Method of preparing textile-supported polymer catalyst

FIELD: catalysts for waste water and emission gas treatment.

SUBSTANCE: invention relates to technology of removing organic and inorganic components from waste waters and emission gases via liquid-phase oxidation, in particular, to preparing textile-supported polymer catalyst consisting of polyacrylonitrile monothreads and complex threads. Knitted cloth is treated with modifying solution at 106 to 150°C for 10 to 30 min when ratio of amounts of polyacrylonitrile units to amount of chlorine-containing hydrazine salt equal to 20-30 and the same to chlorine-containing hydroxylamine salt 10-15, pH of solution being 6-9. After that, cloth is treated with transition metal salts for 1.0-2.0 h until content of metal on catalyst achieves 0.81-1.2 mmol/g. Treatment is followed by washing with desalted water.

EFFECT: simplified catalyst preparation technology and intensified preparation process.

2 cl, 2 tbl, 30 ex

 

The invention relates to methods for catalytic materials for wastewater and gas emissions from organic and inorganic components by the method of liquid-phase oxidation.

Known catalysts for liquid-phase oxidation of pollutants, as a rule, are of various soluble compounds of metals of variable valence [Former J.V. Cleaning gas from the sulfur compounds. M niitekhim (Review), 1976, 31 S.]. Making these toxic and expensive compounds in the waste water is disadvantageous because there is no way their back-pull-out. The use of solid heterogeneous catalysts (e.g., granulated), which can be extracted from the waste water, is disadvantageous for the following reasons. The speed of reactions involving heterogeneous processes is limited by diffusion of the components inside the granules. Therefore, the reactions take place at a low speed.

The solution to this problem may be the use of fibrous forms of the catalysts. Fibers have high external surface, easily accessible to reagents, strong, durable, can be processed using textile techniques and technologies in diverse, easy to use form.

Closest to the claimed solution is a method for textile volume of the fibrous catalyst [(prototype) Pat. R is No. 2145653, Tereshchenko L.Y., Linford R., Vitkovskaya Russia, having got, Dahmas R., Hedderman CD, Ishchenko V. the Method of obtaining textile volume of catalyst. Publ. Bull. izopet. No. 5 of 2000]. The method consists of two-stage processing of knitted fabric consisting of a solid, inert monofilaments of polypropylene, giving the material a three-dimensional form and filament yarn of polyacrylonitrile (PAN). In the first stage of the PAN threads impart ion exchange and complexing properties by treatment with a hot aqueous solution containing hydrochloric acid hydrazine in the number of 5-9 g/l, hydrochloric acid hydroxylamine in the amount of 7 to 14 g/l, sodium carbonate in an amount necessary for complete neutralization entered salts of hydrazine or of hydroxylamine, sodium hydroxide in an amount necessary to create a pH of 9-11, the sodium nitrite in the amount of 10-20 g/l, the solution temperature is 101-105°C, the processing time of 1.6-2.0 hours with further processing of the aqueous solution of sodium hydroxide with a concentration of 50-100 g/l when the temperature 101-105°and processing time of 0.5 to 15 minutes At the second stage, the canvas is treated with an aqueous solution of salt of a metal of variable valence within 24-36 hours. The metal connects with complexing groups that appeared in polyacrylonitrile fiber as a result of processing that leads to obrazovaniyasiga, possessing catalytic properties. The use of compounds of hydrazine leads to intermolecular crosslinking chains of polyacrylonitrile with a sharp increase chemical resistance of the fiber. And the use of salts of hydroxylamine leads to the formation on the fiber amidoxime groups, in which process conditions hydrolyzed to hydroxymelatonin, cyclists education glucosomine and other cycles. Conditions modifications in the prototype is chosen so as to maximize the strength of the fixing metal of variable valence on the fiber (and hence, increase the service life of the catalyst) and high catalytic activity. In particular, for this purpose in modifying the solution in addition to the compounds of hydrazine or of hydroxylamine is introduced sodium nitrite.

Durable frame made of polypropylene yarn gives the material a stable three-dimensional form, providing an intense hydrodynamic regime and, accordingly, intensive contact in the system liquid-air-catalyst in the process of liquid-phase oxidation.

