Method for preparing rare-earth modified zinc-iron composite oxide catalyst and application of catalyst in reaction of preparing butadiene from butene

A composite oxide and catalyst technology, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve problems such as low yield and impact on butadiene yield

Active Publication Date: 2014-02-05
CHINA UNIV OF PETROLEUM (BEIJING)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In recent years, the U.S. ethylene production facilities are mainly cracking natural gas, ethane and shale gas, mixed with C 4 The yield is low, while the cracking raw materials i

Method used

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  • Method for preparing rare-earth modified zinc-iron composite oxide catalyst and application of catalyst in reaction of preparing butadiene from butene
  • Method for preparing rare-earth modified zinc-iron composite oxide catalyst and application of catalyst in reaction of preparing butadiene from butene
  • Method for preparing rare-earth modified zinc-iron composite oxide catalyst and application of catalyst in reaction of preparing butadiene from butene

Examples

Experimental program
Comparison scheme
Effect test

preparation Embodiment 1

[0041] Reactivity of Rare Earth-Free Zn-Fe Catalysts

[0042] 7.44g zinc nitrate hexahydrate (Zn(NO 3 ) 3 ·6H 2 O) was dissolved in 15mL deionized water, and the corresponding molar amount of ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O) dissolved in 20mL deionized water, at the same time. Mix the two solutions to obtain a zinc-iron mixed solution. Mix 50mL of ammonia solution with a mass fraction of 17% and 300mL of deionized water to prepare a pH=12 alkaline precipitant.

[0043] Use a peristaltic pump to slowly drop the zinc-iron mixed solution into the ammonia precipitation agent for co-precipitation. The dropwise addition time is 2 hours, and the magnetic stirring is maintained during the dropwise addition process and the constant temperature water bath is 30°C. After the co-precipitation is completed, continue to keep the constant temperature water bath for aging for 6 hours. After the supernatant was poured out, it was washed repeatedly with deionized water u...

preparation Embodiment 2

[0048] Preparation of rare earth-modified zinc-iron composite oxide catalysts: Specifically, in order to prepare rare earth-modified zinc-iron composite oxide catalysts composed of three metal components with different contents of rare earth, zinc and iron, rare earth: zinc: iron The molar ratio was set at 0.01˜1:0.5˜2:1˜8, thereby preparing fourteen kinds of catalysts. 10.8g lanthanum nitrate hexahydrate (La(NO 3 ) 2 ·6H 2 O) or cerium nitrate (Ce(NO 3 ) 3 ) was dissolved in 50 mL of deionized water, and stirred to dissolve. Zinc nitrate hexahydrate (Zn(NO 3 ) 3 ·6H 2 O) and ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O) were dissolved in 50mL distilled water, stirred to dissolve. Then the rare earth solution, zinc solution and iron solution are mixed and stirred thoroughly. In addition, 100 mL of ammonia solution with pH=14 was prepared with ammonia solution with a mass fraction of 17%. In a water bath at a constant temperature of 90° C. under magnetic stirring...

Embodiment 1

[0055] Oxidative dehydrogenation of butene on the zinc-iron oxide catalyst: The zinc-iron composite oxide catalyst produced in Preparation Example 1 was used to carry out the oxidative dehydrogenation of butene under the following conditions. The XRD diffraction pattern shows that the catalyst is ZnFe-containing 2 o 4 and α-Fe 2 o 3 zinc-iron composite oxides (participated in figure 1 ). At 380°C, the molar ratio of butene:air:steam is 1:0.4:8, and the gas hourly space velocity is 300h -1 The activity of the catalyst is shown in the table below

[0056] Table 3 Zinc-iron oxide catalyst activity varies with the iron ratio in the catalyst

[0057]

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Abstract

The invention relates to a rare-earth modified zinc-iron composite oxide catalyst, a method for preparing the rare-earth modified zinc-iron composite oxide catalyst, and an application of the rare-earth modified zinc-iron composite oxide catalyst in preparing 1,3-butadiene. Specifically, the invention relates to the rare-earth modified zinc-iron composite oxide catalyst which is generated from an alkali solution by using a coprecipitation method, wherein the composite oxide catalyst is used for producing the 1,3-butadiene with high additional values by adopting the butene as a reactant. Due to adoption of the composite oxide catalyst, the yield of the 1,3-butadiene is higher than that of the conventional ferrate (ZnFe2)4), and the temperature for reaction is low.

Description

technical field [0001] The invention relates to a rare earth modified zinc-iron composite oxide catalyst, a method for preparing the modified zinc-iron composite oxide catalyst, and an application of using the modified composite oxide catalyst to prepare 1,3-butadiene. Specifically, the present invention relates to a rare earth-modified zinc-iron composite oxide catalyst, which is produced in an alkaline solution by co-precipitation. The composite oxide catalyst uses butene as a reactant to produce high value-added 1,3-Butadiene. Using this composite oxide has higher than traditional ferrite (ZnFe 2 o 4 ) of 1,3-butadiene yield, and the temperature required for the reaction is lower. Background technique [0002] Butadiene is an important basic organic raw material in petrochemical industry, and its position in petrochemical olefin raw materials is second only to ethylene and propylene. About 90% of the world's butadiene production capacity uses cracking C 4 The mixture...

Claims

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Application Information

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IPC IPC(8): B01J23/83C07C11/167C07C5/48
Inventor 吴志杰窦涛吴宇辰高金森王刚宁国庆
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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