SU1351932A1 - Method of producing 5-oxymethylfurfural - Google Patents

Abstract

The invention relates to heterocyclic substances, in particular the preparation of 5-hydroxymethylfurfural (MF), an intermediate product for the synthesis of polymers, plasticizers and other substances. To increase the yield of MF and reduce the time of hydrolysis of 3-5% aqueous pacTBOjia sucrose at 90-100 ° C in the presence of a catalyst (QD), an acrylamide copolymer, N, N-methyl bis (acryamisamide) and vanadyl-protoporphyrin-X complex (3-. 5 wt.%). CT take in the amount of 5 6 wt.% In relation to the mass of sucrose solution. The method allows to increase the yield of the target MF from 5 to 61% while reducing the process time from 5 to 4 hours. 3 table. 00 SP; about 00 ND

Description

one

135

The invention relates to an improved method for producing 5-hydroxymethylfurfural, which finds use as an intermediate product in the manufacture of polymeric materials, plasticizers and surfactants.

The aim of the invention is to increase the yield of 5-hydroxymethylfurfural and shorten the process time by using the vanadium-protoporphyrin complex IX complex as the metalloporphyrin complex.

The method is described in the following way.

The catalyst is obtained by the copolymerization of acrylamide, N., N-methylene bis-acrylamide with the vanadyl-protoporphyrin-iX complex in the presence of a redox system.

Example 1. Prepare three solutions. First: 60 g of acrylamide and 2 g of methylenebis-acrylamide in 240 ml of water; second: 5.8 g of glycine and 1.2 g of 2-amino-2 (hydroxymethyl) -1,3-propanediol in 200 ml of water; third: 8 g of ammonium persulfate in 200 ml of water. 200.100 and 200 ml of these solutions are respectively placed in a glass reactor, 1 ml of N, N, N, N -tetramethylethylenediamine and 40 ml of ethanol containing 2 g of vanadyl-protoporphyrin-IX are added. The contents of the reactor are stirred and maintained at 20 ° C for 15-20 minutes. The yield of polymer catalysis is 52 g. The yield is 19.2 ml in water.

Example 2. Analogously to Example 1, copolymerization was carried out in the presence of an ethanol solution of protoporphyrin-IX, not containing vanadyl. Thus, a carrier polymer is obtained. The consolidation of the vanadyl is accomplished by depressing the catalyst granules in the vanadyl sulfate solution.

within 1 day. The yield and characteristics of the catalyst are similar to the example.

Purification of the catalyst is carried out. in the following way.

The resulting polymer cell is crushed into granules. The separation of the redox system and monomer residues is carried out by washing the granules and the catalyst 2-3 times with clean water in a glass, followed by decantation and replacing the washing with a new one. Then the catalyst is washed from residual metal 9322

porphyrin with a 30% acidified solution of ethanol in water. After that, the catalyst is washed several times with clean water and dried in air. In the dry state, the catalyst is stable and can be stored indefinitely.

The structure of the catalyst containing 10th vanadyl-protoporphyrin-I complex;

- CH-i-CH

five

0

NH

CHn

I

I

CO

I

 -fcHrCHso

NH

: YNP I with

- CH2-CN - CH5 A-

NS - O-CH

II N

NgS-cHjl j n dfs

0 ..D --yo- N (T

N

NZS

CH2CH2S0011

NCS CH2CH2COOH

Example 3, Preparation of 5-hydroxymethylfurfural .. 1 liter of a 3% sucrose solution is placed in a forced circulation autoclave, heated

up to 100 C and pumped for 3 hours through a wide column with 0 g of catalyst — a three-cross-linked copolymer of acrylamide, W, N-methylenebis-acrylamide and vanadyl porphyrin complex with vanadyl porphyrin content in the catalyst 3 wt.%, Oxymethylfurfurol extract, extracts followed by distilling off the solvent.

hydroxymethylfurfurod, retic,

Example 4. A sucrose thief is placed in a forced circulation autoclave, heated to 90 ° C and pumped for 4 hours through a wide column with 50 g of catalyst — a three-linked N, N -methylene-bis-acrylamide and vanadyl porphyrin copolymer of acrylamide

13.0 g are obtained; ie, 59% of the theoI l of a 5% rast complex with a content of vanadyl porphyrin in the catalyst is 5% by weight. 22.5 g of hydroxymethylfurfural are obtained, i.e. 61% of theoretical.

