SU740743A1 - Method of preparing acrolein - Google Patents

Description

one

The invention relates to methods for producing o (p-unsaturated aldehydes, specifically to a method for producing acrolein, which is widely used in industrial organic synthesis, in particular in the production of acrylic monomers and polymeric materials, as well as for the preparation of glycerol methionine, etc.

The closest to the invention of Yu by technical essence is the method of producing acrolein by catalytic isomerization of propargyl alcohol at 450-630 ° C in the presence of silicate and aluminosilicate catalysts. The greatest yield (68% of theoretical) is obtained on a MoO / SiOj catalyst at 450 ° C 1.

The disadvantages of this method include the insufficiently high 20 yield of the target product, as well as the technological difficulties associated with carrying out the process at a high temperature of 450-630 ° C.

The aim of the invention is to simplify the process and increase the yield of the target product.

This is achieved by the method of producing acrolein by isomerizing propargyl alcohol at a temperature of 300-400 ° C. 30

and a pressure of 10-15 mm Hg. in the presence of an oxide catalyst, molybdenum oxide or tungsten oxide, or rhenium oxide, deposited on a zeolite carrier with a molar SiO2 / Al2O ratio of 20-34: 1, with the following ratio of components, wt.%:

Molybdenum oxide (or

tungsten oxide or

rhenium oxide) 9-10,5

Zeolite

carrierEverything

A distinctive feature of the proposed method is the use of molybdenum oxide or tungsten oxide or rhenium oxide as the oxide catalyst, and a zeolite carrier with a molar ratio of SiO, 3 20 - 34: 1, as the carrier,

The process is usually carried out in a vacuum flow installation, in this case a catalyst is poured into a 10 mm diameter quartz reactor, which is activated for 1 hour in a stream of air at 500 ° C and then in a stream of hydrogen at.

At 300 or 400 ° C propargyl alcohol is passed over the catalyst

at a volumetric rate of 600 h. The pressure in the reactor during the passage of the initial reactant — alcohol is maintained within the range of 10–10 mm Hg. The reaction products are captured in liquid nitrogen and analyzed by gas-liquid chromatography using a katharometer detector, at a column temperature, the carrier gas velocity — gels 60 ml / min, chromatone filler

liquid, impregnated with 5% SE-30i, retention time of acrolein 6 seconds, retention time of propargyl alcohol 8.75 seconds.

To obtain a carrier natural material - zeolite-clinoptilolite - from the Noyembersky deposit, Arm. SSR, having the composition, weight,%: 3 ± O, 68,70; 12.08; CaO 4.44; Nar, O 1.45, K..O 2.12; McfO 0.95, at a molar ratio of SiO2 / Al2O., Equal to 9.7: 1, is treated with hydrochloric acid, followed by cleansing with distilled water and drying.

Example 1, Original zeolite is treated for 3 hours 4 n. with a solution of hydrochloric acid in a thermostat with continuous stirring at. The precipitate is filtered off with distilled water to a pH of 5.2-6.5 and dried at 180 ° C for 3 hours. The resulting support has a wt.%: SiO 80.95; 6.69; CaO 1.42; MgO 0.44; 0.85; 1, -30, at a molar ratio, O, equal to 20.4: 1.

Examples of the preparation of catalysts with different modifiers.

Example 2. 100 g of carrier are thoroughly mixed with a solution of ammonium perrhenate salt (08 g). Then the catalyst is evaporated in a water bath to a homogeneous pasty mass, from which tablets are molded, calcined at 550 ° C for 5 hours and fractionated, the fractions are selected with sizes of 0.25-0.80. The resulting catalyst contains 10% rhenium oxide on a zeolite carrier, Propargyl alcohol in the amount of 2 m is passed over the catalyst (7 g) with a base rate of 600 hours. At 400 ° C, the yield of acrolein is 1.359 g (70.1%).