The main disadvantages of the prototype are given the complexity of the technological scheme of the synthesis, the necessity of using a large number of expensive and toxic reagents, the complexity of the system to maintain a specified rather narrow temperature interval, a big total is the second time of the process. Another disadvantage is the high alkalinity of the modifying solution. Because the solution contains highly toxic nitrogenous bases - hydrazine and hydroxylamine, with the increase of pH they can stand out from the solution in a free form in the environment. In addition, at high pH values their small stability at elevated temperatures and they are prone to destruction. All this results in the unnecessary loss of these reagents. High pH values associated with the need of nitrile hydrolysis and amidoxime groups with the formation of complexing compounds able to hold the metal of variable valence in its composition. From the authors of the technological scheme of receipt of the prototype follows that even when the maximum pH values (11) hydrolysis in the process of conducting alkali-hydrazine powered processing does not proceed to the end. Therefore requires additional processing solution of sodium hydroxide at elevated temperatures. Without this treatment the material does not adsorb metal ions of variable valence and cannot therefore be used as a catalyst.

The technical result of the invention is the simplification of the manufacture of the catalyst by eliminating additional processing aqueous solution of sodium hydroxide, reducing the cost of reagents, the mind is isenia time making while maintaining the catalytic properties of the catalyst and the strength of the fixing metal of variable valence on the fiber.

This object is achieved in that there is a way to obtain textile polymeric catalyst consisting of monofilaments and filament yarn of polyacrylonitrile, which consists in the sequential processing of knitted fabric with a hot alkaline modifier solution of chlorides of hydrazine and hydroxylamine and an aqueous solution of salts of metals of variable valence with leaching demineralized water after each treatment, characterized in that the processing to produce the modifying solution at a temperature of 106-150°C for 10-30 min at achieving a ratio of the number of parts of polyacrylonitrile to the amount of chlorinated salts of hydrazine 20-30, and to the amount of chlorinated salt of hydroxylamine - 10-15, while the solution pH is 6-9, and treatment in an aqueous solution of transition metal salts is carried out for 1.0 to 2.0 hours to metal content in the catalyst 0,81-1.2 mmol/g

In the prior art known to use hot hydrazine-hydroxylamine-alkaline processing for modification of POLYACRYLONITRILE fibres in order to give them anion-exchange and complexing properties, the closest analogue is the material "Bulana AG [Kulinskaya D.A. study of the process of modification of POLYACRYLONITRILE fibres "Bulan" (HP Bulgaria) in order to give them ion exchange and complexing properties. Diss. on saisc. academic Art. K. n L., 1976. S-83.]. Conditions for modification the following: concentration g/l

NH2OH×HCl42
N2H4×2HCl10
Na2CO339
temperature90°
processing time1 hour
the ratio of the mass of the solution to the weight of the loaded PAN
fiber module (baths)50 kg of solution/kg fiber
pH modifying solution6.3-6.5

This material was designed as an ion exchanger, conditions modifications in contrast of the invention is selected so as to hinder hydrolysis of the resulting amidoxime groups, and sorption of metal ions of variable valence on such material is reversible and secure the strength so small and, therefore, the use of this material as a catalyst impossible, because of the possibility of separation of the metal in solution in the process of catalysis, which will cause the weakening of the catalytic properties of the material.

The essential features are that the processing to produce the modifying solution when the tempo is the atur 106-150° C for 10-30 min at achieving a ratio of the number of parts of polyacrylonitrile to the amount of chlorinated salts of hydrazine 20-30, and to the amount of chlorinated salt of hydroxylamine - 10-15, while the solution pH is 6-9, and treatment in an aqueous solution of transition metal salts is carried out for 1.0 to 2.0 hours to metal content in the catalyst 0,81-1.2 mmol/g

For comparability of results, the authors calculated the ratio of PAN fiber-salt of hydrazine for the prototype and the ratio of PAN fiber-salt of hydroxylamine, based on the data shown in the prototype. The ratio of the mass of solution mass of PAN fibres in the prototype should be 50 kg/kg ≈50 l of solution/kg of the fibers or 50 l of a solution/1000 g fiber, or 20 g fiber/l solution, or 20/53=0,377 mol of acrylic units/liters of solution (molecular weight polyacrylonitrile link 53 g/mol), concentrated hydrochloric acid hydrazine in the prototype is 9 g/l or 9/105=0,0857 mol/l (105 - molecular weight hydrazine hydrochloric acid, g/mol). Therefore, the desired ratio will be 0,377/0,0857=4,4 (maximum of 7.9 for the lower limit of the amount of hydrazine in the prototype). The concentration of hydrochloric acid hydroxylamine in the prototype is 14 g/l or 14/69,5=0.2 mol/l (69,5 - molecular weight hydrochloric acid hydroxylamine, g/mol). Therefore, the desired ratio will be 0,377/0,2=1,9. The higher the ratio of PAN/Hydra is in up to 20-30 and PAN/hydroxylamine to 10-15 mean dose reduction of these reagents on 1 kg of processed POLYACRYLONITRILE fibres 4.5 to 6.8 times. Accordingly decreases the concentration of hydrazine or of hydroxylamine in the modifying solution. This reduction of the concentrations of the reactants decrease and the speed of reactions with their participation. In turn, with increasing temperature, this allows you to keep the ratio of the speeds of reactions hydrazidine, gidroksietilirovaniya and hydrolysis, is required to obtain a stable catalytic centers and maintain its strong fibrous structure of the material. The authors experimentally it was found that the consumption of salts of hydroxylamine in the process associated with the consumption of salts of hydrazine simple. Namely, the ratio of the hydroxylamine/Gedrosia for components that have entered the reaction is ˜2. Therefore, the ratio of the salt of the hydroxylamine/polyacrylonitrile fibers in modifying the solution should be approximately two times more salt of the hydrazine/PAN. The performance of these optimal ratios of means, moreover, that in addition to the formation of stable catalytic centers, the reactants are completely consumed in the reaction and not give unproductive and highly toxic waste compounds of hydrazine or of hydroxylamine. The temperature increase is also extremely helps to ensure that the reagents were completely exhausted and were present in waste water after phase modification in the minimum the number.

