SU929556A1 - Method for processing solutions containing sodium, potassium and magnesium chlorides and sulphates - Google Patents

Description

The invention relates to the processing technology of solutions containing chlorides and sulphates of sodium, potassium and magnesium, in particular a chenite uterine solution, and can be used in the processing of polymineral potash ores.

There is a known method for processing solutions containing sodium, potassium and magnesium chlorides and sulfates, including evaporation of the solution, separation of sodium chloride, evaporation of the mother liquor, separation of kainite, desalting and evaporation of the mother liquor, separation of the solid residue and returning it to the second stage of evaporation.

The disadvantage of this method is that the return of the previously unprocessed solid residue to the process of obtaining artificial kainit leads to a deterioration of its crystallization due to the presence of gypsum in the solid residue and partial desulfurization of the solution with calcium chloride, which is present in the "idle phase" impregnating the solid residue.

In addition, the use of a solid residue in this method is limited by the presence of sulfates in the crystallization system of kainite, which are necessary for the conversion of a solid residue. .

The closest in technical essence to the present invention is a method of processing solutions containing sodium, potassium and magnesium chlorides and sulfates, including evaporation of the solution, separation of sodium chloride, evaporation of the mother liquor, separation of kainite, desulfurging and evaporation of the mother liquor, separation of the solid residue, processing it water, taken in an amount of 50% by weight of the solid residue; separation of the magnesium chloride solution; mixing the solid residue with kainite; flotation; and calcining the mixture 23 Agni, when treating a solid residue with water, is carried out without first displacing the impregnating phase containing calcium salts, this leads to contamination of the chloromagnesium solution, deteriorating its quality, and to additional loss of magnesium upon further processing of chlorine magnesium solutions.

In addition, the residue processing technology after separation of mani chloride is a multi-stage process: crushing and grinding the residue, flotation, calcination at a high temperature (673,) and multi-stage, crystallization of the product, which complicates the processing process and leads to loss of potassium chloride.

The purpose of the invention is to increase the degree of recovery of magnesium chlorides and some implementation of the proposed method.

LIAH.

The goal is achieved by the method that the solution is evaporated, the sodium chloride is separated, the mother liquor is evaporated, the kainite is separated, the 25 solution is evaporated and the mother liquor is evaporated, the solid residue is separated and washed with water in two stages. in an amount of 6–15% by weight of the solid residue, the mother liquor is separated and sent to the desulfurization stage, water is added in an amount of 15–30 from the mass of magnesium chloride solution, the residue is mixed with kainito Was added to a mixture of the starting solution in a weight ratio of 6: 1-3 and at a temperature b5-8os separated solution containing magnesium and potassium chlorides. In addition, the magnesium chloride solution is returned to the stage of evaporation of the uterine kainitic solution or sent to the storage. The addition of water in the first stage in an amount of less than 6% by weight of the residue leads to the contamination of the chlorine magnesium solution with calcium ions. If water is added more than 15 mg chloride partially dissolves and is lost with calcium salts. Adding in the second stage less than 15 water leads to a decrease in the degree of extraction of magnesium chloride, and the addition of water in an amount of more than 30 leads to a significant dissolution

Kelium salts and potassium loss with a chloro-magnesium solution.

A decrease in the treatment temperature of the residue with the initial solution below 65 ° C leads to a decrease in the degree of extraction of potassium and magnesium chlorides into the solution, and at a temperature above 80 ° C, the formation of hard-growing langbeinite is observed, which also leads to a loss of K and Mg with the residue. A decrease in the ratio of residue: 1: 3 stock solution reduces the solubility of potassium-magnesium salts, increases the loss of potassium and magnesium with the residue. Increasing the 1: 6 ratio leads to dilution of the potassium-magnesium solution and to a decrease in the extraction of potassium and magnesium.

