SU782297A1 - Process for preparing methylethyl ketone - Google Patents

Abstract

1. METHOD OF OBTAINING MEMO OF ETHYLKETON nyt dehydration of 1.3-6-utandiol at a temperature of 9 in the presence of oxide copper-chromium-containing katrye trr at a volumetric feed rate of 0.1-3.0 h in the presence of nitrogen and with the fact that, in order to increase the exhaust of the target product, a catalyst is used as an oxide honey 4 zinc-containing catalyst that additionally contains oxide in the following ratio of components, wt.%: CuO 35-42, 2gCO 25-29, 1-2, AljO, 30 -36, and the process is carried out at 5b-270®s.

Description

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| This invention relates to organic chemistry, in particular to an improved method of producing ketones, which are widely used in industry as solvents. A known method for the preparation of methylethyl ketone (MEK) by dehydrating 1,3-butanediol to a catalyst system comprising Cu, Co, NI, Pi, or Zn on nisMae or silica gel, the process being carried out at 150 ° C ° C. The composition of the catalyst is not specified. The disadvantage of this method is the low yield of MEK (74% of the theoretically possible). The method closest to the pre-parangamide method is the production of methyl ethyl ketone by dehydration of 1,3-butanediol on zinc copper oxide catalyst containing 78-82 wt.%, Wt.%, 7po 6-8 wt.%, While the process is carried out in the gas phase at a temperature of re 210-240 s, the volumetric feed rate is 0.1-3.0, in the presence of at a feed rate of IfO50, 0 m kg-h. The disadvantages of this method are the high yield of n-mas al dehydration (8–16% of theory, which significantly complicates the system for the division of pure IEC. In addition, the yield of the latter does not exceed 82–83% of the theoretically possible. The aim of the invention is to increase the yield of methyltilton ketone. T - Set Goal achieved by the fact that when carrying out the method of producing methyl ethyl ketone by dehydrating 1,3-butanediap at elevated temperature in the presence of an oxide copper-zinc-containing catalyst at a volumetric feed rate of O, -1-3, O h in the presence of nitrogen at a feed rate of 1.050, 0 m /to MS as oxide. a copper zinc-containing catalyst uses a catalyst that additionally contains alumina in the following ratio of components,%: CuO 35-42, Zn O 25-29, Cr2Oz 1 2, AlgOj 30-36, and the process is carried out in the gas phase at a temperature of 150270 ° C and atmospheric pressure. The catalyst is prepared from natural methods by mixing a co-centrated solution of metal nitrates (copper, zinc and aluminum) with oxalic acid, drying, calcining, mixing with copper dichromate solution, graphite and tablet catalytic mass. The catalyst is used in industry and in the process of Low-Temperature Conversion carbon monoxide.

