SU1583163A1 - Catalyst for condensation of oil aldehyde to butylbutyrate - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular a catalyst for the condensation of oil aldehyde to butyl butyrate. The goal is to increase the activity of the catalyst. Catalyst composition, wt.%: Aluminum butylate 22.65-24.29

ALCL 3 1.94-4.67

ZNO 0.63-6.11 and butyl butyrate up to 100. This catalyst in the specified process provides butyl butyrate performance up to 350 mol / mol versus 175 mol / mol during aldehyde conversion up to 86.78% and process time up to 165 min versus 1260 min. 1 tab.

Description

The invention relates to the preparation of catalysts for the condensation of oil aldehyde by the reaction of Gishchenko to butyl butyrate, used as a solvent for paints and adhesives, as an aromatic perfume.

The aim of the invention is to increase the specific activity of the catalyst due to the content of zinc oxide as a zinc compound with a certain content of components.

Example 1. The catalyst is prepared under conditions that prevent moisture from entering the reagents, as follows. Aluminum chips (27 g) are dissolved by heating in stoichiometric amounts of absolute n-butanol (246 g). Aluminum butoxide (3 g) is used as a promoter. At the end of the reaction, the aluminum butylate melt is separated by decantation from insoluble impurities. In a hermetically sealed glass reactor equipped with a magnetic stirrer, 24.26 wt.% Aluminum butylate and 72.80 wt.% Butyl butyrate are mixed and stirred with a magnetic stirrer. 1.94% by weight of aluminum chloride is gradually added to the suspension with stirring and stirred at 40 ° C for 24 hours. To the resulting suspension is added 1.00% L of zinc oxide and stirred at 40 ° C for 24 hours. The catalyst thus prepared can be used immediately or store. In the latter case, the catalyst suspension before use should be activated by stirring at 40 ° C for 10-20 h0

The resulting catalyst is tested as follows,

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with

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In a reactor with a heat exchange jacket equipped with a thermometer, a sensor for monitoring the concentration of oil aldehyde, dropping funnels for dosing the catalyst and aldehyde, and magnetic stirring, after purging with dry argon, pour in 10 ml of the aldehyde, turn on the cooling and start stirring with stirring the catalyst and aldehyde at such a rate that the temperature of the reaction mixture was in the range of 10-30 ° C. After introducing the entire amount of aldehyde, the catalyst is continued to be added dropwise until the concentration of oil aldehyde is 10%. A total of 50 minutes is added for 44.2 g of oil aldehyde and 2.9 g of catalyst. The reaction mixture was measured for another 60 minutes and then analyzed. The content of the individual components is, wt.%: Butyraldehyde 6.86, butanol 0.13, butyl butyrate 91.27, solid catalyst 1.74. The specific catalyst activity is 199 mol of butyric aldehyde converted into butyl butyrate per 1 mol of aluminum butylate, the condensation process is 110 minutes.

Example 2. Catalyst composition, wt%: aluminum butyl 24.29, aluminum chloride 2.86, zinc oxide 1.03 (butyl butyrate 71.82, prepared according to example 1.

The catalyst was tested as in Example 1, mixing 41.30 g of oil aldehyde and 2.05 g of catalyst. After 106 minutes, the reaction mixture of the composition, wt.%, Is obtained: oil aldehyde 4.00, butanol 0.10, butyl butyrate 94.57, solid catalyst 1.33. The specific activity is 272 mol / mol.

Example 3. Catalyst composition, wt.%: Aluminum butyl 23.85, aluminum chloride 4.67, zinc oxide 0.96f butyl butyrate 70.52, prepared according to example 1.

The catalyst was tested as in Example 1, mixing 38.25 g of aldehyde oil and 2.00 g of catalyst. After 100 minutes, the reaction mixture of the composition was obtained, wt%: aldehyde oil 4.81, butanol 0.10, butyl butyrate 93.63, solid catalyst 1.46. The specific activity is 246 mol / mol.

Example 4. The catalyst composition, wt.%: Aluminum butoxide 23.96, aluminum chloride 3.63, zinc oxide

0.63, butyl butyrate 71.78, prepared as in Example 1.

The catalyst was tested as in Example 1, mixing 40.15 g of oil aldehyde and 1.75 g of catalyst. After 165 minutes, a reaction mixture of the composition, wt.%, Is obtained: aldehyde oil 8.20, butanol 0.12, butyl butyrate 90.50, solid catalyst 1.18. The specific activity is 299 mol / mol.

