The method of obtaining coagulase-flocculation reagent and method of water treatment

 

(57) Abstract:

The invention relates to technology of inorganic substances and can be used to obtain iron coagulants-flocculants for water treatment, deposition of mineral solids from aqueous suspensions and concentration of dissolved metals in them. The inventive coagulase-flocculation reagent is produced by processing zhelezorudnogo material 5 - 25% sulfuric or hydrochloric acid when the flow rate of 60 - 100 % of stoichiometry to provide in the reaction solution molar ratio of Fetotal: SiO2= 1: 0,2 - 1,7. As zhelezorudnogo material use waste ore enrichment and final slag metallurgical plants containing fayalite and/or olivine. As a solution of sulfuric or hydrochloric acid using acidic pickling solutions metallurgical production, or leaching sulfuric acid sulfuric acid production, or agathou hydrochloric acid from the production of caustic soda. Water treatment is performed by the introduction coagulase-flocculation reagent containing a salt of iron and colloidal silicic acid, when regulating the pH of the liquid phase forming the first technical result consists in obtaining iron coagulase - flocculation reagent, with high resistance to polymerization and containing a reduced amount of ballast components, as well as to improve the purity of the water by providing processing capabilities in a wider range of pH. 2 S. and 3 C.p. f-crystals.

The invention relates to technology of inorganic substances and can be used to obtain iron coagulants-flocculants for water treatment, deposition of mineral solids from aqueous suspensions and concentration of dissolved metals in them.

A method of obtaining coagulating reagent (see RF Patent N 2085509, IPC6C 02 P 1/52, 1997), including the processing of red mud from alumina production 3 - 5% hydrochloric acid at a ratio of T : W = 1 : 5-10, processing the obtained solid residue 50 - 55% sulfuric acid at 100 - 110oC and the ratio of T : W = 1 : 6-8, filtering the slurry and adding to the resulting solution of concentrated sulfuric acid to ensure its total content in the solution is 25 to 50 wt.%, then the solution was incubated for 10-20 h and separating the precipitate. Get coagulating reagent contains, wt%: Al2O32 - 10; Fe2O32 -10; H2SO4total40 - 60 (including H2S the CI obtained when using coagulant does not exceed 91%.

The disadvantages of this method are its complexity, high energy consumption, the limited scope of the received reagent due to the high content of free sulfuric acid at low concentrations of coagulating agents (Al2O3and Fe2O3), as well as insufficient high degree of purification with significant (up to 1.5 g/l) reagent costs.

A method of obtaining coagulase-flocculation reagent (see RF Patent N 2049735, IPC6C 02 F 1/58, C 02 F 1/52, 1995), including processing almacenista material 1-12% solution of sulfuric acid in its consumption 100 - 105% from stoichiometry to ensure a relationship of Al2O3: SiO2= 1:2-3:10.

There is also known a method of water treatment described in the above patent RF N 2049735, including the introduction coagulase-flocculation reagent containing an aluminium salt and colloidal silicic acid in a molar ratio of Al2O3: SiO2= 1 : 2 to 3 : 10, when regulating the pH of the liquid phase formed suspension in the range of 7.0 - 9.5 and separating the liquid phase from the precipitate by filtration.

The disadvantages of the known methods of obtaining coagulase - flocculation reagent and water treatment I the th receive increases the amount of sludge hydrolysis and increases the residual content of aluminum and silicon in alkaline medium using the reagent, as well as a significant presence ballast components, such as the K+and Na+that increase the salinity of the treated water.

The present invention is directed to solving the problem of obtaining iron coagulase-flocculation reagent with high resistance to polymerization and containing a reduced amount of ballast components. The invention is also aimed at solving the problem of increasing the purity of the water by providing processing capabilities in a wider range of pH.

The problem is solved in that in the method of obtaining coagulase-flocculation reagent by treating the metal - silicon-containing material with a solution of sulfuric acid, according to the invention as metallochemistry material used zhelezokremnistykh material and its processing are 5 - 25% sulfuric or hydrochloric acid when the flow rate of 60 - 100% of stoichiometry to provide in the reaction solution molar ratio of Fetotal) : SiO2= 1 : 0,2 - 1,7.

