Propane dehydrogenation method catalyzed by transition metal oxide-silica molecular sieve catalyst

A technology for catalysts to catalyze propane and transition metals, applied in the field of propane dehydrogenation, can solve the problems of complex moving bed technology, expensive equipment investment, easy carbon deposition and deactivation, etc., achieve energy saving, emission reduction, production safety risks, reduce production safety risks, Solve the serious effect of carbon deposition

Active Publication Date: 2022-07-08
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

For example, the Pt / Sn catalyst used in the UOP process technology is basically non-toxic to the environment and has a long catalytic life, and its supporting moving bed technology can regenerate the catalyst on-line to ensure continuous reaction, but Pt is expensive and has poor toxicity resistance. (the sulfur content in the raw material should not be greater than 50ppm), the corresponding moving bed technology is complicated, the device investment is expensive and the power consumption is high
Chromium-based catalyst Cr used by Lummus 2 o 3 / Al 2 o 3 Although the catalytic activity is higher than that of Pt / Sn, and it has the advantages of good tolerance to raw material impurities and low price, but it also has the disadvantages of easy carbon deposition and deactivation, short single-pass life, frequent regeneration, and strong biological toxicity.

Method used

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  • Propane dehydrogenation method catalyzed by transition metal oxide-silica molecular sieve catalyst
  • Propane dehydrogenation method catalyzed by transition metal oxide-silica molecular sieve catalyst
  • Propane dehydrogenation method catalyzed by transition metal oxide-silica molecular sieve catalyst

Examples

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Effect test

Embodiment 1

[0027] Example 1: Application of MFI type Na / VS-1 molecular sieve catalyst in propane dehydrogenation

[0028]The MFI-type framework-doped VS-1 catalyst is synthesized by a hydrothermal method. The synthesis method refers to the literature published by the inventor's team (Journal of the American Chemical Society 2020 142(38), 16429-16436). The specific synthesis steps are as follows: 0.5 g of ammonium metavanadate (NH 4 VO 3 ) was dissolved in 10 ml of deionized water, stirred for 10 min and then added 1.0 g of oxalic acid, and continued to stir for 20 min until fully dissolved to obtain a V-oxalic acid solution. Another 6.60 g of TPAOH (aqueous tetrapropylammonium hydroxide, 40% wt) and 6.93 g of TEOS (tetraethyl silicate) were added sequentially to 16.9 ml of deionized water. After stirring for 0.5h, 2.89g of the aforementioned V-oxalic acid solution was added dropwise, and finally stirred for 8h. The final solution was transferred to a stainless steel reactor lined with...

Embodiment 2

[0037] Example 2: Application of MFI type K / MoS-1 molecular sieve catalyst in propane dehydrogenation

[0038] The MFI-type framework Mo-doped K / MoS-1 catalyst was synthesized by a hydrothermal method, similar to Example 1, and the specific synthesis steps were as follows: 0.5 g of ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O) was dissolved in 10 ml of deionized water, and stirred for 10 min to obtain an ammonium molybdate solution. Another 6.60 g of TPAOH (aqueous tetrapropylammonium hydroxide, 40% wt) and 6.93 g of TEOS (tetraethyl silicate) were added sequentially to 16.9 ml of deionized water. After stirring for 0.5h, 2.89g of the aforementioned ammonium molybdate solution was added dropwise, and finally stirred for 8h. The subsequent hydrothermal crystallization and post-treatment methods are the same as those in Example 1, and the final product obtained is MFI-type framework-doped MoS-1. 2g MoS-1 was placed in 50ml 0.5M potassium nitrate solution and stirred at ...

Embodiment 3

[0041] Example 3: Application of MFI type Mg / CrS-1 catalyst in propane dehydrogenation:

[0042] The MFI-type framework Cr-doped CrS-1 catalyst was synthesized by a hydrothermal method, similar to Example 1, and the specific synthesis steps were as follows: 1.0 g of chromium nitrate nonahydrate was dissolved in 10 ml of deionized water to obtain a solution. Another 6.60 g of TPAOH (aqueous tetrapropylammonium hydroxide, 40% wt) and 6.93 g of TEOS (tetraethyl silicate) were added sequentially to 16.9 ml of deionized water. After stirring for 0.5h, 2.89g of the aforementioned chromium nitrate solution was added dropwise, and finally stirred for 8h. The subsequent hydrothermal crystallization and post-treatment methods are the same as those in Example 1, and the final product obtained is MFI-type skeleton-doped CrS-1. 2g of CrS-1 was placed in 50ml of 0.2M magnesium nitrate solution and stirred at 60°C for 2h, filtered, dried, and calcined at 550°C for 2h in a muffle furnace. Th...

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PUM

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Abstract

The invention relates to propane dehydrogenation technology, and aims to provide a transition metal oxide-silica molecular sieve catalyst catalyzed propane dehydrogenation method. In the method, the transition metal oxide-silica molecular sieve catalyst is loaded into a fixed-bed reactor, and then a reaction gas containing propane is introduced; the temperature of the catalyst bed is controlled to be 400-700° C., and the feed mass space velocity of propane is in the range of 0.01~100h ‑1 . The present invention maintains relatively high propane conversion rate and propylene selectivity, and the reaction temperature is obviously lower than that of the mature process, which is of great significance for energy saving, emission reduction and production safety risk reduction. The catalyst used has excellent anti-coking performance and a single-pass life much higher than that of industrial catalysts, and the hydrogen / hydrocarbon ratio in the product can be greater than 80% in a long-term stable working state. Part of the catalyst can still work continuously for more than 200h in the pure propane atmosphere without any protective gas at normal pressure, which is of great significance to improve the space-time yield of olefins, reduce the power consumption of the reaction process and the cost of product separation.

Description

technical field [0001] The invention belongs to propane dehydrogenation technology, and particularly relates to a method for catalyzing propane dehydrogenation with a metal oxide-silica molecular sieve catalyst. Background technique [0002] Propylene is one of the two basic organic chemical raw materials with the highest output in the world. Its downstream derivatives, such as polypropylene (accounting for more than 50% of propylene demand), acrylonitrile, acrylic acid, propylene oxide, etc., play an indispensable role in the development of today's society. or missing roles. It can be said that the production of propylene is one of the important links connecting the upstream and downstream industries of the petrochemical industry. [0003] At present, the production of propylene in my country mainly relies on the by-product / co-production of traditional refining processes such as naphtha steam cracking and catalytic cracking. The energy consumption is large and the yield is...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C5/333C07C11/06B01J29/04
CPCC07C5/3332B01J29/04B01J29/046C07C11/06Y02P20/584
Inventor 王亮周航肖丰收
Owner ZHEJIANG UNIV
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