Example 5: Catalyst composition, wt.%: Aluminum butyl 23.31, aluminum chloride 3.54, zinc oxide 3.38, butyl butyrate 69.77, prepared according to example 1.

The catalyst was tested as in Example 1, mixing 39.3 g of aldehyde oil and 1.50 g of catalyst. After 160 min, the reaction mixture of the composition, wt.%, Is obtained: oil aldehyde 8.69, butanol 0.11, butyl butyrate 90.09, solid catalyst 1.11. The specific activity is 350 mol / mol.

Nimerb. The catalyst composition, wt.%: Aluminum butyl 22.65, aluminum chloride 3.44, zinc oxide 6.11, butyl butyrate 67.80, prepared according to example 1.

The catalyst was tested as in Example 1, mixing 49.65 g of oil aldehyde and 2.50 g of catalyst. After 157 minutes, the reaction composition is obtained, the weight of the composition, wt.%: Oil aldehyde 3.07, butanol 0.10, butyl butyrate 95.29, solid catalyst 1.54. The specific activity is 290 mol / mol.

Example 7 (comparative). The catalyst composition, wt.%: Aluminum butyllate, 20.32, aluminum chloride, 0.70, zinc oxide, 0.78, butyl butyrate, 78.20, prepared according to example 1.

The catalyst was tested as in Example 1, mixing 37.70 g of oil aldehyde and 8.70 g of catalyst. After 160 min, the reaction mass of the composition is obtained, wt%: oil aldehyde 3.49, butanol 0.11, butyl butyrate 92.31, solid catalyst 4.09. The specific activity of 70 mol / mol

PRI me R 8 (comparative). The catalyst composition, wt.%: Aluminum butyl 23.66, aluminum chloride 5.43 zinc oxide 0.94, butyl butyrate 69.97 prepared according to example 1.

The catalyst was tested as in Example 1, mixing 42.60 g of oil aldehyde and 4.00 g of catalyst. After 156 min get the reaction

mass of the composition, ks-to: oil aldehyde 84.33, butanol 0.11, butylbutyrate 12.98, solid catalyst 2.58. The specific activity is 12 mol / mol.

Example 9 (comparative), Catalyst composition, wt%: aluminum butylate 24.08, aluminum chloride 3.65, zinc oxide 0.20, butyl butyrate 72.07, prepared according to example 1.

The catalyst was tested as in Example 1, mixing 40.10 g of aldehyde oil and 4.80 g of catalyst. After 165 min, the reaction composition is obtained in mass, wt%: aldehyde oil 11.35, butanol 0.11, butyl butyrate 85.55, solid catalyst 2.99. The specific activity is 103 mol / mol.

Example 10 (comparative). The catalyst composition, wt.%: Aluminum butyllate, 22.80, aluminum chloride, 3.46, zinc oxide, 6.78, butyl butyrate, 66.96, prepared according to example 1.

The catalyst slurry is unstable and therefore non-technological and of little use as a condensation catalyst.

Example 11 (comparative). Catalyst composition, wt.%: Aluminum butyllate 26.12, aluminum chloride 2.30, zinc oxide 0.98, butyl butyrate 70.60, prepared according to example 1.

Catalyst slurry thickens when attempting to heat a slurry.

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above 40 C, the catalyst activity decreases sharply

Example 12 (known) 0.2 g of chlorine is added to 40 g of butyl butyrate, after which 10 g of aluminum are added.

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mini crumbs, 0.3 g of mouth bleach; and, 0.3 g of iodine. The reaction mixture is brought to a boil and absolute butanol is added dropwise to just 74 g. Duration of addition is 5-20 hours. After cooling the reaction mass to 40 ° C, 8 g of anhydrous zinc chloride are added. The resulting catalyst has the following composition, wt.%:

Aluminum butylate 62.73 Aluminum chloride 0.19 Zinc chloride 6.18 Butyl butyrate 30.90 The catalyst was tested as in Example 1.

The specific activity of this catalyst is 175 mol of butyric aldehyde converted into butyl butyrate per 1 mol of aluminum butylate, the condensation time is 21 h.

The results of testing the catalysts are presented in the table.

Claims (1)

25 claims Catalyst for condensation of aldehyde oil into butyl butyrate, including aluminum butylate, aluminum chloride, zinc compound and butyl butyrate, characterized in that, in order to increase the specific activity of the catalyst, it contains zinc oxide in the following ratio, wt.%: Aluminum Butyl Aluminum chloride Zinc oxide Butyl butyrate five ABOUT 22.65-24.29 1.94-4.67 0.63-6.11 Else