Set suprasolv and final slag metallurgical enterprises containing fayalite and/or olivine.

The problem is solved and the fact that as a solution of sulfuric or hydrochloric acid using acidic pickling solutions metallurgical production, or leaching sulfuric acid sulfuric acid production, or agathou hydrochloric acid from the production of caustic soda.

The solution of this problem is provided by the fact that in the method of water treatment comprising an introduction coagulase-flocculation reagent containing a metal salt and colloidal silicic acid, when regulating the pH of the liquid phase of the resulting suspension and separating the liquid phase from the precipitate, according to the invention as a reagent used coagulase-flocculation reagent obtained under item 1, containing as the metal salt, iron salt, and the regulation of the pH of the liquid phase is carried out in the range of 3.5-11,0.

The solution of this problem is provided by the fact that before separating the liquid phase from the precipitate suspension defend.

The essence of the proposed method to obtain coagulase-flocculation reagent is that zhelezokremnistykh material is treated with 5-25% sulfuric or hydrochloric acid at a flow rate of acid 60-100% of STV as zhelezorudnogo material can be used in waste mining industries and final slag metallurgical enterprises the main mineral component which is fayalite 2FeOSiO2or olivine (Mg, Fe)2SiO4. During the processing of such raw materials with sulfuric or hydrochloric acid in solution are formed respectively sulfates or chlorides of iron and soluble silicic acid:

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Get H4SiO4able to form true solutions, but weakly dissociates. Physico-chemical properties of solutions of H4SiO4depend on the temperature, the concentration of silica, salt solutions, acidity, time, and other factors. The main property of solutions of silicic acid is the desire for polymerization and polycondensation, which explains their flocculation properties. The flocculation mechanism of action of silicic acid is close to the mechanism of flocculation with organic polymers, such as polyacrylamide.

Processing zhelezorudnogo material 5 - 25% sulfuric or hydrochloric acid because the acid concentration of less than 5 % increases the time of decomposition of the raw materials and the ratio of Fetotal:SiO2becomes more than 1.7 with a corresponding decrease in the concentration of the coagulating agent is iron. Controlsa properties of the reagent and creates difficulties when using it.

When the consumption of acid is more than 100% increase in the share of unreacted acid, which is impractical, and when the consumption of acid is less than 60% reduced extraction koaguliruemogo agent and decreases the resistance of the resulting reagent for polymerization.

When the ratio of Fetotal:SiO2less than 1: 0,2 reduced flocculation agent properties of the reagent, and when the ratio is about 1:1.7 to create an excess of SiO2that reduces the stability of the reagent for polymerization. The ratio of Fetotal: SiO2can be adjusted in various ways: changing consumption of acid by the decomposition of iron-silicon material or the use of acid solutions containing iron salts and free acid, or a combination of these two techniques.

Zhelezokremnistykh material may be treated with solutions containing iron salts and free sulfuric acid, for example, the solutions obtained by etching different grades of steel in metallurgical plants, as well as other kinds of substandard sulfuric or hydrochloric acid, such as leaching sulfuric acid, Abhazia hydrochloric acid, waste acids, acidic effluents, etc.

In water treatment, regulation of the pH of the liquid phase is carried out before the pay water from harmful impurities. When the pH value of the liquid phase less than 3.5 and more 11,0 coagulation and flocculation does not occur and the water is not cleaned from impurities.

Upholding the suspension before separating the liquid phase from the precipitate is due to the fact that the hydrolysis product zhelezorudnogo reagent has a stable structure and firmly holds adsorbed impurities. The desorption of impurities in the purified water does not occur.

Above the nature and advantages of the invention can be illustrated by the following examples.

