SU1792923A1 - Method of group element extraction from natural waters and sewage - Google Patents

Description

The invention relates to methods for group recovery of elements of Pb, Co, Cd, Mo, Fe, Zn, N1, Cr) from natural and hollow (Sewage waters.

The goal is to increase selectivity and recovery. This goal is achieved by the method of extraction preSP known methods of group extraction of elements using various polymer chelate sorbents.

However, these methods do not provide spurious elements from solutions by introducing

high selectivity and completeness extracted! ba l!

nickel, chromium in the presence of macro amounts (item 10 ⁶ %) of other elements.

non-trace elements: copper, lead, cattle, cadmium, manganese, iron, zinc,

The closest in technical essence and the achieved effect to the proposed method is a group recovery of elements, mainly for their subsequent analytical determination, by introducing a polymeric chelated sorbent - polystyrene am1 | 1no-4-nitro-6-sulfophenol.

of the polymeric chelate sorbent prlistirol-azo-2-hydroxy-3-methyleneiminodiacetic acid, the sorption is carried out first at pH 1.5-3.0 and then at pH 5-7.5 at room temperature for 120 minutes. New chelate sorbent polystyrene-azo2-0 xi-3-methyl ene and nodiacetic acid: (CV ^ COOH) ₂ HC / ^ N = N- <C ^ -0H

1792923 A1, However, this method does not have sufficient selectivity for the extraction of these elements, since it does not extract lead, cadmium and chromium.

It is a fine powder of dark brown color, insoluble in water, acids, alkalis and organic solvents.

The sorption capacity of the sorbent for recoverable metals is 12.9 mg Σ

Cu, Pb, Co, Cd, Mn, Fe.Zn, Ni, Cr / g of sorbent.

The dependence of the degree of sorption on the pH of the medium is presented in table I. Quantitative sorption (R = 95-100%) is observed in the following pH values: for copper 1.5-3.0: for lead 4.0-7.0: for cobalt 6.5-10.0; for cadmium 2.0-4.5: for manganese 2.5-5.5: for iron 1.5-3.0: for zinc 2.0-4.0: for nickel 4.5-10.0; for chromium 1.0-3.0.

Joint quantitative extraction of Cu, Pb, Co, Cd, Mn, FeZn, Ni, Cr occurs in the range of pH 1.5-3.0, and then at pH 5.0-7.5.

Table 2 presents comparative results on the selectivity of group sorption of Cu, Pb, Co, Cd, Mn, Fe, Zn, Ni, Cr by the proposed sorbent and the most widely used polystyrene-imino-4-nitro-6sulfophenol, as well as polymer thioether. From the table it follows that the selectivity of the group sorption of these elements by the proposed sorbent is an order of magnitude higher than the known sorbents. The proposed method allows the quantitative extraction of Cu, Pb, Co, Cd, Mn, Fe, Zn, NI, Cr from natural and waste waters in the presence of p10-p10-fold excess quantities

Ca, Mg, K, Na, Sr, Ba.LI, Mo, AI, TI,

The essence of the method is that in the analyzed water, after creating the appropriate medium with a pH of 1.5-3.0, add 100 mg of sorbent, the mixture is stirred for at least 50 minutes at room temperature, then at pH 5.0-7.5 stirred for another 60 minutes After which the solution is filtered through a white ribbon filter, the concentrate is washed with water and the elements are stripped with 2 M HCI. In the eluates, elements are determined by atomic absorption spectroscopy or any other suitable method.

Example, Determination of copper, lead, cobalt, cadmium, manganese, iron, zinc, nickel, chromium in natural and waste waters.

To 500 ml of analyzed water, adjusted to a pH of 1.5-3.0 1 M HCI, 100 mg of the sorbent polystyrene-azo-2-hydroxy-3-methyleneiminodiacetic acid is added. The solution was stirred on a magnetic stirrer for 60 m.in, after which the pH was adjusted to 5.0-7.5 1 M NaOH and stirring was continued for 60 minutes. Stirring is carried out at room temperature. The sorbent is filtered through a white ribbon filter, the concentrate is washed 3-4 times with distilled water and Cu, Pb.Co, Cd, Mn, Fe, Zn, NI, Cr 2 M HCI are stripped.

In the resulting solution, the elements are determined by atomic absorption spectroscopy, the work was carried out with a three-gap burner in an acetylene-air flame. Sources of resonant radiation were hollow cathode tubes. Table 3 presents the results of the determination.

