SU1122644A1 - N-(beta-hydroxyethyl)-glucamine as starting products for synthesis of boron-selective sorbent - Google Patents

Abstract

M-(p)-Oxyethyl)-glucamine of the formula (OH)4-CH2-III-CH2-CH2-OH as a starting product for the synthesis of a boron-selective sorbent.

Description

1

The invention relates to a new compound N-(p-oxyethyl)-glucamine of the formula, not described in the literature

CH20H- CH(OH)4-CH,2-NH-CH -CH2-O

which can be used as a starting product for obtaining a boron-selective sorbent, which, in turn, is used in the processes of purifying natural and industrial water from boron compounds.

The use of 4-methylglucamine as a starting product for the synthesis of sorbent 15 is known.

However, the sorbent obtained on its basis has a reduced capacity for boron.

The aim of the invention is to find a new starting product for obtaining a sorbent with improved sorption capacity for boron.

The set goal is achieved by a new compound N-(|J-oxyethyl)glucamine.

M-(p)-hydroxyethyl)-glucamine is obtained by the known method C 23 in two successive stages.

In the first stage, glucose is condensed with monoethanolamine in an aqueous medium. The reaction is carried out at room temperature and atmospheric pressure for 1-1.5 hours with constant stirring. The resulting condensate, containing an aqueous solution of N-(|1-hydroxyethyl)-glucamine, is hydrogenated in the second stage to a secondary amine at 70-80°C and a pressure of 5.0-10.0 MPa in the presence of skeletal nickel. Both stages of the process are carried out periodically in a glass and steel reactor. The reaction product N-(p-hydroxyethyl)-glucamine is obtained after distillation of water, precrystallization from a saturated sodium solution and drying with a purity of up to 94.3%.

The obtained N-(/1-hydroxyethyl)-glucamine is loose yellowish crystals and has the following characteristics: mol.m 225; melting point 89-91C; total nitrogen content 6.08%; secondary and tertiary nitrogen 5.92 and 0.16%, respectively; content of the main substance 94.3%.

26442

The new compound K1-(/1-hydroxyethyl)glucamine can be used as a starting material for the synthesis of a new boron-selective sorbent. The synthesis consists of amination of NT (1-hydroxyethyl)-glucamine of a chloromethylated copolymer of styrene with divinylbenzene.

Example 1. An aqueous solution of monoethanolamine (450 g of monoethanolamine in 1050 g of water) is loaded into a 3-liter glass reactor equipped with a reflux condenser, funnel, and stirrer. While stirring, 1327 g of glucose is added through the funnel. After the entire portion of glucose has been added, stirring is continued for 1.5 hours.

The obtained aqueous solution of M-(roxiztil)-glucamine in the amount of

2827 g are sent for hydrogenation to a batch reactor with an electromagnetic drive. The leached skeletal material is also transferred here.

5 nickel catalyst in an amount of 4% of the weight of the compound being hydrogenated.

The skeletal nickel catalyst is prepared by leaching the alloy (TU 485-76-73) grade H 45A-55, containing 45% nickel and 55% aluminum. 2.5 l of a 20% aqueous solution of caustic soda are poured into a three-necked flask equipped with a reflux condenser, stirrer and funnel and 1000 g of the alloy are added for t h, activation

5 conducts until 20% of aluminum is leached, which is controlled by the amount of hydrogen released using a gas clock.

The hydrogenation reaction is carried out in

intensive hydrodynamic mode at 75°C and a pressure of 10.0 MPa until complete absorption of hydrogen. Under these reaction conditions, the final product is formed in the amount of 1257.9 g

5 with a yield of 87.5%, 179.7 g (12.5%) of polyamine hydroxide, the catalysate is subjected to vacuum distillation to remove water, the solid still residue is recrystallized from a saturated alcohol solution, filtered and dried in a vacuum desiccator at 50°C. Light loose crystals are obtained in an amount of 1150.1 g containing 94.5% of the main substance N-(|3-hydroxyethyl)-glucamine and 5.5% of tertiary amine.

Example 2, Condensation of glucose with an aqueous solution of monoethanol3

The amine is carried out under the conditions of Example 1. The resulting aqueous solution of 4-(p1-hydroxyethyl glucamine in an amount of 2827 g is hydrogenated in an autoclave in the presence of a skeletal nickel catalyst at 80 °C and a hydrogen pressure of 5.0 MPa until complete absorption of hydrogen. The hydrogenate contains 1178.8 g (82%) of secondary amine, 258.8 g (18%) of polyamine compound. After distilling off water and recrystallizing from a saturated alcohol solution, the catalyzate is dried in a vacuum desiccator at . Light loose crystals are obtained in an amount of 1006.3 g, containing 89.9% of the main substance and 10.1% of tertiary amines.