In addition, the temperature increases dramatically reduces the time the modification. Another important advantage of increased temperature is that, as determined experimentally, increasing the porosity of the fiber (in comparison with the prototype). And porosity significantly reduces the processing time at the stage of processing of the fibers with an aqueous solution of a metal of variable valence. However due to the fact that at higher temperatures are more fully the processes of hydrolysis of nitrile and amidoxime groups, and due to the more porous structure of the obtained fiber additional stage of the alkali treatment is unnecessary.

The amount of complexing groups on the fiber also increases with temperature processing, which increases the strength of the fixing metal of variable valence on the fiber, and does it in turn unnecessary use of additional reagents carbonate and sodium nitrite.

The manufacturing process consists in the following. At the first stage of processing of textile fabric, for example, associated method "poluting" type equipment, containing in its composition an inert solid Foundation, for example, from polypropylene filaments (TU-6-06-537-86) and PAN complex thread (for example, on the EAST 6-06-2-80), the ratio of the mass of the monofilaments of the carrier to the weight PAN complex n the TEI 60,7-82.3 per cent the linear density of the PAN threads 32/2-32/4 Tex, surface module loop 3,17-3,35, the total linear density of warp and weft threads 156, 3mm-211,7 Tex, immersed in an autoclave containing an aqueous solution of salts of hydrazine and hydroxylamine salt, the ratio of PAN/salt of hydrazine should be 20-30, the ratio of PAN/salt of hydroxylamine should be 10-15, the pH of the solution beforehand by means of sodium hydroxide should be brought to 6-9. The canvas at a given temperature (106-150° (C) incubated for 10-30 minutes, then pull out and washed with demineralized water. In the second stage, the cloth is dipped in an aqueous solution of a salt of a metal of variable valence, for example, concentration of metal ion 1-5% and kept there for 1-2 hours, after washing demineralized water and drying in the drying chambers or drums at a temperature of not higher than 120°the catalyst is ready for use.

As the parameter characterizing the catalytic activity of the material was selected degree of conversion of oxidizable substances for a certain time of the reaction. As the characteristic strength of the fixing metal on the fiber (and, consequently, the stability of the catalyst over a long period of time) was selected degree of metal extraction in the processing of acidic buffer solution composition: 0.04 M H RHO4, 0.04 N CH3COOH, 0.04 N NVO2·N2Oh, X NaOH, pH 2, the processing time 160-170 hours. The higher the degree of extraction of the metal, the less secure the strength of the metal on the catalyst.

Examples.

Example 1.

Textile fabric, for example, associated method "poluting" type equipment, containing in its composition an inert solid Foundation, for example, from polypropylene filaments (TU-6-06-537-86) and PAN complex thread (for example, on the EAST 6-06-2-80), the ratio of the mass of the monofilaments of the carrier to the weight of POLYACRYLONITRILE filament yarn 66%, the linear density of the PAN threads 32/3 Tex, surface module loop 3,19, the total linear density of warp and weft threads 180 Tex, immersed in an autoclave containing an aqueous solution of salts of hydrazine and hydroxylamine salt, the ratio of PAN/salt of hydrazine should be 0,952 mol/l/0,0381 mol/l =25, the ratio of PAN/salt of hydroxylamine should be 0,952 mol/l/0,0793 mol/l =12, the pH of the solution beforehand by means of sodium hydroxide should be increased to 7. The canvas at a given temperature (106° (C) was incubated for 15 minutes, then pull out and washed with demineralized water, then the cloth is dipped in an aqueous solution of a salt of a metal of variable valence, for example, concentration of metal ion (Ni2+) 3% and kept there for 1.5 hours, after washing demineralized water and drying in usilnych chambers or drums at a temperature of not higher than 120° With the catalyst is ready for use.