The drawing shows the scheme

The solution containing chlorides and sulphates of sodium, potassium and magnesium is fed to the evaporation stage 1, solid sodium chloride is separated, the mother liquor is fed to the evaporation stage 2, sodium chlorine is separated, the mother liquor is fed to the evaporation stage 3, cainite is separated, the mother liquor is fed the solution at the stage of desulfurization 4, by adding the calcium chloride solution and then to the evaporation stage 5, the magnesium chloride solution is separated and sent to the storage, the solid residue is sent to the first stage of the water treatment 6, the mother solution is removed at the stage 7 and return it to the desulfurization stage k, the solid residue in stage 8 is treated with water, the chlorine solution is separated in stage 9, which is sent to the evaporation stage 5 or to the storage, the resulting residue is mixed with kainite obtained in the 3 stages of evaporation and processed stage 10 original solution. Example 1. Take 10 kg of a solution containing: KC1 9-9,15; MjCl i, 96; MgS04 5.73; NaCl 11.69 and 68.2, the solution is evaporated until 60% by weight of sodium chloride is liberated (0.75 kg). Then the mother liquor is evaporated until half of the remaining sodium chloride is liberated, and 0.27 kg of sodium chloride is obtained. The mother liquor containing in wt .: K 6.29: NaCl 7, Cl 11.00; 504.9,50 and НдО 61,85 - in the amount of 5.9 kg, evaporated to release 1.65 kg of Cainite of the following composition, wt .: K 15.00; , 61; NaCl 10.60; Cl 14.70; SO 2i, 32; 28.17 including KCl 28.60 and obtaining 3.10 kg of uterine Cainite solution containing, in May,%: K 3.20; 5.35; NaCl 3.60; Q- 13.94; ,nineteen; 67.72. The mother liquor is subjected to a desulfurization by adding 1.08 kg of a solution of calcium chloride, to obtain 0.40 kg of gypsum and 3.73 kg of a protein-free solution of the next sos.tava, May. %:, 67; ., 5j; NaCl 3.10; C1 15.40, 74.41. Then jDacTBOp is evaporated until the isolation of 0.589 kg of solid residue of the following composition, May. %: KC1 35.24; KClMgCL. 611.0 22.04; NaCl 32.64; CaSa CaClg 0.65; HuOcpoF. 5.3 or KS1 nosobl L1b and MgCl 7.55 and 2.04 l kg of chlorine solution of composition, May. %: K 0.80; , 51; , 59; NaCl 0.82; C1 23.63; SOf - 0.08; 66.57 or MgCl2. 29.36. And KQ. 1.52.

The solid residue is treated with water in two stages at a temperature of:, a bath.

In the first stage, 0.035 kg of species (6% of its mass) are mixed for 6 minutes to 0.589 kg of the solid residue, filtered, and 0.050 kg of the calcium salt solution and 0.574 kg of the solid residue are obtained.

The composition of the solution of calcium salts, May. %:,; .90; , 27; NaCl l, 3t; Cl 19.78; SOJ 0.05; 71.29.

The composition of the solid residue, May. %: K 21.58; , 6l; ,ten; MaCl 33.30; Cl, 23.89; S0pj4; 18.78 or KCl 41.15; MgCl2. 5.57.

The washed solid bed in the amount of 0.574 kg is treated with 0.086 kg of water (15% of its volume), filtered for 20 minutes, and 0.141 kg of chlorine magnesium solution containing May is obtained. %: KS1 1.81; MgCl 28.90; NaCl 1.88; CaSO + CaClQ. 0.08; 67.33 and about 0.519 kg eoetava, May. %: K 29, H7; ,20; ,12; NaCl 30, .20; SG 27.60; ,50; NO 11.41 or KC1-57.15 and MgCla. 1.23.

A pot in the amount of 0.519 kg and one-second Cainite with a third etad of evaporation in the amount of 1.65 kg are treated with an initial solution in the amount of 13,014 kg (May ratio) at a temperature of 40 minutes.

Separate the solution. (14,980 kg), containing, May. %: KC1 12.3; MgCl

5,10; MgS04 5.17; NaCl 11.37; HgO 65.83 and Oatatka (needles) 0.203 kg of eoetava, May. : 1.78; , 28; ,nineteen; NaCl 84.10; Cl2.33; , 57; 10.75 or KCl 3.38.

The degree of recovery of magnesium chloride from a solid potassium chloride smelter is $ 1,521, and potassium chloride — into a rotor containing potassium and magnesium chlorides, and the chlorine solution is 89.59%.

Example 2. Take 10 kg of a solution containing, May. : KC1 8.33; MgCl 26.25; MgS04. 5, 7; .iiCl 10.85 and 68.60 evaporate it until precipitation is 60 May. % sodium chloride (0.70 kg). Then the uterine cavity is evaporated by isolating half of the sodium chloride (0.24 kg).

