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A kind of 1,4-butanediol dehydrogenation preparation gamma-butyrolactone catalyst and its preparation method and application

A catalyst and butanediol technology, applied in 1, can solve the problems of poor anti-coking ability, catalyst poor anti-coking ability, catalyst poor anti-coking ability, etc., and achieve strong anti-coking ability, good activity and selection The effect of the properties, the preparation method is simple

Active Publication Date: 2016-11-09
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN99113276.9 discloses a method for preparing a copper-containing catalyst. The obtained catalyst contains 10% to 90% of copper oxide, 0% to 50% of the oxide of the promoter component, and 5% to 40% of aluminum oxide. 0.1%~4.0% alkali metal oxide, this catalyst can be used for the hydrogenation of organic reaction or dehydrogenation reaction, and the range described in this patent is very wide, and the catalyst that its embodiment obtains is used for preparing gamma- When using butyrolactone, the effect is not satisfactory, mainly due to the poor anti-coking ability of the catalyst and the inability to maintain the activity
[0005] In the prior art, for the reaction of 1,4-butanediol dehydrogenation to γ-butyrolactone, Cu-Cr and Cu-Mn catalysts have better reaction performance and stronger anti-coking ability, but the process There are many side reactions such as dehydration in the medium, and more tetrahydrofuran and n-butanol are produced
In addition, Cr has adverse effects on the environment and human health.
Cu / SiO prepared by impregnation method 2 Catalysts are more expensive
When Cu-Zn and Cu-Zn-Al composite oxide catalysts are used for 1,4-butanediol dehydrogenation to prepare γ-butyrolactone, although they have better reaction performance, the conversion rate and selectivity are better than Cu -Cr and Cu-Mn series catalysts, but the catalysts have poor anti-coking ability and cannot run for a long period of time
Therefore, Cu-Zn and Cu-Zn-Al catalysts cannot completely replace Cu-Cr catalysts, mainly because the former has poor anti-coking ability during the reaction process and cannot maintain good reactivity for a long time.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] 136.7gCu(NO 3 ) 2 ·3H 2 O and 164.5gZn(NO3) 2 ·6H 2 O was dissolved in 2L of distilled water, and 23.8g of TiCl was added 4 well mixed. 106gNa 2 CO 3 Prepared into 1mol / L aqueous solution. Add a small amount of water into a 5L beaker and place it in a water bath. The temperature of the water bath is controlled at about 80°C. Under stirring conditions, add the above two solutions into the large beaker in parallel to complete the co-precipitation. During the precipitation process, the pH value is controlled at 8.0. Aging is carried out after the precipitation is completed, the aging temperature is controlled at 105°C, the aging pH value is 9.0, and the aging time is 15h. After the aging is completed, the precipitate filtered and washed is dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain Catalyst A , composed of: CuO 45%, ZnO 45%, TiO 2 10%. After the catalyst powder is tabletted and pulverized, 10-30 mesh particles are sieved.

Embodiment 2

[0025] 91.2gCu(NO 3 ) 2 ·3H 2 O and 201.0gZn(NO3) 2 ·6H 2 O was dissolved in 2L of distilled water, and 35.6g of TiCl was added 4 well mixed. Precipitation temperature is 75°C, pH value is 7.8; aging temperature is 115°C, pH value is 9.3, aging time is 8h, catalyst B is prepared according to the method in Example 1, and the composition is CuO 30%, ZnO 55%, TiO 2 15%. After the catalyst powder is tabletted and pulverized, 10-30 mesh particles are sieved.

Embodiment 3

[0027] 167.1gCu(NO 3 ) 2 ·3H 2 O and 109.7gZn(NO3) 2 ·6H 2 O was dissolved in 2L of distilled water, and 35.6g of TiCl was added 4well mixed. The precipitation temperature is 83°C, the pH value is 8.5; the aging temperature is 113°C, the pH value is 9.3, and the aging time is 10h. Catalyst C is prepared according to the method in Example 1, and the composition is CuO 55%, ZnO 30%, TiO 2 15%. After the catalyst powder is tabletted and pulverized, 10-30 mesh particles are sieved.

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Abstract

The invention discloses a catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its preparation method. The catalyst is a composite oxide of Cu-Zn-Ti, the catalyst comprises the following components by weight: 30%-55% of CuO, 30%-55% of ZnO and 25%-15% of TiO; and preferably 40%-50% of CuO, 40%-50% of ZnO and 28%-12% ofTiO. The preparation method of the catalyst for dehydrogenating the 1,4-butanediol to prepare the gramma-butyrolactone comprises the following steps: (1) preparing a mixed solution containing Cu, Zn and Ti and a precipitant solution; (2) merging and adding the mixed solution containing Cu, Zn and Ti and the precipitant solution for a co precipitation reaction with the precipitation temperature controlled to be 70-90 DEG C and the pH value to be 7.5-9 in the precipitation process; (3) after the precipitation, aging, controlling the aging temperature to be 20-50 DEG C higher than the precipitation temperature, the aging pH value to be 0.5-2 higher than the precipitation pH value and the aging time to be 5-20h; and (4) filtering by suction, washing, drying, baking, and forming the aged materials to prepare the final catalyst. The catalyst does not contain Cr, is high in activity and high in carbon deposition resistance, and can run stably for a long time.

Description

technical field [0001] The invention relates to a catalyst for preparing gamma-butyrolactone by dehydrogenating 1,4-butanediol and its preparation method and application. Background technique [0002] γ-butyrolactone (abbreviated as γ-BL or GBL), also known as 1,4-butyrolactone. Its own structure is a compound containing a five-membered heterocyclic ring. γ-Butyrolactone is a colorless liquid with acetone-like odor, high boiling point and high solubility. It has good reaction performance, high conductivity, good stability and safe use. As an important organic solvent, γ-butyrolactone is widely used in petroleum industry, medicine, synthetic fiber, synthetic resin, pesticide and many other aspects. As an important fine chemical and organic chemical raw material, it is mainly used to synthesize pyrrolidone, N-methylpyrrolidone, vinylpyrrolidone and other products, and many new uses are constantly being developed. γ-butyrolactone has different technological routes for indust...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/80C07D307/33
Inventor 苏杰陈明
Owner CHINA PETROLEUM & CHEM CORP