As a test of catalytic activity was selected, as in the prototype, the oxidation of sulfide in aqueous solution on Nickel-containing catalyst. The content of divalent Nickel is 0.81 mmol/g secure the Strength of metal on the fiber, characterized by a degree of recovery of its acidic buffer solution was 30%. During the oxidation process 48 min, the concentration of S2-2000 mg/L. oxidation of sulfide sulfur was 99,1%, which does not differ from the respective figures of the prototype (see Example 21).

Examples 1-3

demonstrate the effect of temperature salecelebrities processing characteristics of the catalyst. Reducing the temperature below 106°impractical because it leads to a decrease in strength and fixing of metal and catalytic activity to a level below the prototype. The increase of treatment temperature above 150°it is impossible, because it will lead to destruction of the fibrous structure of PAN fibers and the destruction of the polypropylene base.

Examples 4-6

demonstrate the impact of relationships PAN/salt of hydrazine on the characteristics of the catalyst. The decrease of this ratio below 20 is impractical, as it would lead to a decrease in the strength of the fixing metal on the fiber and catalytic activity to the level of the others like the prototype. The increase above 30 is impractical for the same reason.

Examples 7-9

demonstrate the impact of relationships PAN/salt of hydroxylamine on the characteristics of the catalyst. The decrease of this ratio below 10 is impractical, as it would lead to a decrease in the strength of the fixing metal on the fiber and catalytic activity to a level below the prototype. The increase above 15 is impractical for the same reason.

Examples 10-12

demonstrate the effect of pH of salecelebrities processing on the technical characteristics of the resulting catalyst. Lowering the pH below 6 leads to a decrease in strength and fixing of metal on the fiber and catalytic activity to a level below the prototype. Raising the pH above 9 does not lead to further increase in the strength of fixing of metal on the fiber and catalytic activity of the sample, and only leads to the reduction of mechanical strength of the modified PAN fibres due to increased degradation of the polymer chains and overhead reagents.

Examples 13-15

demonstrate the influence of time salecelebrities processing to secure the strength of metal on the fiber and the catalytic activity of the samples. Reducing the processing time less than 10 min leads to a decrease in the content of metal on the fiber due to insufficient degrees of reactions and to decrease p is echnosti fastening metal and catalytic activity up to a level significantly below the prototype. The increase in processing time above 30 minutes does not lead to further increase in the strength of fixing of metal on the fiber and catalytic activity.

Examples 16-18

demonstrate the effect of time of treatment with a solution of salts of metals of variable valency on the characteristics of the catalyst. Reduced processing time less than 1 hour leads to a decrease of the metal content in the catalyst and reduce its catalytic activity to a level below the prototype. The increase in processing time with the salt solution of the above 2 hours does not lead to a further increase of catalytic activity.

Example 19

demonstrates the use of a monofilament of polyester instead of polypropylene for the manufacture of the catalyst.

Example 20

demonstrates the use of monochloride hydrazine instead of the average salt in the manufacturing process of the catalyst.

Example 21 (prototype)

demonstrates the features of the prototype needed for comparison with examples 1 to 20 in the oxidation of sulfides in aqueous solution.

Example 22

demonstrates the possibility of oxidation of mercaptide sodium in aqueous solution with oxygen in the claimed catalyst.

Example 23 (prototype)

demonstrates the characteristics needed for comparison with example 22 prototype in the oxidation of mercaptides.

Examples 24-27

demonstrate the ability oxide is placed (discoloration) of the dye acid blue 45" in aqueous solution by oxygen and hydrogen peroxide at Co 2+, Fe3+Pt4+and EN4+containing samples.

Examples 28-30 (prototype)

demonstrates the characteristics needed for comparison with the results of experiments 24-27 prototype in the reaction of the bleaching of the dye acid blue 45" With2+Pt4+and EN4+containing samples. While experiments 29 and 30 set by the authors to compare the results obtained in the present samples, with the results of the prototype in the case of platinum and ruteniysoderzhaschim catalysts.