782297 The effectiveness of the proposed method is illustrated by the following examples. Example 1 (for comparison J. A cathesing agent of known composition, wt.%: CoO 78.0, Ct-16, 6.0, is loaded into a flow-type reactor. Freshly distilled 1,3-butanediol is fed to a reduced hydrogen at 180-2 ° C. characteristics: t, bale 200-203 s, nj 1.4367, d 1.0053 in the amount of 120 g / h. Reaction temperature 160 ° C, atmospheric pressure, volumetric rate 0.1 hG, nitrogen supply rate 50. Dehydration balance Loaded, g (1,3-butanediol 120.0 (100.0); total 120.0 (100, OK Received, g (%): IEC 77.04 (64.20), acetone 4.56 (3 , 80), n-butyric aldehyde 14.76 (12.30), water 21.84 (18.201, gas 0.60 (0.50 ;; prteri 1.20 (1.00); total 120.0 (100.0 ;. 75.9 g of IEC 79.1% of the theory for the initial 1,3-butane-1ol) are separated from the resulting catalyzate by distillation with the following indicators: t, bale. 79 ,, p 1.3788, 804. Example 2 (for comparison, a known catalyst of composition, wt.%: CuO 80.0, Cr2O5 13.0, Zn O 7.0, is charged to a flow type reactor. On the reduced hydrogen at 180-260 ° C. The catalyst serves 1,3-butadiol with characteristics as in example 1, in an amount of 120 g / h o The reaction temperature, a space velocity of 2.4 hours, the feed rate of nitrogen 20. Balance dehydration. Loaded, g (.%): 1,3-butanediol 120.0 (100.0); total 120.0 (100.0 |. Obtained, g (%): methyl ethyl ketone 78.72 (65.6), acetone 2.88 (2.4 /,: n-butyric aldehyde 13.44 (11.2 (v) 22.32 (18.6), gas (0.84 (0.7), loss: 1.80 (1.5); total 120.0 (100.0). From the resulting catalyzate of rectification, 77, 5 g of MEK (80.8% of the theory of the initial 1, 3-butanediol) with the following characteristics: bp 79.5 ° C n | I 1.3787, df 0.805. P. Example 3. A flow type reactor is loaded catalyst composition: wt.%: CuO 35.0, A12Oz 36.0, Oi 2.0.0 p, about 27.0. 1,3-butanediol with characteristics as in example 1 is fed to the catalyst reduced by 180-260 with hydrogen. in the amount of 120 g / h. Temperature reaction 150 C, volumetric rate 0.1 h, l ... J t V. ..jjf l., nitrogen supply rate 50. Dehydration balance. Loaded, g (%): 1,3-butanediol 120.0 (100, 0); total 120.0 (1 O, 0 Received, g (%): methyl ethyl ketone: 83.2 (69.3), acetone 11.2 (9.3), n-butyric aldehyde 1.6 (1, 4), water 20.6 117.2), gas 2.2 (1.8); | loss 1.2 (1.0, total 120.0 (100 01,. From the obtained catalyzate, distillation resulted in 81.9 g IEC (85.3% of theory) with the following characteristics: bp. 79.6 C, rtSf 1.3788, df 0.804. Example 4. A catalyst in a flow-type reactor was loaded with the catalyst, wt.%: CuO 42.0, MgO 32.0, Cr2 Oj 1.0, Zr O 25.0. At the reduced hydrogen at $ 180-260, the catalizer is supplied with 1,3-butanediol with the characteristics as in example 1, c. the amount of 120 g / h. The reaction temperature is 220 ° C, the volumetric rate is 0.5 h-, the feed rate of nitrogen is 5 m / kg-h. Loaded, g (%): 1,3-butanediol 120.0 (100.0); total 120.0 (100.0), Obtained, g (%): methyl ethyl ketone 85.4 (71.2 /, acetone 6.0 (5.0), n-butyric aldehyde 1.8 (1.5) , water 21.4 (17.8), gas 3.0 (2,. loss i, 4 (2.0); total 120.0 (100.0). From the resulting catalyzate, 84jl g of MEK (87 , 6% of theory I with the following characteristics: boil 79.5 s, p 1.3787, df 0.806. Example 5. In a flow reactor, the catalyst is loaded, weight,%: Cu 39.5, 30 , 0, .i fi O 29.0. On a hydrogen reduced at 180-260 ° C, the catalyst serves 1,3-butanediol with the characteristics as in example 1, in a quantity of 120 g / h. Temperature 7; reactions, volumetric speed 3.0 H, s Nitrogen feed rate of 1 m VKr h. Balance of dehydration, Loaded, g (%): 1,3-butanediol 120.0 (100, total 120.0 (100.0). Received, g (%): methylztilketone 84.7 (70.7), acetone 7.4 (6.2), n-butyric aldehyde 1.1 (0.9, water 21.2 (17.6), gas 3.6 (3.0) -, porety 2.0 (1.6); total 120.0 (100.0). 83.4 g of IEC (87.0% of theory / s following) are obtained by distillation; 79 ,, n 1.3789, 6.806. Example 6. In the flow type reactor load the catalyst composition, wt.% CuO 37.0, A12Oz 33.0, 2.0, 2 "O 28.0. A 1, 3-butanediol with the characteristics as in Example 1 in an amount of 120 g / h is fed to the catalyst reduced by hydrogen at 180–26 ° C. The reaction temperature is 220 ° C, the volumetric rate is 2.0 h, the feed rate is 20 MVKr. h. Balance dehydration. Loaded, g (%): 1,3-butanediol 120.0 (100, Oh total 120.0 (100.0). Received, g (%) .: methyl ethyl ketone 85.0 (70.8), acetone 7, 2 16.0), n-aldehyde oil .2.0 (1.7), water 21.0 (17.5), gas 2.4 (2.0); loss of 2.4 (2.0); total 120.0 (100.0). From the obtained catalyzate by distillation, 83.7 g of MEK (87.2% of theory) were isolated with the following characteristics: bp, 79.5 ° C, n 1.3787, 0.804. The results of the dehydration of 1,3-butanediol are given in the table.

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Claims (1)

1. METHOD FOR PRODUCING METHYLETHYL KETONE by dehydration of 1,3-butanediol at elevated temperature in the presence of an oxide-copper zincchromium-containing catalyst at a bulk feed rate of 0.1-3.0 h ** in the presence of 'nitrogen, melting and The reason is that, in order to increase the yield of the target product, a catalyst additionally containing aluminum oxide in the following ratio of components, wt.%: CUO 35-42, 'ZnO 25-29, С2 ₂ О _{Э will be used} as an oxide copper-zinc-chromium catalyst 1-2, AljOa 30-36, and the process is carried out at * 50-270®s. m 00 th ju <1