A method of obtaining modified sorbents

 

(57) Abstract:

Use: production of sorbents based on strong basic anion polymerization, the water in the purification of drinking water, wastewater. The inventive modification of highly basic polymerization anion exchange resin in hydroxyl form carry out processing in static conditions 4,5 - 5,5% solution of ferric chloride once when the ratio of solid - liquid 1 : 12-1 7,then washed once with water at 75 - 95oC, then once treated with alkali at a ratio of solid - liquid 1 : 0,8-1,2, followed by washing with water and transfer to the salt form. table 2.

The invention relates to a process for the production of sorbents based on strong basic anion polymerization. The proposed sorbents can find application in water treatment in the purification of drinking water and wastewater.

A method of obtaining a modified ion exchange resin by treatment with strong base anion polymerization in Cl--form solution of sulphate of iron (III) with a concentration of 4 to 5 g/l at a pH of from 1.8 to 2.0 for 12 - 16 hours [1]. In the ion exchanger are formed fragile complex compounds with iron and it gets way what about the thiocyanate ions is 160 volumes of solution, containing ions SCN-the amount of sorbent. The concentration of SCN-is 0.2 g/l Anion exchange resin is treated with a solution of sulphate of iron (III) in static conditions. Washing the resulting product is produced in a dynamic environment, a small amount of distilled water.

The disadvantage of this method of sorbent impurities from water is that the resulting material can not work in a wide pH range, supplied to it solutions. He is operable in a neutral environment because of the low resistance formed on the anion exchange resin of iron compounds. In addition, the process of obtaining long-term, and the resulting sorbent does not allow sverkhekvivalentnoi to absorb sulfide ions.

A method of obtaining ferromagnetic exchange resin by treating the resin in Cl-form the mixture of the solutions of the chlorides of iron (II) and (III) in the ratio 1 : 2 with a concentration of 20 - 30% and subsequent treatment with alkali concentration of 12 - 17% in static conditions [2]. After the formation of magnetite in the ion-exchange resin it is treated with NaCl concentrations of 10% for payment in Cl--form. The static exchange capacity of the anion exchange resin is practically not reduced.

This method of producing anion exchange resin, Modific is a consequence of its sorption capacity for sulfide and thiocyanate ions is low. In addition, the use of a solution of chloride of iron (II) and (III) with a concentration of 20 to 30% causes the formation of precipitation in the phase of anion exchange resin and in solution phase, which increases the consumption of reagents and reduces the amount of iron hydroxide in the phase of the anion.

Analysis of the current level of technology shows that closest to the proposed technical solution is the method of obtaining modified hydroxide iron (III) sorbent impurities sulfides from water [3] on the basis of highly basic polymerization, anion exchange resin in hydroxide form type AB-17-10P by processing it in dynamic conditions in the column with a solution of ferric chloride (III) 4,5 - 5,5% concentration of 10 volumes on the volume of anion exchange resin, washing with water in a quantity of 25 volumes per volume of sorbent, treatment with alkali concentration of 4.5 - 5.0% in the amount of 20 volumes per volume of sorbent, washing with distilled water in an amount of 25 volumes per volume of sorbent and translation in the salt form.

In the modification get the sorbent, which allows for the amount of downloads 10 cm3, initial ion concentration S2-equal to 10 mg/DM3and the speed of filtration 9 m/h (6 ml/min) to reduce the concentration of sulfide ion 90 - 95% at the responsive is m this method, the sorbent is involuntarily large consumption of reagents for modification and as a result, a significant amount of wastewater. The total consumption of reagents and wash water is 80 volumes to 1 volume of the sorbent prior to transfer into the salt form.

The disadvantage of this method, the sorbent is also the duration of the process (at least 24 hours) and the heterogeneity of the obtained product from one technological cycle (iron content in the final product in the samples ranges from 0.2 to 0.5 wt.%). The heterogeneity of the product significantly reduces the sorption capacity and stability during water treatment.

In this regard, there is a technical problem - the development of a method of producing a sorbent impurities from water at improving the quality of the finished product.

The essence of the invention is that the processing of highly basic polymerization, anion exchange resin in hydroxyl form is carried out in static conditions under stirring once with a solution of ferric chloride (III) 4,5 - 5,5% concentration with the correlation of phases T : W from 1.0 to 1.2 to 1.1 : 1,7, followed by a single washing of the sorbent demineralized water at a temperature of 75 - 95oC and subsequent single treatment with alkali to 4.5 - 5.0% concentration with the correlation of phases T : W 1.0 : 0.8 to 1.0 : 1,2. Next Sarbinowo sorbent is carried out in accordance with the conditions of the experiment for determination of the sorption capacity of the sorbent of the known technical solutions [3]. In column load 10 cm3the sorbent is passed through the solution containing 10 mg/DM3ions S2-when the speed of the filter 9 m/h (6 cm3/min). Define the content in the filtrate is the number of ions in accordance with [3]. The stop passing the solution by increasing the concentration of ions in the filtrate above 0.5 mg/DM3. Determine the number of missing volumes of solution per volume of the loaded sorbent.

The amount of sorption capacity on the thiocyanate ions is carried out in accordance with examples of technical solutions [1]. In a column load of 1 g of sorbent and passed through it at a rate of 1 ml/min solution containing 5 g/l ion KNO3, 5 g/l K2SO4, 0.2 g/l NH4CNS. The filtrate determine the content of the CNS-ion-known method. Filtering is terminated by the appearance of ions CNS-in the filtrate.