Table 1

Technical parameters of manufacture of the catalyst.
The amount of acrylic fiber in the solution ˜50 g/l
ExampleThe first stage of modificationThe second stage
The parameters of alkali-hydrazine powered processingThe processing time of a solution of salt of metal of variable valence, h
Temperature, °the ratio of the number of parts of polyacrylonitrile to the amount of chlorine-containing salts of hydrazineThe salt concentration of hydrazine in terms of hydrazine hydrochloric acid, g/lthe ratio of the number is the number of polyacrylonitrile links to the number of chlorine-containing salt of hydroxylamine The salt concentration of hydroxylamine in terms of hydrochloric acid hydroxylamine neutral salt, g/lpHthe processing time min
ValuePAN/Salt of hydrazineValuePAN/Salt of hydroxylamine
1.2.3.4.5.6.7.8.9.10.11.
1.106250,952/0,03814,00120,952/0,07935,517151,5
2.135250,952/0,03814,00120,952/0,07935,517151,5
3.150250,952/0,03814,00120,952/0,07935,517151,5
4.135200,952/0,04765,00120,952/0,07935,517151,5
5.135250,952/0,0381 4,00120,952/0,07935,517151,5
6.135300,0952/0,03173,33120,952/0,07935,517151,5
7.135250,952/0,03814,00100,952/0,09526,626151,5
8.135250,952/0,03814,00120,952/0,07935,517151,5
9.135250,952/0,03814,00150,952/0,0634to 4.419151,5
10.135250,952/0,03814,00120,952/0,07935,516151,5
11.135250,952/0,03814,00120,952/0,07935,517151,5
12.135250,952/0,0381 4,00120,952/0,07935,519151,5
13.135250,952/0,03814,00120,952/0,07935,517101,5

25
1.2.3.4.5.6.7.8.9.10.11.
14.135250,952/0,03814,00120,952/0,07935,517151,5
15.135250,952/0,03814,00120,952/0,07935,517301,5
16.135250,952/0,03814,00120,952/0,07935,517151
17.135250,952/0,03814,00120,952/0,07935,517151,5
18.1350,952/0,03814,00120,952/0,07935,517152
19.*135250,952/0,03814,00120,952/0,07935,517151,5
20.**135250,952/0,03814,00120,952/0,07935,517151,5
21. (prototype***)1014,40,377/0,085891,90,377/0,20114712036
22.135250,952/0,03814,00120,952/0,07935,517151,5
23. (prototype***)1014,40,377/0,085791,90,377/0,20114712036
24.135250,952/0,03814,00120,952/0,07935,517151,5
25. 135250,952/0,03814,00120,952/0,07935,517151,5
26.135250,952/0,03814,00120,952/0,07935,517151,5
27.135250,952/0,03814,00120,952/0,07935,517151,5
28. (prototype***)1014,40,377/0,085791,90,377/0,20114712036
29. (prototype***)1014,40,377/0,085791,90,377/0,20114712036
30. (prototype***)1014,40,377/0,085791,90,377/0,20114712036
* As inert monofilament selected thread from Dacron.

** As a chlorine-containing salts of hydrazine was selected monochloride of hydrazine.
< / br> *** The number of polyacrylonitrile fibers in a solution of 20 g/l In the first processing stage in the modifier solution is injected additionally: Na2CO3the number 19,76 g/l NaNO2in the amount of 20 g/l, in addition, after alkaline hydrazine powered processing is carried out, an additional treatment with an aqueous solution of alkali with the following parameters: concentration of NaOH 100 g/l, temperature 101°, 15 minutes

Ni2+
Table 2

Examples of the application of textile fibrous catalyst
ExampleMetal ion catalystThe metal content in the catalyst, mmol/gThe degree of metal removal after processing the acidic buffer solution*, %The degree of conversion, %
1.2.3.4.5.
Oxidation of S2-in the solution during the oxidation process 48 min, the concentration of S2-2000 mg/l
1.Ni2+0,8130of 99.1
2.Ni2+0,922599,6
3.Ni2+1,052499,3
4.0,9527of 99.1
5.Ni2+0,922499,6
6.Ni2+0,893099,3
7.Ni2+0,912699,2
8.Ni2+0,922499,6
9.Ni2+0,8530of 99.1
10.Ni2+0,813099,2
11.Ni2+0,922499,6
12.Ni2+1,082499,3
13.Ni2+0,893099,2
14.Ni2+0,922799,6
15.Ni2+0,952599,7
16.Ni2+0,8823of 99.1
17.Ni2+0,922699,6
18.Ni2+ 0,943099,6
19.Ni2+0,922699,6
20.Ni2+0,922699,6
21. (prototype)Ni2+0,8130of 99.1
The oxidation of the mercaptan, the time of the process 20 min, initial concentration of CH3SNa - 300 mg/l
22.Ni2+0,9230100
23. (prototype)Ni2+0,813099,9

td align="center"> 99,7
1.2.3.4.5.
The oxidation dye acid blue 45", during the process 15 min, initial concentration of dye (20 mg/l
24.With2+1,22192
25.Fe3+0,851078
26.Pt4+0,94599,8
27.EN4+0,967
28. (prototype)With2+1,152273,1
29. (prototype)Pt4+0,91899,8
30. (prototype)EN4+0,921099,7
* The composition of the buffer: 0.04 M H3RHO4, 0.04 N CH3COOH, 0.04 N NVO2·N2Oh, X-NaOH, pH=2, the processing time 160-170 hours.

