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Reaction process for preparing 1, 3-butadiene by oxidizing and dehydrogenating 1-butene with carbon dioxide

A carbon dioxide, oxidative dehydrogenation technology, applied in carbon compound catalysts, catalysts, organic chemistry, etc., can solve the problems of low 1,3-butadiene selectivity, catalyst carbon deposition, poor stability, etc., to improve the resistance to carbon deposition. performance, extended life, and improved stability

Active Publication Date: 2020-07-31
TIANJIN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0013] The technical problem to be solved by the present invention is that the existing carbon dioxide oxidative 1-butene dehydrogenation to 1,3-butadiene reaction process faces severe carbon deposition on the catalyst, poor stability and the selection of 1,3-butadiene. To solve the problem of low stability, provide a new reaction process for carbon dioxide oxidation of 1-butene dehydrogenation to 1,3-butadiene

Method used

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  • Reaction process for preparing 1, 3-butadiene by oxidizing and dehydrogenating 1-butene with carbon dioxide
  • Reaction process for preparing 1, 3-butadiene by oxidizing and dehydrogenating 1-butene with carbon dioxide
  • Reaction process for preparing 1, 3-butadiene by oxidizing and dehydrogenating 1-butene with carbon dioxide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] The oxidative dehydrogenation catalyst was prepared according to Example 22 in the patent CN201711157473.2.

[0031] Reaction evaluation process and conditions: The oxidative dehydrogenation reaction is carried out in a quartz tube fixed-bed reactor with an inner diameter of 7.6 mm, where the reaction pressure is normal pressure, the reaction temperature is 600 ° C, and the mass space velocity based on 1-butene is 4.5 grams 1-butene / g catalyst·hour, the molar ratio of 1-butene to carbon dioxide is 1:9, water is the diluent, the ratio of water to ene (water / 1-butene) is 5.0 (molar ratio), and the amount of catalyst is 0.2 g .

[0032] The results of the oxidative dehydrogenation reaction performance of Example 1 and the carbon deposition of the catalyst after the reaction are shown in Table 1.

Embodiment 2~5

[0034] Under the reaction conditions of Example 1, the catalyst in Example 1 was used to investigate the water-ene ratio in the carbon dioxide oxidation 1-butene dehydrogenation process conditions, so as to obtain the best water-ene ratio. Set the ratio of water to ene to 8.0, 9.0, 10.0, 11.0 respectively. The conversion rate of 1-butene, CO 2 The conversion rate, the selectivity of 1-butene to 1,3-butadiene, the space-time yield of 1,3-butadiene and the carbon deposition of the catalyst after 1 hour of reaction are used as indicators, and the obtained results are shown in Table 1.

[0035] It can be concluded from the results that after the introduction of water vapor, the space-time yield of 1,3-butadiene of the catalyst decreases, and it presents a "volcanic" distribution with the increase of the water-ene ratio, and when the water-ene ratio is 10.0 Extreme values ​​appeared, in which the conversion rate of 1-butene was 76%, the selectivity of 1-butene to 1,3-butadiene was...

Embodiment 6~7

[0039] Under the reaction conditions of Example 4, the catalyst in Example 1 was used to investigate the reaction temperature in the carbon dioxide oxidation of 1-butene dehydrogenation process conditions, in order to explore the best reaction temperature. Set the reaction temperature as 500°C and 550°C respectively. The conversion rate of 1-butene, CO 2 The conversion rate, the selectivity of 1-butene to 1,3-butadiene and the space-time yield of 1,3-butadiene are indicators, and the obtained reaction performance results are shown in Table 2. It can be seen from Table 2 that the activity of the catalyst is not as high as that at 600°C when the reaction temperature is 500°C or 550°C. Therefore, 600°C is the optimal temperature for the reaction.

[0040] Table 2 Catalysis of CO by catalysts at different reaction temperatures 2 Reaction result of oxidative dehydrogenation of 1-butene

[0041]

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Abstract

The invention provides a reaction process for preparing 1, 3-butadiene by oxidizing and dehydrogenating 1-butene with carbon dioxide. According to the reaction process, water vapor is introduced intoa reaction system so as to reduce the carbon deposition of a catalyst during the reaction process, such that the catalyst is regenerated, the reaction heat during the high temperature reaction is removed, the fine adjustment effect on the surface morphology of the catalyst is generated, and the carbon deposition resistance, the reaction activity and the stability of the catalyst are improved.

Description

technical field [0001] The invention relates to a reaction process for preparing 1,3-butadiene by oxidizing 1-butene and dehydrogenating carbon dioxide, in particular to a reaction process for preparing 1,3-butadiene by introducing water vapor through oxidizing 1-butene and dehydrogenating carbon dioxide. Background technique [0002] 1,3-Butadiene is an important organic chemical raw material, which is widely used in the petrochemical industry to produce rubber, resin, and plastics. It is also an intermediate for the preparation of adiponitrile, sulfolane, and cyclooctadiene. With the development of the global economy, the market demand for 1,3-butadiene is increasing. According to the previous technology, the production of 1,3-butadiene is mainly extracted from naphtha steam cracking C4. However, the development of more and more light hydrocarbons from natural gas and refinery gas to ethylene, propylene, and coal to olefins will not be conducive to the development of stea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C5/333C07C11/167
CPCC07C5/3332C07C2523/86C07C11/167Y02P20/584
Inventor 闫冰陈全鑫窦洪鑫姜涛李健
Owner TIANJIN UNIV OF SCI & TECH
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