Determination of sorption capacity on ions Pb2+carry out passing a solution containing 1 mg/DM3ions Pb2+through the volume of the sorbent 10 cm3with a speed of 9 m/h (6 cm3/min). The filtrate determine the content of the ion Pb2+. Filtering stop when reaching the ion concentration Pb2+the filtrate above MCL (0.1 mg/DM3). Oprita use gel and macroporous strong basic Quaternary ammonium anion exchange resin based on a styrene-divinylbenzene in the hydroxide form, for example, the anion exchange resin types: AV-17-8 es, AV-17-10P manufactured according to GOST 20301-74 with changes 1, 2, 3, 4, or AMBERLITIRA 900.

Determination of iron content is performed by the method of annealing. When this determination is performed on three samples of sorbent from one technological cycle.

Analysis of the proposed method of obtaining modified hydroxide iron (III) sorbent and known technical solutions shows that there is no set of features, identical to the technical nature of the claimed. Comparative analysis of the proposed solutions with the prototype shows that the claimed solution differs from the prototype conditions modification.

Thus, the inventive method of obtaining corresponds to the criteria of the invention of "novelty."

In literature and practice, there is no information about obtaining identical proposed, and it is not obvious from the prior art. This allows us to conclude that the claimed solution meets the criterion of "inventive step".

The proposed solution provides the achievement of the technical result can be implemented in water treatment and enables repeated playback is here".

The invention is illustrated by examples.

Example 1. Strong basic anion exchange resin curing AV-17-10P (OH-form) in an amount of 1 DM3placed in a reactor, poured 1,5 DM34,5 - 5,5% solution of FeCl3, stirred for 6-10 minutes, the solution is poured and poured 3,0 DM3demineralized water, heated to 95 - 100oC for 5 - 10 minutes, maintaining the temperature of the pulp 805oC under stirring. The solution is poured, poured 1,0 DM34.5 to 5.0% NaOH solution during 60 - 180 minutes. The solution is drained, washed sorbent from alkali demineralized water at ambient temperature, Prilepa 2.0 DM3water during 5 - 10 minutes. After reaching the solution over the sorbent negative reaction to phenolphthalein translate it in salt, i.e., in this case, HCO3-form.

Placed 10 cm3the obtained sorbent in the column with an inner diameter of 12 mm and passed through a solution containing 10 mg/DM3ions S2-when the speed of the filter 9 m/h (6 cm3/min). The filtrate determine the content of ions S2-. Upon reaching the concentration of S2-0.5 mg/DM3filtering stop. Determine the volume proposea solution containing 0.2 g/l of ions NH4CNS at the rate of 1 ml/min Filtration cease when the thiocyanate ion in the filtrate. Determine the amount of the missed solution.

In a column with an inner diameter of 12 mm was placed 10 cm3sorbent and passed through it to a solution containing 1 mg/DM3ions Pb2+with a speed of 9 m/h (6 cm3/min). Filtering stop when reaching the concentration of Pb2+0.1 mg/DM3(MPC). Determine the amount of the missed solution.

Determination of iron content carried out by selecting from the resulting technological cycle of sorbent three samples. Mass fraction of iron (%) is determined according to GOST 12868-77 in three samples from the received sample.

The settings how you want to receive sorbent and the quality indicators of the sorbent are shown in table. 1 and 2.

Examples 2 to 4. Analogously to example 1.

Examples 5 to 8 (overseas). Analogously to example 1, except that do not determine the sorption capacity for CNS--ion and Pb2+-Jonah. In examples 5 and 7 do not determine the iron content in the sorbent.

Example 9 (prototype). Carried out analogously to example 1. In column loaded sorbent modified with iron hydroxide coz the different examples and tables 1 and 2 shows, that holding inoculation of highly basic anion exchange resin curing type in static conditions can reduce the number of volumes of processing solutions to 21.5, which is more than 2 times higher than the known technical solution.

The decrease in the ratio of phases T : W in the processing solution of ferric chloride (III) below 1.0 : 1,2 leads to a significant degradation of the sorbent by sulfide ions. The increase of this ratio above 1.0 to : 1,7 leads to increased consumption of all reagents without improving the properties of the sorbent.

Holding a single washing of the sorbent from a solution of ferric chloride (III) demineralized water with a temperature of 95 - 100oC due to the fact that repeated washing with demineralised water at this temperature does not improve the quality of the material. Processing demineralized water with a temperature below 75oC does not allow you to avoid washing away the iron hydroxide (III) if further treatment with alkali and reduces the sorption capacity of the material.

The treatment of the sorbent of 4.5 - 5% alkali solution at a ratio of phases T : W 1.0 : 0.8 to 1.0 : 1,2 promotes fixation of iron hydroxide (III) on the sorbent. At a lower content of alkali produced quantity of demineralized water for washing from its excess.

The proposed method of sorbent various impurities from the water, modified hydroxide iron (III), allows 2.6 times to reduce the consumption of reagents and waste water, to increase the sorption capacity for ions S2-1.5 times, to adsorb ions CNS-and Pb2+that it was virtually impossible when using the technical solutions of the prototype.

A method of obtaining modified sorbents, including the processing of highly basic polymerization, anion exchange resin in hydroxyl form first 4,4 5,5% solution of ferric chloride (III), and then 4,5 5,0% alkali solution, washing with water after each treatment and conversion to the salt form, wherein the processing carried out once in static conditions, and the volume ratio of the solid and liquid phases in the processing solution of ferric chloride (III) is (1,0 1,1) (1,2 1,7), while treatment with alkali 1 (0,8 1,2), rinse with water after treatment with a solution of ferric chloride (III) carry out once with 75 95oC.

 

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