Example 1. Handle 25% hydrochloric acid 100 g svezheosazhdennoi of metasilicate iron containing, wt.%: Fetotal42,4; SiO245,5 at 100% from the stoichiometry of the acid consumption and the process temperature 73oC. the Treatment is carried out for 20 min to provide in the reaction solution molar ratio of Fetotal:SiO2= 1 : 0,2. The resulting suspension liquid phase which contains, g/l: Fetotal83,8; SiO218.2, and diluted with water to a working concentration of Fe, equal to 2% and used as coagulase-flocculation reagent. The solution is not polymerized, and in the process of long-term storage gradually allocated Smagulova SiO2. Ballast components otsutstvuet "Pechenganickel", contains, wt% : Fetotal27,1; SiO240,7; MgO 8,7; Al2O36,5; CaO 4,7, when 90% from the stoichiometry of the acid consumption and the process temperature 73oC. the Treatment is carried out for 20 min to provide in the reaction solution molar ratio of Fetotal:SiO2= 1 : 1,2. The resulting suspension liquid phase which contains, g/l: Fetotal47,0; Al 5,8; SiO256,3; MgO 13,0, dilute with water 2 times and used as coagulase-flocculation reagent. The polymerization solution of the reagent is 42 hours Ballast components are missing, as Al hydrolyzed, a Mg salt forms of rigidity, which increase the coagulating action of the reagent.

Example 3. Handle 15% sulfuric acid 100 g of slag dump of "Severonikel" smelter, containing, wt.%: Fetotal45,2; SiO223,1; MgO 3,8; Al2O34,7; CaO 3,5; Ni 0,07; Cu 0,26 at 100% from the stoichiometry of the acid consumption and the process temperature 67oC. the Treatment is carried out for 20 min to provide in the reaction solution molar ratio of Fetotal: SiO2= 1: 0,5. The resulting suspension liquid phase which contains, g/l: Fetotal70,1; SiO237,5; MgO 6,9; Al 1,8; Ni 0,06; si 0,09, after dilution to working concentrarse 46 PM Ballast components are missing, as Al hydrolyzed, a Mg salt forms of rigidity, which increase the coagulating action of the reagent. The trace amounts of Ni and si seacadets with hydroxide sludge during wastewater treatment using reagent.

Example 4. Handle 100 g of slag dump of "Severonikel" smelter composition according to example 3 leaching with sulfuric acid in this plant, diluted to 10% concentration and containing, g/l: H2SO4free.106,2; Cu 0,64; Ni 1,12; Co 0,03; As 0,22; Os 0,0025, with 80% from the stoichiometry of the acid consumption and the process temperature 63oC. the Treatment is carried out for 20 min to provide in the reaction solution molar ratio of Fetotal: SiO2= 1 : 0,48. The resulting suspension liquid phase which contains, g/l: Fetotal52,8; Al 1,2; SiO227,2; MgO 4,0; Ni 1,19; Cu 0,64; Co 0,03; As 0,22; Os 0,0025, diluted 2-fold with water and used as coagulase-flocculation reagent. The polymerization solution of the reagent is 56 hours After dilution, the solution is not polymerized, and during storage of the solution stands out Smagulova SiO2. Ballast components are missing, as Al hydrolyzed, a Mg salt forms of rigidity, the cat who ohms and are concentrated in the processing of waste water using reagent.

Example 5. Handle 100 g of slag dump of "Severonikel" smelter, containing, wt.%: Fetotal39,1; SiO226,1; MgO 3,3; Al2O33,9; CaO 3,2; Ni 0,061; Cu 0,28 hydrochloric acid solution from the pickling of steel containing, g/l: Fe2O353,2 and HClfree.62,1 (6% HCl) at 60% from the stoichiometry of the acid consumption and the process temperature 43oC. the Treatment is carried out for 0.5 h to provide in the reaction solution molar ratio of Fetotal: SiO2= 1 : 0,2. The resulting suspension liquid phase which contains, g/l: Fetotal72,43; SiO216,8; MgO 2,7; Al 0,85; CaO 2,6, dilute to a working concentration of Fe, equal to 2% and used as coagulase-flocculation reagent. The polymerization of the reagent solution without dilution is 52 hours Ballast components are missing, Al hydrolyzed, and Ca and Mg form hardness salts, which increase the coagulating action of the reagent. The trace amounts of Ni and Cu seacadets with hydroxide sludge during wastewater treatment using reagent.