The method of obtaining textile polymeric catalyst consisting of monofilaments and complex polyacrylonitrile filaments, which consists in the sequential processing of knitted fabric first hot alkaline modifier solution of chlorides of hydrazine or of hydroxylamine, and then an aqueous solution of salt of a metal of variable valence with leaching demineralized water after each treatment, characterized in that the processing of the modifying solution is carried out at a temperature of 106-150°C for 10-30 min so that the ratio of the number of parts of polyacrylonitrile to the amount of chlorinated salts of hydrazine 20-30, and to the amount of chlorinated salt of hydroxylamine 10-15, while the solution pH is 6-9, and treatment with an aqueous solution of salts transition metals is carried out for 1.0 to 2.0 h before the content is of atalla catalyst 0,81-1.2 mmol/g



 

Same patents:

FIELD: waste water and gas emission treatment.

SUBSTANCE: invention relates to methods for preparing catalytic materials to clean waste waters and gas emissions via removal of organic and inorganic components by liquid-phase oxidation process. Method comprises consecutive treatment of knitted cloth with hot alkali solution containing 14-42 g/L hydroxylamine chloride and an aqueous solution of variable-valence metal salts. In the first stage, treatment is carried out with modifying hydroxylamine chloride and ethylenediamine-containing solution wherein molar ratio of polyacrylonitrile unit number to ethylenediamine ranges from 2 to 10 and solution pH is 6-9. Treatment temperature is 95-105°C and treatment time 1-1.6 h. In the second stage, treatment with aqueous solution of variable-valence metal salts is carried out for 0.5 to 2 h.

EFFECT: simplified manufacture technology, reduced expenses on reagents, and reduced process time without loss in the firmness of fixation of variable-valence metal salts on cloth.

2 tbl, 21 ex

The invention relates to methods for textile surround the fibrous catalysts and can be used in chemical, petrochemical, light industry, in particular for the treatment of wastewater and gas emissions from sulphides, organic impurities, dyes

FIELD: waste water and gas emission treatment.

SUBSTANCE: invention relates to methods for preparing catalytic materials to clean waste waters and gas emissions via removal of organic and inorganic components by liquid-phase oxidation process. Method comprises consecutive treatment of knitted cloth with hot alkali solution containing 14-42 g/L hydroxylamine chloride and an aqueous solution of variable-valence metal salts. In the first stage, treatment is carried out with modifying hydroxylamine chloride and ethylenediamine-containing solution wherein molar ratio of polyacrylonitrile unit number to ethylenediamine ranges from 2 to 10 and solution pH is 6-9. Treatment temperature is 95-105°C and treatment time 1-1.6 h. In the second stage, treatment with aqueous solution of variable-valence metal salts is carried out for 0.5 to 2 h.

EFFECT: simplified manufacture technology, reduced expenses on reagents, and reduced process time without loss in the firmness of fixation of variable-valence metal salts on cloth.

2 tbl, 21 ex

The invention relates to methods for textile surround the fibrous catalysts and can be used in chemical, petrochemical, light industry, in particular for the treatment of wastewater and gas emissions from sulphides, organic impurities, dyes

FIELD: waste water and gas emission treatment.

SUBSTANCE: invention relates to methods for preparing catalytic materials to clean waste waters and gas emissions via removal of organic and inorganic components by liquid-phase oxidation process. Method comprises consecutive treatment of knitted cloth with hot alkali solution containing 14-42 g/L hydroxylamine chloride and an aqueous solution of variable-valence metal salts. In the first stage, treatment is carried out with modifying hydroxylamine chloride and ethylenediamine-containing solution wherein molar ratio of polyacrylonitrile unit number to ethylenediamine ranges from 2 to 10 and solution pH is 6-9. Treatment temperature is 95-105°C and treatment time 1-1.6 h. In the second stage, treatment with aqueous solution of variable-valence metal salts is carried out for 0.5 to 2 h.

EFFECT: simplified manufacture technology, reduced expenses on reagents, and reduced process time without loss in the firmness of fixation of variable-valence metal salts on cloth.

2 tbl, 21 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to manufacture of ion-exchange fibers with special properties, which can be used as sorbent or as a sorbent constituent for cleaning liquid media, largely natural and waste waters. Method consists in performing alkali hydrolysis of polyacrylonitrile fiber in presence of hydrazine at elevated temperature completed by treatment of fiber with active agent causing degradation of chromophore groups of fiber. Alternatively, ion-exchange fiber is manufactured via alkali hydrolysis of polyacrylonitrile fiber in presence of hydrazine at elevated temperature, hydrolysis reaction being effected in concentrated solution of salt of alkali metal with weak acid followed by treatment of fiber with active agent as above.

