thereof. The catalyst is used for a propylene gas-phase epoxidation reaction for preparing the propylene oxide, which takes molecular oxygen (O2) or nitric oxide (NO) as an oxidant; reaction conditions are moderate and no inhibitor is needed; the catalyst has high catalytic activity. The catalyst takes a SiO2 mesoporous material Bi2SiO5 / SiO2 containing bismuth silicate (Bi2SiO5) as a carrier, MoO3 as an active component and TiO2 as an auxiliary agent. The catalyst comprises following components in percentage by mass: 64.6%-98.8% of the carrier Bi2SiO5 / SiO2, 1.1%-22.8% of the MoO3 and 0.1%-12.6% of the TiO2. The mol ratio of Si to Bi in the carrier Bi2SiO5 / SiO2 is 30-200. The catalyst is synthesized by using a hydrothermal method; molybdenum and titanium precursors in the active component MoO3 and the auxiliary agent titanic oxide are immersed into the carrier by an ultrasonic-assisted immersion method to prepare the catalyst.

Description

technical field [0001] The invention belongs to the field of petrochemical catalyst preparation methods, and more specifically relates to a catalyst for preparing propylene oxide and a preparation method thereof, especially a catalyst for preparing propylene oxide by gas-phase epoxidation of propylene and a preparation method thereof. Background technique [0002] Propylene oxide, referred to as PO, is an important chemical raw material, a very important organic compound raw material, and the third largest propylene derivative after polypropylene and acrylonitrile. At present, the main methods of producing PO in industry are chlorohydrin method and co-oxidation method. Among them, the chlorohydrin method is still the main production method of PO, which has the advantages of short process, low investment, good selectivity, and high efficiency. However, the hypochlorous acid produced in the production process of this process severely corrodes equipment, and produces a large am...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/28C07D301/08C07D301/03C07D303/04
CPCY02P20/52
Inventor 陈晓晖郑勇魏可镁
Owner FUZHOU UNIV
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