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Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof

A technology of low-carbon alkanes and catalysts, which is applied in the production of basic organic chemical raw materials, can solve the problems of low conversion rate of raw materials, and achieve the effect of improving dispersion and activity

Active Publication Date: 2010-07-14
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In Chinese patent CN200910091226.6, SAPO-34 is used as a catalyst carrier for dehydrogenation of low-carbon alkane to olefins, and better olefin yield and selectivity are obtained, but when only SAPO-34 is used as a carrier, the conversion rate of raw materials is relatively low. Low, such as in the process of propane dehydrogenation to propylene, although the propylene selectivity can reach more than 90%, but the conversion rate of raw material propane is only 20%

Method used

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  • Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof
  • Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof
  • Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] First, SAPO-34 molecular sieve and alumina are mixed, granulated into spherical shape, the particle size ranges from 20 to 100 microns, and the mass ratio of SAPO-34 to alumina is 2.3; then the carrier is 0.16M SnCl 2 .2H 2 The catalyst was impregnated in O solution at 80°C for 10 hr, and the loading of Sn in the catalyst reached 1 wt%, and then dried at 120°C for 6 hr. The dried samples were then calcined in an air atmosphere in a muffle furnace at a temperature of 550° C. for 4 hrs. Sn / SAPO-34 / Al after firing 2 o 3 powder with 0.03M H 2 PtCl 6 ·6H 2 The O solution was impregnated at 80° C. for 4 hr, so that the mass percentage of Pt in the final catalyst was 0.5%. It was then dried at 120°C for 6hrs, and then fired in a muffle furnace at 550°C for 4hrs. Prior to reaction evaluation, all catalyst samples were dechlorinated with steam at 500°C for 8 hr; then reduced with hydrogen at 550°C for 12 hr.

[0028] The catalyst evaluation conditions are as follows: fix...

Embodiment 2

[0032] The catalyst in Example 1 was regenerated, chlorinated, refreshed and reduced after 8 hours of reaction, and then propane dehydrogenation reaction was carried out. The regeneration temperature is 650°C, the regeneration atmosphere is water vapor and nitrogen, the partial pressure of water vapor is 50%, and the regeneration time is 2hr; 2 Cl 2 h 4 , CCl 4 、C 2 Cl 4 h 2 、C 2 Cl 2 h 2 and C 3 Cl 2 h 4 , the chlorination temperature is 500°C, the chlorination space velocity is 10ml / g / hr, and the chlorination time is 2hr; the reducing agent is pure hydrogen, the reduction temperature is 500°C, and the reduction time is 4hr.

[0033] The catalyst evaluation conditions are as follows: fixed bed reactor, catalyst loading 1g, reaction temperature 620°C, weight space velocity 2.00hr -1 , the reaction pressure is 0.1MPa, the H in the raw material 2 The molar ratio to propane is 0.3. When the reaction was carried out for 2hr -1 The experimental results are shown in T...

Embodiment 3

[0038] Mix SAPO-17, SAPO-18, SAPO-44, SAPO-53 and SAPO-5 molecular sieves and alumina respectively, and granulate into a clover shape with an equivalent diameter of 3mm, wherein the content of alumina in the mixed carrier is 25wt% . Then the carrier was in 0.20M SnCl 2 .2H 2 The catalyst was impregnated in O solution at 80°C for 10 hr, and the loading of Sn in the catalyst reached 10 wt%, and then dried at 120°C for 6 hr. The dried samples were then calcined in an air atmosphere in a muffle furnace at a temperature of 550° C. for 4 hrs. Sn / SAPO-34 / Al after firing 2 o 3 powder with 0.03M H 2 PtCl 6 ·6H 2 The O solution was impregnated at 80 °C for 4 hr, so that the Pt content in the final catalyst was 2 wt%. It was then dried at 120°C for 6hrs, and then fired in a muffle furnace at 550°C for 4hrs. Prior to reaction evaluation, all catalyst samples were dechlorinated with steam at 500°C for 8 hr; then reduced with hydrogen at 550°C for 20 hr. Catalyst made of Pt / Sn / SAP...

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Abstract

The invention discloses a catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof, belonging to the technical field of preparation of basic organic chemical materials. The catalyst takes silicoaluminophosphate molecular sieve and alumina mixture as carriers, VIII group or IVA group elements as active components and alkaline-earth metal or rare-earth elements as auxiliary agents for the process of olefin preparation by ethane, propane, butane or pentane dehydrogenation. In the process of olefin preparation by low-carbon alkane dehydrogenation, catalyst is firstly reduced by hydrogen and then reacts, and finally the catalyst is in charcoaling regeneration and chlorination update; and reaction regeneration process flow has big choice, the reactor can adopt a fixed bed, a moving bed, a fluidized bed or a double-particle fluidized bed, and catalyst regeneration can be carried out in a device or out of the device. Compared with the existing catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, the catalyst provided by the invention ensures that low-carbon alkane selectivity is above 95% in the olefin preparing process by low-carbon alkane dehydrogenation under high conversion rate.

Description

technical field [0001] The invention relates to a catalyst for dehydrogenating low-carbon alkanes to olefins and its application, and belongs to the technical field of basic organic chemical raw material production. Background technique [0002] Propylene is an important organic chemical raw material, widely used in the preparation of polymer materials such as polypropylene and polyacrylonitrile, and products such as butanol, octanol, propylene oxide, isopropanol, and acrylic acid. Different from other chemicals, the current production of propylene is generally based on the co-production or by-product of naphtha steam cracking process and catalytic cracking process. Since the 1990s, the growth rate of my country's demand for propylene has exceeded that of ethylene. The original propylene Sources can no longer meet demand. A large amount of low-carbon alkanes are by-produced in catalytic cracking, naphtha steam cracking, MTO / MTP and other processes, so how to convert low-carb...

Claims

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Application Information

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IPC IPC(8): B01J29/85B01J29/90C07C5/333C07C11/06C07C11/04C07C11/08C07C11/10
CPCY02P20/52Y02P20/584
Inventor 魏飞山尼汤效平褚玥王垚
Owner TSINGHUA UNIV
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