Example 3. On. the zeolite carrier is applied by impregnation with ammonium molybdate (ND) 4 NlO so that after calcination in the catalyst it is 9% MoO. The catalyst is evaporated to a paste, granulated, dried at 120 ° C, calcined for 4 hours and fractionated. Over 7 g of catalyst, 2 ml of propargyl alcohol are passed through and at 30ff C, 1.288 g of acrolein a is removed, which is 66.4%, and when the yield of acrolein is 69.7%.

Example 4 Amount of ammonium wolfgimate / impregnated on zeolitic carrier (NODO,. ,, -12.1 The mixture is thoroughly mixed, evaporated on WATER. JAR bath until formation of plastic mass, molded, dried, calcined at, 550 ° C 4 hours, then fractionated. When working on a catalyst with tungsten oxide () FipH 400 ° C, the yield of acrolein is 55.7%.

To obtain a carrier with a maximum ratio of 34.2: 1, proceed in the following way.

Example 5. Natural zeolite is treated b h b n. with a solution of hydrochloric acid in a thermostatic sucker with continuous stirring at 96 ° C. The carrier is filtered, washed with distilled water until the pH of the wash water is 5.6-6, -5, and dried at 120 ° C. The resulting zeolite carrier has a composition, wt.%: SVOn84,30; O i 4,20; CaO 0.52; MgO 0.34; 0.80; 1.00, with molar

v

  34.2: 1,

ratio

Days on the basis of catalysts; this support is impregnated with ammonium perrhenate solutions, ammonium tungsten and ammonium ammonium a solution according to the procedure specified in Examples 2,3,4,

PRA 14 EP 6, Through a reactor filled with a catalyst containing 10% MoO on a zeolite carrier (7 g), proparoyl alcohol in an amount of 2 ml is passed at a rate of 600 h at. The yield of acrolein is 89% at 400 ° C 90.6%,

Example 7. A reactor filled with a zeolitic catalyst, sob.arzha1Dim 9% / O under the same conditions, from 2 fvoi of propargyl alcohol at 1.55 ° C., 1.55 g of acrolein (conversion 81%) and at 400 ° C. - 1.77 g of acrolein (convert 93.3).

PREMIER 8.. In the case of PC1 on a catalyst containing 10.5% .. at a space velocity of 600 hours, the yield of acrolein is 93.1% at 300 ° C and 96% at

All catalysts exhibit a selectivity of 100% to the isomerization of propargm alcohol. Conversion of alcohol to acrolein reaches 96%. Formula inventions

The method of producing acrolein by isomerizing propargyl alcohol at elevated temperatures in the presence of an oxide catalyst on a silicon-containing carrier is also distinguished by the fact that, in order to simplify the process and to reduce the yield of the target product, the process at an ZbO-400 ° C temperature and 101z pressure is low. from., as a oxide catalyst, molybdenum oxide or volFram oxide or rhenium oxide is used, and as silicon 7407436

containing carrier - zeolitic Sources of information,

carrier with molar ratio taken into account during the examination.

SiO2 / Al2 O 20-34: 1 with the following

the ratio of components, wt.%:

Molybdenum oxide (or 1. Musseg A.V., Xipteridis V.Kh.

tungsten oxide, or Chuhaj m G.A. Heterogeneous conversion of rhenium) 9-10,5nie propargyl alcohol on the topCeto ity catalysts. -Arm.him.zh.,

the carrier of the Others 1975,28 (8), pp. 674-675 (prototype).

Claims (1)

Formula. Inventions of the radiation of acrolein of isomeryegyl alcohol at a temperature in the presence of a catalyst on silicon are distinguished, in order to simplify the yield, the process is carried out at a temperature of ~ C and a pressure of 10 as tungsten oxide, or as silicon. and with the process, and. product, temperature 300-400 15 mm Hg, to Ator al ali of molybdenum or rhenium oxide, and ³ 740 743 contain a carrier - zeolite carrier having a molar ratio of 5 different ₂ / _g About A1 = 20-34: 1, with the following component ratio, wt.%: Molybdenum oxide (or tungsten oxide or rhenium oxide) Zeolite carrier 9-10.5 Rest