Example 6. Process 5% sulfuric acid 100 g originalarray waste plant Pechenganickel composition according to example 2 at 100% from the stoichiometry of the consumption of acid and cootnoshenie Fetotal: SiO2= 1 : 1,7. The resulting suspension liquid phase which contains, g/l: Fetotal12.7mm; Al 2,2; SiO223,2; MgO 3,8; 0,02 Ni; Cu 0,002 use as coagulase-flocculation reagent. The reagent solution does not polymerize more than 3 months. Ballast components are missing, as Al hydrolyzed, a Mg salt forms of rigidity, which increase the coagulating action of the reagent. The trace amounts of Ni and Cu seacadets with hydroxide sludge during wastewater treatment using reagent.

The nature and advantages of the method of water treatment are explained by the following examples.

Example 7. A sample of wastewater from the site galvanic plating and grinding, with a volume of 1 l, with a pH environment of 6.7, containing, mg/l : suspended solids 178; petroleum products; 1363; Cr(VI) 357; Fetotal5,3, treated with 7.5 ml coagulase-flocculation reagent obtained in example 1, to pH < 2 with mechanical stirring for 10 min for recovery of chromium to the trivalent state, then stopping stirring mass, dolomite injected to ensure a pH of 3.5, which begins the hydrolysis and coagulation, with further increase in pH to 8.2. The resulting suspension assert within 1 hour, LM is e substances 15,7; oil 4,0; Fetotal0,1. The purification of water is, %: suspended solids 91,7; Cr 100; Fetotal98,1. The precipitate is dense, brown has a humidity 94-95%.

Example 8. Sample wastewater Murmansk pig "Suburban", 1 liter, pH of the medium 6,6 containing, mg/l: suspended solids 16919; total nitrogen 3587; ammonia nitrogen 841,2; phosphates 459,2 with mg O2/l : COD (chemical oxygen demand) 21363 and BOD5(patiserie biological oxygen demand) 6372, treated with 10% lime milk suspension to pH 11 - 12 when mixing with compressed air, then stopping stirring mass, enter 8,5 ml coagulase-flocculation reagent, obtained according to example 2. After stirring the wastewater within 10 min the pH of the liquid phase is 8 - 9. The resulting concentrated slurry assert within 1 h, the liquid phase is separated from the precipitate by decantation. The treated wastewater has a residual content, mg/l: suspended solids 63,0; total nitrogen 778,4; ammonia nitrogen 39,5; phosphates 23,7; COD 576,8 and BOD5247. The purification of water is, %: suspended solids 99,6; total nitrogen 78,3; ammonia nitrogen to 95.3; phosphates 94,8; COD 97,3 and BOD596,1. Condensed balance represents the d with the "Severonikel" smelter, a volume of 1 l, with a pH of 8.1, containing, mg/l: suspended solids 238; Cu 22,3; Ni 31,5; Co 1,35; platinum metals: Pt, Pd, lr, Ru, Rh - 0,037, treated with lime milk to pH to 11.56 under mechanical stirring for 5 minutes, then stopping stirring mass, fractional inject 1.2 ml coagulase-flocculation reagent, obtained according to example 3, with the gradual lowering of the pH of the liquid phase to 11, which begins the hydrolysis and coagulation, with further lowering of the pH to 8.3. The resulting suspension advocate for 0.5 h, the liquid phase is separated from the precipitate by decantation. The treated wastewater has a residual content, mg/l: suspended solids less than 5; Cu 0,113; Ni 0,33; Co 0,01; Fetotal0,09; Al 0,12; platinum metals traces. The purification of water is, %: Cu 99,5; Ni 99,0; 99,3; Fetotal99,8; Al 89,7; platinum metals > 99,5. The precipitate is dense, brown has a humidity 94 - 95%.