Cu, Pb, Co, Cd, Mn, Fe, Zn, NI, Cr in standard samples certified for the content of these elements.

The synthesis of a new sorbent of polystyrene-2-hydroxy-3-methylene iminodiacetic acid is given below:

A. Preparation of Intermediate 2-hydroxybenzylamine diacetic acid The drug was obtained by the interaction of phenol with formaldehyde and iminodiacetic acid according to the Mannich reaction.

In a three-necked flask with a capacity of 500 ml. equipped with a stirrer, dropping funnel, thermometer, and placed in a bath, 18.8 g (0.2 M) of phenol are dissolved in 100 ml of glacial acetic acid with stirring. Then, an aqueous solution of the iminodiacetic acid monosodium salt is poured into the flask, prepared as follows: 27 g (0.2 M) of iminodiacetic acid is placed in a glass, 30 ml of distilled water are poured into the flask, and the suspension is neutralized by stirring with a 30% sodium hydroxide solution. up to pH 7-8 for universal indicator paper. The contents of the flask are cooled in an ice bath to 5-10 ° C and, maintaining this temperature, 15 g (0.2 M) of a 37% formaldehyde solution are added dropwise over 20 minutes with stirring. The temperature in the bath is raised to 20 ° C and the solution is stirred at this temperature for 2 hours. • Stir in a porcelain cup and evaporate in a water bath until a wet precipitate forms. Add 500 ml of ethanol, stir and filter the precipitate on a No. 2 glass filter. The precipitate is wrung out and washed with acetone. The yield of the air dry preparation is 59-60 g.

B. Diazotization of the styrene aminopolymer with divinylbenzene. 3 No. 31 g (0.2 M) of the hydrochloride salt of the styrene amino copolymer with DVB macroporous structure of composition 15/100, mixed with 300 ml of water and 40 ml of conc. HCI. The mixture is cooled in an ice bath and at a temperature of 0-5 ° C diazotized with a solution of 14 g of No. N02 (0.2 M) in 50 ml of water added over 2 hours. The diazotization reaction is monitored using iodine starch paper until a clear blue color occurs. The diazotized copolymer is filtered off, washed with water and used in the azo coupling reaction with 2-hydroxybenzyl-iminodiacetic acid.

B. Azo coupling of a diazotized styrene copolymer with DVB. Dissolve 48 g (0.2 M) of 2-hydroxybenzyliminolylacetic acid in 500 ml of water and neutralize with a 20% NaOH solution to pH 7-8. The solution is cooled in an ice bath to 0-5 ° C. Then, with stirring, a diazonium copolymer of styrene with DVB and at the same time a 20% solution of IgCO3 are added to the solution of the nitrogen component while maintaining a pH of 9-10. Azo coupling is carried out at 0 ~ 5 ° С for 6 h and then at room temperature for 12 h. Then, the precipitate is filtered off on a No. 4 glass filter and washed repeatedly with water, 2 M HCI and again with distilled water until the colored organic impurities are removed. The yield of 5 air-dry preparation of the sorbent of polystyrene-azo-2-hydroxy-3-methylene iminodiacetic acid is 31-32 g in the form of a fine powder of dark brown color.

Claims (2)