Uterine roentvor eoetava, May. %:

K 5.66; , 94; NnCl 5.67; Cl 12.25; , 87; 61.61 — In a quantity of 6.03 kg, the residues of Cainite, containing May, are evaporated. %: K + 13.97; Mc2-- 7.04; NaCl 10.39; SG

14.33; , 56; H, 28.71;

OR

KCl 26.64 and obtaining 3.10 kg of uterine kainitic solution of eoetava, May. %: K- 2.76; , 48; NaCl 3.71; Cl 14.30; , 68; 68.07.

The latter is subjected to a desulfurization at a pressure of 1.01 kg of a 29% calcium chloride solution; 0, 3 kg of gypsum and 3.73 kg of a calcined sulfate containing solution are obtained, in May. %: ,50; , 51; , 41; NaCl 3.40; SG 15.14; 0.14; 74.90.

The esterifacies are retrofitted until a recovery of 0.597 kg of solid residue of the following composition, May. %: KC1 26.94; .0 32.53; NaCl 30.40; CaS04fCaCli 1.04; 9.09 or KClopmee35,67 and MgCl 11J4 and 1,953 kg of chlorine magnesium radiation

eoetava, may. %: K 0.71; ,"9; , 66; NaCl 0.90; C1-23.61; S04 0.08; 66.55 or MgCl 29, 34 and KC1 1.36.

The solid residue is treated with water in two stages at a temperature of 22 ° C.

Claims (2)