Example. A solution of chloromethylated styrene copolymer with 10% divinylbenzene, obtained in the presence of 100 vol.% H-decane, is kept for 1 h in 0.01 ml dimethylformamide (DMF) for swelling. 30 g of N-(p-oxyethyl)-glucamine dissolved in 50 ml DMF are added to the resulting mixture. The amination reaction is carried out for 10 h at 90 ° C. The finished anion exchanger is filtered, washed with water and analyzed. Nitrogen content is 4.69%. The sorption capacity for boron extraction from solutions with a boron concentration of Cg of 100 mg / l is 32 mg / g, from solutions with Cg of 10 mg / l - 10.5 mg / g.

Example A. A solution of chloromethylated copolymer of styrene with 12% divinylbenzene, obtained in the presence of 80 vol.% BN-1 gasoline, is kept for 1 hour in 30 ml of dimethyl sulfoxide (DMSO) for swelling. 30 tons of N-(p)-oxyethyl)-glucamine, dissolved in 40 ml of DMSO, are added to the resulting mixture. The amination reaction is carried out for 10 hours at 90°C. The finished anion exchanger is filtered, washed with water and analyzed. The nitrogen content is 4.54%. The sorption capacity for boron extraction from solutions with a boron concentration of C 100 mg/l is 35 mg/g, from solutions with Cu 10 mg/l 8.7 mg/g.

Example 5 (for comparison). A sorbent is synthesized using the known product f-methylglucamine (based on the copolymer of Example 3). 10 g of chloromethylated copolymer of styrene with 10% divinylbenzene, obtained in the presence of

100 vol.% n-decane is added to the resulting mixture, and allowed to swell in 30 ml of dimethylformamide for 1 hour. 30 g of N-methylglucamine are added to the resulting mixture.

The amination reaction is carried out for 15 hours at 90C. The finished sorbent is filtered, washed with water and analyzed. Nitrogen content is 4.42%. JQ Sorption capacity for boron extraction from solutions with a boron concentration of C 100 mg/l is 25 mg/g, from solutions with C 10 mg/l is 8.0 mg/g.

Thus, the tests showed that the sorbent obtained on the basis of N-(p,-oxyethyl)-glucamine has an increased capacity for boron. The determination of the sorption capacity for boron is carried out in accordance with TU 6-05-211-1221-81. The method is based on the complexation of boron with mannitol.

Method for determining the concentration of boric acid.

25 100 ml of boric acid solution are titrated with 0.1 N hydrochloric acid solution in the presence of methyl red until the indicator changes color, then another 0.5 ml is added. The flask is boiled for 10 min with a reflux condenser. Then the excess hydrochloric acid is neutralized with 0.02 N NaOH until a yellow color appears. Then 4 drops of phenol red solution are added and neutralization is continued until a red color appears. 1 g of mannitol is added to the flask and mixed. If the color has changed, titration is performed with NaOH solution until a red color appears. Then 1 g of mannitol is added again and titration is carried out. Additions of new portions of mannitol and titration are continued until the solution stops changing color.

a -T -YOO

s V

where a is the total amount of 0.02 n,

NaOH solution, ml; T - titer of 0.02 N NaOH solution,

mgV/ml; V is the volume of water taken for determination.

division.

Conducting tests of anion exchange resin under dynamic conditions.

The anionite is loaded into a column filled with distilled water and connected to a pressure tank.

containing a solution of boric acid with a concentration of 10 mg B/l. The solution is passed from top to bottom with a specific load of 5 ml/ml.g. In the filtrate, which is collected in portions of 250 ml, the boron content is determined using the described method. By summing up the number of portions in which boron is not detected, the volume of the filtrate before the VP breakthrough is determined.

The dynamic sorption capacity before breakthrough, mg/ml, of the anion exchanger is determined by the formula

npF - - °DCE -,

"n

where C is the concentration of the solution

boric acid in terms of boron, mg/l;

- volume of boric acid solution passed through the anion exchanger, l;

V,

- volume of anion exchanger.

ai

emergency

Conducting tests of anion exchange resin under static conditions.

1 g of anionite in a flask is poured with 100 ml of boric acid solution and kept for 24 hours. Then the solution is separated and the concentration of boron in it is determined. The amount of extracted boron and, accordingly, the sorption capacity of the anionite in mg-Zq/g are determined by the difference between the initial and final concentrations.

As can be seen from examples 3-5, the sorbent obtained on the basis of -(rgsk ethyl)-glucamine has an increased capacity for boron.