Claim 1. The method of group extraction of elements from natural and wastewater by sorption with a polymeric chelate sorbent ', characterized in that, in order to increase the selectivity and degree of extraction, polystyrene-azo-2-hydroxy-Z is used as a polymer sorbent -methyleneiminodi acetic acid, and sorption is carried out first at pH 1.5-3.0 and then at pHJ5-5.7, 2. The method according to claim 1. Characterized in that the sorption is carried out at room temperature for 120 minutes Table 1 Dependence of the degree of sorption of Cu, Pb, Co, Cd, Mn, Fe, Zn, NI, Cr polystyrene-azo-2-hydroxy-3-methylene iminodiacetic acid on the pH of the medium. Sorption conditions: The volume of the solution is 50 ml, the mass of the sorbent is 100 mg, the stirring time is 120 minutes at room temperature. pH The degree of sorption (R),% environment Si Pb With Cd Mp Fe Ζπ Νί Cr 1,0 20,0 50,0 15.0 25.0 25.0 25.0 35.0 30,0 95.0 1,2 50,0 53.0 17.0 40,0 35.0 30.0 45.0 43.0 100.0 1.5 95.0 60.0 21.0 50,0 45.0 95.0 65.0 53.0 100.0 2.0 100.0 66.0 30,0 95.0 73.0 100.0 95.0 60.0 100.0 2,5 100.0 72.0 35.0 100.0 95.0 .100,0 100.0 67.0 100.0 2.7 100.0 78.0 38,0 100.0 100.0 100.0 100.0 78.0 100.0 3.0 95.0 80.0 43.0 100.0 100.0 95.0 100.0 81.0 95.0 3,5 90.0 90.0 50,0 100.0 100.0 45.0 100.0 87.0 95.0 4.0. 83.0 95.0 57.0 100.0 100.0 30,0 95.0 92.0 70.0 4,5 78.0 • 100.0 65.0 95.0 100.0 25.0 95.0 95.0 60.0 5,0 74.0 100.0 71.0 90.0 100.0 20,0 85.0 100.0 50,0 5.5 70.0 100.0 79.0 80.0 95.0 18.0 75.0 100.0 40,0 6.0 66.0 100.0 87.0 70.0 90.0 17.0 65.0 ιοο; ο 35.0 6.5 63.0 100.0 95.0 63.0. 80.0 15.0 60.0 100.0 35.0 7.0 60.0 100.0 98.0 53.0 72.0 10.0 50,0 100.0 35.0 7.5 58.0 95.0 100.0 41.0 65.0 10.0 45.0 100.0 35.0 8.0 55.0 75.0 100.0 30,0 60.0 10.0 40,0 100.0 35.0 8.5. 55.0 70.0 100.0 25.0 58.0 9.0 37.0 100.0 35.0 ί 9.0 55.0 68.0 100.0 20,0 57.0 9.0 35.0 100.0 35.0 9.5 , 55.0 66.0 100.0 15.0 56.0 8.0 , 33.0 100.0 35.0 : Yu.O. 55.0 64.0 100.0 10.0 55.0 • 8.0 32,0 100.0 35.0 Ί Sorption selectivity Σ Cu, Pb, Co, Cd, Mn, Fe, Zn.NI, Cr by polymer chelate sorbents. table 2 Element (Me). Selectivity factor [Me]: [Σ Cu, Pb, Co, Cd, Mn, Fe, Zn, Ni, Cr] Suggested sorbent * Polystyrene-methylene-4-nitro-6-sulfophenol Polymer Thioether Na • π 10 ⁵ π 10 ⁴ π 10 ⁴ TO π 10 ⁵ π 10 ⁴ π 10 ⁴ Mg π 10 ⁴ π 10 ⁴ π 10 ⁴ Ba π 10 ⁴ π 10 ⁴ π 10 ⁴ Sa π 10 ⁴ π 10 ² π 10 ⁴ Al P 10 ² π 10 ² π 10 ³ Cg (U I) 'π 10 ⁴ π 10 ² π 10 ' ¹ Cr (lll) π 10 π 10 π 10 ' ¹ Sr π ΊΟ ⁴ π 10 ⁴ π 10 ' ¹ Li π 10 ³ π 10 π 10 ' ¹ Mo π 10 ⁴ π 10 ⁶ π 10 ' ¹ Ti π 10 ⁴ π 10 ⁶ π 10 ' ¹ so? • π 10 ⁶ π 10 ⁴ π 10 ⁴ ροΛ π 10 ⁶ π 10 ⁴ π 10 ⁴ F π 10 ⁴ π 10 ⁴ π 10 I * Polystyrene-azo-2-hydroxy-3-methyleneiminodioacetic acid Table 3 The results of determination of Cu, Pb, Co, Cd, Mn, Fe, Zn, NI, Cr in standard samples of the composition of aqueous solutions of metal salts (Volume = 100 ml, n = 10, P = 0.95). An object Content according to the passport, mg / l Found ’by the proposed method, mg / l Sr 1 2 3 4 GSORM-23 GSORM-24 GSORM-26 Cadmium I Manganese. 1.0 ± 0.01 1.0 ± 0.01 1.0 ± 0.015 1.0 ± 0.013 0,025 0,022 Continuation of table.Z i ¹ 2 3 4 Lhlihk 1.0 ± 0.01 1.0 ± 0.012 0.016 Ci • Indian 2.0 ± 0.02 2.0 ± 0.035 0,062 Ks balt 1.0 '± 0.01 1.0 ± 0.03 0,027 Μ eat • 1.0 ± o, oi; - 1.0 ± 0.03 0,025 Iron 1.0 ± 0.01 1.0 ± 0.04 0,038 Η lkel 1.0 ± 1.01 1.0-- ± 0.02 0,026 Xi ) 0M 1.0 ± 0.01 1.0 ± 0.013- 0,021