EFFECT: improved characteristics of fiber at lower consumption of reagents and stabilized manufacturing process to provide ion-exchange fiber with desired number of chelating sorption groups due to appropriate balance of acid and basic groups resulting from hydrolysis.

18 cl, 5 tbl, 16 ex

FIELD: sorbents.

SUBSTANCE: invention relates to technology for preparing sorbents with fibrous structure by using waste of industrial manufacture. Method involves treatment of fibrous matrix from waste of tanning leather chips with polyelectolyte an aqueous solution obtained by alkaline hydrolysis of polyacrylonitrile or copolymer based on thereof. Prepared sorbent shows the improved capacity for extraction of different components from different aqueous media.

EFFECT: improved preparing method, improved and valuable properties of sorbent.

2 cl, 1 tbl, 2 ex

FIELD: sanitary and hygienic facilities.

SUBSTANCE: invention relates to technology of manufacturing chemisorption materials for use in municipal hygiene sphere. Method consists in treatment of chemisorption carboxyl-containing material in Na form with 0.5-1.0% aqueous acid solution, e.g. hydrochloric acid solution, at modulus (ratio of weight of chemisorption material to acid solution volume) 1:30 and treatment time 0.5-1.0 h to transfer material into H-form. Chemisorbent is then washed with softened water to pH 5-6, after which material in H-form is treated for 0.5-1.0 h with 0.5-1.0% potassium hydroxide solution, modulus 1:30. At the expiration of treatment time, material is washed with softened water to pH 5.0-6.5. Presence of three-dimensional lattice, both during treatment time of chemisorption material in the form of fibers or nonwoven material and upon use of products from this material, prevents dissolution of polymer in water or in aqueous solution of acid or potassium hydroxide. Owing to filtration, chemisorbent entraps in water heavy metal ions contained therein and water is saturated with potassium ions so that chemisorption material acquires at least 4 mmol/g of carboxyl groups in K-form.

EFFECT: optimized manufacture conditions.

2 ex

The invention relates to a method for macrosector of the anion exchange resin is a crosslinked copolymer with aminoalkenes groups, which can be used in the chemical, nutritional and microbiological industry for the purification of solutions of biologically active substances
The invention relates to a method for producing cross-linked polymers and resins

The invention relates to methods for ion exchange fibers based on polyacrylonitrile (PAN) and its copolymers and can be used in the extraction of metal ions Hg and Cr precise water from industrial complex salt composition
The invention relates to a method for producing anion exchange resin curing type used in various reactions of ion exchange in water treatment and hydrometallurgy, which allows to increase the osmotic stability and mechanical strength of the resulting anion exchange resin
The invention relates to methods for complexing ion exchangers designed for the recovery of precious metals from solutions, and can be used in analytical chemistry and in hydrometallurgy for the selective concentration and recovery of platinum metals from solutions

FIELD: sanitary and hygienic facilities.

SUBSTANCE: invention relates to technology of manufacturing chemisorption materials for use in municipal hygiene sphere. Method consists in treatment of chemisorption carboxyl-containing material in Na form with 0.5-1.0% aqueous acid solution, e.g. hydrochloric acid solution, at modulus (ratio of weight of chemisorption material to acid solution volume) 1:30 and treatment time 0.5-1.0 h to transfer material into H-form. Chemisorbent is then washed with softened water to pH 5-6, after which material in H-form is treated for 0.5-1.0 h with 0.5-1.0% potassium hydroxide solution, modulus 1:30. At the expiration of treatment time, material is washed with softened water to pH 5.0-6.5. Presence of three-dimensional lattice, both during treatment time of chemisorption material in the form of fibers or nonwoven material and upon use of products from this material, prevents dissolution of polymer in water or in aqueous solution of acid or potassium hydroxide. Owing to filtration, chemisorbent entraps in water heavy metal ions contained therein and water is saturated with potassium ions so that chemisorption material acquires at least 4 mmol/g of carboxyl groups in K-form.

EFFECT: optimized manufacture conditions.

2 ex

FIELD: sorbents.

SUBSTANCE: invention relates to technology for preparing sorbents with fibrous structure by using waste of industrial manufacture. Method involves treatment of fibrous matrix from waste of tanning leather chips with polyelectolyte an aqueous solution obtained by alkaline hydrolysis of polyacrylonitrile or copolymer based on thereof. Prepared sorbent shows the improved capacity for extraction of different components from different aqueous media.

EFFECT: improved preparing method, improved and valuable properties of sorbent.