In the first stage of the study, 0.97 kg of solid residue is added, 0 PSW kg of water (10.5 of its mass) is stirred for 6 minutes, filtered and 0.090 kg of calcium salt solution and 0.570 kg of solid residue are obtained. The composition of the calcium solution, May,% ./fl; , 92:, 25; NaCl 1.40; Cl 19, S0.o, 07; And .. About 71.01. The composition of the solid residue, May. %; ,ten; ,thirty; ,P; NaCl 20.04; SG23.47; , 02; 23.96 or HC1 36.43 and MgCl2.8.25, 0.570 kg of the solid residue are treated with 0.128 kg of water with C22.5 from its mass for 20 minutes, filtered off, and 0.210 kg of chlorine magnesium solution is obtained with the following composition by weight. KC1 1.70; MgCla 29.10; NaCl 1.90; CaS04 + CaCl2 0.10; Н2р 67,20 and О., 46В kg of the remainder of the composition, May. %: K 22.93; , 40; Ca 0.14; NaCl 28.64; C1 21.26; SOj0.82; H2.0 25.81; or KC1 43.72 and MgClz 1.18. The residue in the amount of 0.488 kg and and the organic kainit from the third stage of evaporation in the amount of 1.78 kg is treated with the initial solution in the amount of 10.206 kg (mass ratio 4.5: 1) at a temperature of 70 ° C for 40 minutes. A solution is obtained containing potassium and magnesium chlorides, 12.164 kg of a suitable compound of May. %: KC1 12.42; MgCla. 5.90; MgS04 4.86; NaCl 11.21; Hgp 65.61 and residue (tails) 0.310 kg composition, May. %: 1.20; ,thirty; , 18; NaCl 81.90; SG 2.01; , 55; % .0 13.86 or KC1 2.28. The degree of extraction of magnesium chloride from the solid residue of a magnesium magnesium chloride solution is 91.88, and that of potassium chloride in a solution containing potassium chlorides and magnesium and in a chloromagnesium solution of 89.95. PRI me R 3. Take 10 kg of a solution containing chlorides in May. %: KC1 7.20; MgS04: 6.17; MgCl. 7.83; NaCl 9.94 and 68.86 or 3.78 and Mg 3.39, evaporates it by evaporation on 60 May. % sodium chloride (0.64 kg). The mother liquor is subjected to evaporation in the second stage, by isolating the remaining half of sodium chloride (0.22 kg). The mother liquor composition, MA.D.:, 02; , 65; NaCl 4.20; SOj 10.16; Cl-13.51 and HjjO 61.43 in the amount of 6.08 kg are evaporated to release. 1.85 kg of Cainite of the next composition, May 6. |: K 13.27; , 22; NaCl 10.18; , 06; SG13.86; H2, o29,4l including KS1 25.30 and obtaining 3.09 kg of uterine kainitic solution of soetaw, May. , 33; , 62; NaCl 3.82; S0jf5.21; Cl 14.66 and. 68.36. At the end of the day, obessulfuvaniyu when adding 0.91 kg of a 29% calcium chloride solution is obtained, 0.34 kg of gypsum and 3.66 kg of an oeuleulfated solution of the following somatic preparation are obtained in May,%:, 27:, 58; Ca 0.45; NaCl 3.31; SOT 0.16; SG 15.14; 75.09. The esophageal solution is evaporated until the release of 0.604 kg of solid residue of the following composition, May. %: KC1 18.56; kCl MgS046H4.0 43.31; NaCl 26.15; CaSQi + CaClo 1.44; H 0 cv 10.5. Or 18, and MgClji. 14.84 and chlorine magnesium solution 1.856 kg of composition, May. %: K 0.66: 7.54; , 83; NaCl 0.74; , 09; C1 23.89; 66.25 or MgCl2 29.54 and KCl 1.26. The solid furnace is treated with water in two stages at a temperature of 22 ° C. In the first stage, 0.804 kg of solid residue is added to 0.080 kg of water (15% from Mayor), stirred for 6 minutes, filtered, and 0.112 kg of calcium salt solution and 0.572 kg of solid residue are obtained. The composition of the solution of calcium salts, May: K 0.35; Mg 5.89; Ca 38; NaCl 0.80; 5040.07; C1-19.89; 0.0 71.68. . Soetav solid Oetatka, May. : K 16.60:, 03; ,15; NaCl 26.34; 30 | -0.96; SG23.45; H20 29.47 or KC1 31.65 and MgCl 11.27. The solid residue a quantity, 0.572 kg, is treated with 30 water, i.e. 0.172 kg, within 20 minutes, filtered and receive 0,282 kg of a chlorine-magnesium solution of the following composition, May: KC1 1.52; MgCli 29.30; NaCl 1.80; CaSO + CaClj. 0.06; 0 67.32; and about 0.462 kg eoetava, May. %: K 22.60; , 23; , l8; NaCl 25.80; SG20,89; S04 0.80; 29.50 or KC1 43.09 and MgCl 0.54. An amount of 0.462 kg and an artificial Cainite with a third digestive process of 1.85 kg are treated with an initial solution in an amount of 6.936 kg (mass ratio 3: 1) at a temperature of 40 minutes. Get 8,904. Kg solution of composition, May. I: KC1 12.77; MgCl, 6.09; MgSO 6.06; NaCl 9.71; 65.37 and 0, kg residue composition, May. %: K- 0.92; , 36; , 23; NaCl 82.22; SP, 75; S0 | 0.72; H-O 13.80 or KC1 1.75. The degree of recovery of magnesium chloride from the solid residue to the chloromagnesium solution is 92.18% and chloride of calcium in the solution containing potassium and magnesium chlorides and in the chloromagnesium solution 9Q.1%. As follows from the examples, the proposed method allows to significantly increase the degree of extraction of magnesium and potassium chlorides in comparison with the known method, since in the known method the degree of extraction of magnesium chloride is 88.5, and the degree of extraction of potassium chloride VC, E7%. . Claim 1. Method of processing solutions containing sodium and potassium and magnesium chloride sulphates, including evaporation of the solution, separation of sodium chloride, evaporation of the mother liquor, separation of kainite, desulfurization and evaporation of the mother liquor, separation of the solid residue and washing it with water, characterized in In order to increase the degree of extraction of magnesium and potassium chlorides, washing the solid residue with water is carried out in two stages, with water in an amount of 6-15% by weight of the solid residue being added to the first stage. The mother liquor and naphtha are separated. equal it to the stage of desalting, water is added to the resulting residue in an amount of 15-30% of its mass, the magnesium chloride solution is separated, the residue is mixed with kainite, the initial solution is added to the mixture in a mass ratio of 6: 1-3: 1 at a temperature of 65-80 ° C and. Separate the solution containing potassium and magnesium chlorides. 2. The method according to claim 1, wherein the solution of magnesium chloride solution is returned to the stage of evaporation of NiIa uterine kainitic solution or sent to storage. Sources of information taken into account in the examination 1. M. Pos. Mineral salt technology. L., Himi, 1970, pp. 1775176. 2. US patent number 3 32258, cl. 23-91, 1969 (prototype). $ v91l patintof