In examples 10 and 11 shows the processes of wastewater treatment of "Severonikel" smelter coagulase-flocculation reagents, obtained by the proposed method and the prototype, using the same leaching with sulphuric acid.

Example 10. A sample of wastewater of "Severonikel" smelter, 1 liter, pH of the medium to 8.2, containing, mg/l: vzvesei for 5 min, after stopping stirring mass, fractional enter 1,32 ml coagulase-flocculation reagent obtained in example 4, with the gradual lowering of the pH of the liquid phase to 8.46, in which the most intense hydrolysis and coagulation. The resulting suspension assert within 1 h, the liquid phase is separated from the precipitate by decantation. The treated wastewater has a residual content, mg/l: suspended solids less than 5; Cu 0,07; Ni 0,31; Co 0,008; As < 0,01; Fetotal0,13; Al 0,41; SiO20,6; Os - traces. The purification of water is, %: Cu 99,8; Ni 99,3; 99,2; As > 96,3; Fetotal99,6; Al 71,7; SiO296,6; Os > 99,6. The precipitate is dense, brown, weight 1,0274.

Example 11. Process 100 grams of nepheline concentrate leaching with sulfuric acid composition in example 4, diluted to the concentration of H2SO4free.equal to 50 g/l, at a ratio of 1 : 1.06 in for 20 minutes. The liquid phase of the suspension has a chemical composition, g/l: Al2O312,6; SiO215,1; Fe2O30,7; Na2O 6,6; K2O 2,85; Ni 0,56; Cu 0,32; As 0,11; Co 0,02. The molar ratio of Al2O3:SiO2= 1 : 2. In a sample of wastewater of "Severonikel" smelter in example 10, enter 7 ml aluminosilicate coagulant to pH 3,66. Filtered 0,5 SUB>2O 46,2; K2O 20,0; Ni 46,3; Cu 31,9; As 0,77; Co Of 1.07. The second half of the sample is neutralized with 5% ammonia water to pH 8,21 and are settling in for 1 h, the clarified layer decanted. The treated wastewater has a residual content, mg/l: Al2O36,0; SiO27,6; Fe 0,01; Na2O 46,2; K2O 20,0; Ni 10,3; Cu 8,7; As 0,25; Co 0,3; Os 0,01. The purification of water is, %: Al2O393,5; SiO297,2; Fe 99,7; Ni 77,8; Cu 72,7; As 67,5; Co 72,0; Os 42,9.

As seen from the above examples, the present invention allows to obtain iron coagulase-flocculation reagent having high resistance to polymerization and containing a low content of ballast components, as well as to increase efficiency of water purification in a wider range of pH when using it.

1. The method of obtaining coagulase-flocculation reagent by treatment metallochemistry material with a solution of sulfuric acid, characterized in that as metallochemistry material used zhelezokremnistykh material and its processing are 5 - 25% sulfuric or hydrochloric acid when the flow rate of 60 - 100% of stoichiometry to provide in the reaction solution molar ratio of Fetotaluse waste ore enrichment and final slag metallurgical enterprises containing fayalite and/or olivine.

3. The method according to PP.1 and 2, characterized in that as a solution of sulfuric or hydrochloric acid using acidic pickling solutions metallurgical production, or leaching sulfuric acid sulfuric acid production, or agathou hydrochloric acid from the production of caustic soda.

4. The method of water treatment, including the introduction coagulase-flocculation reagent containing a metal salt and colloidal silicic acid, when regulating the pH of the liquid phase of the resulting suspension and separating the liquid phase from the precipitate, characterized in that the reagent is used coagulase-flocculation reagent obtained under item 1, containing as the metal salt, iron salt, and the regulation of the pH of the liquid phase is carried out in the range of 3.5 - 11,0.

5. The method according to p. 4, characterized in that before separating the liquid phase from the precipitate suspension defend.

 

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