2 cl, 1 tbl, 2 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to manufacture of ion-exchange fibers with special properties, which can be used as sorbent or as a sorbent constituent for cleaning liquid media, largely natural and waste waters. Method consists in performing alkali hydrolysis of polyacrylonitrile fiber in presence of hydrazine at elevated temperature completed by treatment of fiber with active agent causing degradation of chromophore groups of fiber. Alternatively, ion-exchange fiber is manufactured via alkali hydrolysis of polyacrylonitrile fiber in presence of hydrazine at elevated temperature, hydrolysis reaction being effected in concentrated solution of salt of alkali metal with weak acid followed by treatment of fiber with active agent as above.

EFFECT: improved characteristics of fiber at lower consumption of reagents and stabilized manufacturing process to provide ion-exchange fiber with desired number of chelating sorption groups due to appropriate balance of acid and basic groups resulting from hydrolysis.

18 cl, 5 tbl, 16 ex

FIELD: waste water and gas emission treatment.

SUBSTANCE: invention relates to methods for preparing catalytic materials to clean waste waters and gas emissions via removal of organic and inorganic components by liquid-phase oxidation process. Method comprises consecutive treatment of knitted cloth with hot alkali solution containing 14-42 g/L hydroxylamine chloride and an aqueous solution of variable-valence metal salts. In the first stage, treatment is carried out with modifying hydroxylamine chloride and ethylenediamine-containing solution wherein molar ratio of polyacrylonitrile unit number to ethylenediamine ranges from 2 to 10 and solution pH is 6-9. Treatment temperature is 95-105°C and treatment time 1-1.6 h. In the second stage, treatment with aqueous solution of variable-valence metal salts is carried out for 0.5 to 2 h.

EFFECT: simplified manufacture technology, reduced expenses on reagents, and reduced process time without loss in the firmness of fixation of variable-valence metal salts on cloth.

2 tbl, 21 ex

FIELD: catalysts for waste water and emission gas treatment.

SUBSTANCE: invention relates to technology of removing organic and inorganic components from waste waters and emission gases via liquid-phase oxidation, in particular, to preparing textile-supported polymer catalyst consisting of polyacrylonitrile monothreads and complex threads. Knitted cloth is treated with modifying solution at 106 to 150°C for 10 to 30 min when ratio of amounts of polyacrylonitrile units to amount of chlorine-containing hydrazine salt equal to 20-30 and the same to chlorine-containing hydroxylamine salt 10-15, pH of solution being 6-9. After that, cloth is treated with transition metal salts for 1.0-2.0 h until content of metal on catalyst achieves 0.81-1.2 mmol/g. Treatment is followed by washing with desalted water.

EFFECT: simplified catalyst preparation technology and intensified preparation process.

2 cl, 2 tbl, 30 ex

FIELD: chemical technology, resins.

SUBSTANCE: invention relates to a method for preparing polyhalide strong-basic anion-exchange resins of gel and macroporous structure designated for disinfection of water in closed ecological objects, domestic drinking water and water from non-checked sources. Polyhalide anion-exchange resins is prepared from strong-basic quaternary ammonium anion-exchange resins in chloride form by their iodination with J2 solution in KJ at stirring, thermostatic control and washing out. Iodination is carried out with triiodide solution on conditioned strong-basic anion-exchange resins in chloride form in the content of strong-basic groups 80%, not less, in the mole ratio anion-exchange resin : triiodide = 1.0:(1.1-1.5). Ready product is kept at 20-55°C additionally. Invention provides preparing polyhalide anion-exchange resins characterizing by high resource in water disinfection and in simultaneous reducing iodine release in disinfecting water in retention of high disinfecting indices.

EFFECT: improved preparing method.

1 tbl, 8 ex

Abstract // 2293061

FIELD: ION-EXCHANGE MATERIALS.

SUBSTANCE: invention relates to a process of preparing gel-like cationites for use in treatment and purification processes. Gel-like cationites are prepared by inoculating-incoming process wherein (a) aqueous suspension of microcapsulated cross-linked styrene polymer in the form of granules and containing cross-linking agent is provided as inoculating polymer; (b) inoculating polymer is left to swell in monomer mixture composed of vinyl monomer, cross-linking agent, and radical initiator, namely peracid aliphatic ester; (c) monomer mixture is polymerized in inoculating polymer; and (d)resulting copolymer is functionalized via sulfatization. Process is characterized by that, in step (a), content of cross-linking agent in cross-linked styrene copolymer amounts to 3.5-7 wt % and inoculum-to-income ratio in step (b) amounts to 1:(0.25-1.5).

EFFECT: enabled preparation of gel-like cationites having high osmotic and mechanic stabilities as well as improved oxidation resistance.

7 cl, 9 tbl, 9 ex

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