Example 5. Similar to the conditions of example 2, the catalyst was repeatedly used, thoroughly rinsing it with water after each experiment. In the second, third, fifth, and decade of use, hydroxymethylfurfural is obtained with a theoretical yield of 61, 60.60 and 56%, respectively. Similarly, this catalyst can be used up to 15 times to obtain oxymethylfurfural with high yield.

The temperature range of the process is .90-100 C. At higher temperatures, the yield of the target product decreases, at lower temperatures, the duration of the process increases (see Table 1).

The content of vanadyl porphyrin in the catalyst is set in the range of 3-5 wt.%. A high content of vanadylporphyrin leads to a deterioration in the swelling capacity of the catalyst in water, a lower content - to a decrease in the concentration of catalytic centers. As a result, in both cases, the yield of the target product decreases (see Table 2).

Options

Amount of catalyst

r60

The concentration of sucrose in the initial solution, wt.%

Temperature,

/

The duration of the process, h, The concentration of hydroxymethylfurfural in the hydrolyzer, wt.%

The output of hydroxymethylfurfural,% of theoretical

32 4

The concentration of the catalyst is 5-6% by weight of the sucrose solution. A lower concentration of the catalyst leads to a decrease in the catalytic effect, and a large decrease in the filtration of the sucrose solution through the catalyst layers, as a result of which the yield of the target product does not increase (see Table 3).

Thus, the proposed method allows to increase the yield of the target product from 48-51 to 59-61% and reduce the duration of the process from 5 to 4 hours.

Claims (1)

Invention Formula The method of producing 5-oximes 1 furfural by hydrolysis of a 3-5% by weight aqueous solution of sucrose at 90–100 ° C in the presence of 5–6% by weight relative to the weight of the sucrose solution of the catalyst5, which is a three-acrylamide copolymer len-bis (acrylamide) and metal porphyrin complex containing 3–5 wt.% metal porphyrin, about 1 and thirty due to the fact that. In order to increase the yield of the target product and reduce the duration of the process, a vanadl-protoperphyry-like complex is used as a metal porphyrin complex (X complex. Table I  F The volume of sucrose solution 1 l 60 60 60 60 1.30 1.10 0.88 60 59 50 40 513519326 table 2 T Options. The volume of sucrose solution 1 l Vanadyl porphyrin concentration in the catalyst, wt.% 1 2 3 5 6 8 Duration process, ch6 4 3 2.5 2.52 The concentration of hydroxymethylfurfural in hydrolysate, wt.%. 0.97 1.10 1.30 1.32 1.19 1.05 The yield of hydroxymethylfurfurol,% of theoretical 44 50 59 60 54 48 Note, the amount of catalyst 60 .g; initial sucrose concentration of 3 wt.%; temperature T a b l and c 9 3 Options Amount of catalyst r30 Duration of pro- Cessa, p2,5 Hydroxymethyl concentration furfural in hydrolysis, wt.% 0,99 The output of ximetiffurfural,% of theoretical 46 Note. Baseline sucrose concentration 3 wt.%; temperature 100 ° C; the content of vanadyl porphyrin in the catalyst is 5 wt.%. Compiled by I.Di chenko Editor E.Sligan Tehred A..Kravchuk Proofreader, Shekmar Order 5538/21 Circulation 372Subscription VNIIPI USSR State Committee for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5 Production and printing company, Uzhgorod, Projecto st., 4 The amount of sucrose solution 1l