Collector composition, collector and use thereof

Abstract

The present invention provides a collector composition, a collector and its application. The collector composition comprises, in molar percentage, 75-85% of aliphatic amine and 15-25% of aliphatic sulfate, wherein the carbon chain length of the aliphatic amine is C 10 ~C 22 The carbon chain length of aliphatic sulfate is C 10 ~C 20 . will include carbon chain length C 10 ~C 22 The fatty amine with carbon chain length C 10 ~C 20 The collector obtained by mixing components of aliphatic sulfates with the above-mentioned carbon chain lengths improves the collector's flotation capture efficiency for minerals. The preferred fatty amines and preferred aliphatic sulfates with the above-mentioned carbon chain lengths increase the collector's adsorption capacity at the bubble / flotation liquid interface. When the above collector is used in potassium chloride forward flotation, it also achieves a high potassium chloride flotation yield while significantly reducing costs. The collector also exhibits excellent low-temperature resistance, and the resulting potassium chloride product has a high purity.

Description

Technical Field

[0001] The present invention relates to the technical field of collectors, and in particular to a collector composition, a collector and applications thereof. Background Art

[0002] Collector is a key agent in the flotation process of potassium chloride. It changes the surface activity of potassium chloride, creates a hydrophobicity difference between potassium chloride and other minerals, and adheres to the surface of bubbles to achieve the purpose of flotation separation.

[0003] Currently, aliphatic primary amines with a carbon chain length of more than 12 are mainly used as potassium chloride collectors worldwide. Dodecylamine hydrochloride is mainly used for potassium chloride flotation abroad, while octadecylamine hydrochloride is mainly used as a potassium chloride flotation collector in my country.

[0004] In the potassium salt flotation process, flotation yield is influenced not only by factors such as the chemical composition of the system and the amount of collector used, but also to a significant extent by temperature. In actual production, due to the long winters in the Qarhan Salt Lake area of ​​Qinghai Province, when temperatures drop below 5°C, the flotation yield of potassium chloride drops significantly. To improve the flotation yield of potassium chloride, the amount of collector used is typically increased. This significantly increases costs and reduces the purity of the potassium chloride product. Summary of the Invention

[0005] The main purpose of the present invention is to provide a collector composition, a collector and its application, so as to solve the problems of low flotation yield and low purity of potassium chloride in the flotation of potassium chloride in salt lakes at low temperatures in the prior art.

[0006] In order to achieve the above object, according to one aspect of the present invention, a collector composition is provided, which comprises, by mole percentage, 75-85% of aliphatic amine and 15-25% of aliphatic sulfate, wherein the carbon chain length of the aliphatic amine is C 10 ~C 22 The carbon chain length of aliphatic sulfate is C 10 ~C 20 .

[0007] Furthermore, in terms of molar percentage, the above-mentioned fatty amine includes a first fatty amine and a second fatty amine, wherein the carbon chain length of the first fatty amine is C 10 ~C 17 , the carbon chain length of the second fatty amine is C 18 ~C 22 , preferably the first fatty amine is dodecylamine and / or hexadecylamine, and preferably the second fatty amine is octadecylamine and / or eicosylamine.

[0008] Furthermore, the molar ratio of the first fatty amine to the second fatty amine is 1:4 to 1:2.

[0009] Furthermore, the carbon chain length of the above-mentioned aliphatic sulfate is C 12 ~C 16 Preferably, the aliphatic sulfate is selected from any one or more of sodium lauryl sulfate, potassium lauryl sulfate, sodium hexadecyl sulfate, and potassium hexadecyl sulfate.

[0010] Furthermore, the collector composition comprises, by mole percentage, 20% of dodecylamine, 60% of octadecylamine and 20% of sodium lauryl sulfate.

[0011] According to another aspect of the present invention, a collector is provided, which is prepared by mixing a collector composition, and the collector composition is the aforementioned collector composition.

[0012] According to another aspect of the present invention, there is provided an application of a collector, comprising: adding carnallite to water to prepare a saturated mother liquor, and adding a collector to the saturated mother liquor for flotation, wherein the collector is the above-mentioned collector.

[0013] Furthermore, the above application also includes filtering the foam obtained by flotation to obtain a filter cake, washing, dehydrating and drying the filter cake to obtain potassium chloride, and preferably the collector is an aqueous solution with a mass concentration of 0.25-1.25%.

[0014] Furthermore, the potassium content in the carnallites is 10 to 20 wt %, and the mass ratio of the collector to the carnallites is preferably 3:1600 to 1:320.

[0015] Furthermore, the mass ratio of the carnallite to water is 1.2 to 2.5:1, preferably 2:1.

[0016] Applying the technical solution of the present invention, the carbon chain length is C 10 ~C 22 The fatty amine with carbon chain length C 10 ~C 20The collector is obtained by mixing the components of aliphatic sulfates of the present invention. The aliphatic amine as the cationic part and the aliphatic sulfate as the anionic part neutralize the anionic and cationic properties, thereby reducing the electrostatic repulsion between the collector molecules and the critical micelle concentration of the collector, thereby improving the flotation collection effect of the collector on minerals. The preferred aliphatic amine with the above carbon chain length helps to improve the hydrophobicity of the surface of the collector molecules after adsorption on the surface of potassium chloride crystals. The preferred aliphatic sulfate with the above carbon chain length helps to obtain a more stable adsorption layer and a higher adsorption layer density for the collector, thereby increasing the adsorption amount of the collector at the bubble / flotation liquid phase interface. When the above collector is used for potassium chloride positive flotation, even without adding other auxiliary agents such as frothers and inhibitors, the flotation yield of potassium chloride is very high, while the cost is greatly reduced. The collector has excellent low-temperature resistance. In particular, when the flotation liquid phase temperature is low (below 5°C), the collector still has good potassium chloride collection ability, and the obtained potassium chloride product has a high purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0018] Figure 1 A simplified flotation process diagram of potassium chloride provided in Example 1 of the present application is shown;

[0019] Figure 2 Schematic diagrams showing the flotation results of potassium chloride at (a) 23° C. and (b) 5° C. for collectors of different mass concentrations according to Example 1 and Comparative Example 1 of the present application;

[0020] Figure 3 Schematic diagram showing the flotation results of potassium chloride at (a) 23° C. and (b) 5° C. for collectors of different mass concentrations according to Example 2 and Comparative Example 2 of the present application; and

[0021] Figure 4 Schematic diagrams are shown of the flotation results of potassium chloride with collectors of different mass concentrations according to Example 3 and Comparative Example 3 of the present application at (a): 23° C. and (b): 5° C. DETAILED DESCRIPTION

[0022] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0023] As analyzed in the background technology of this application, the prior art has problems of low flotation yield and low purity of potassium chloride in the flotation of potassium chloride in salt lakes at low temperatures. In order to solve this problem, this application provides a collector composition, a collector and its application.

[0024] In a typical embodiment of the present application, a collector composition is provided, which comprises, by mole percentage, 75-85% of aliphatic amine and 15-25% of aliphatic sulfate, wherein the carbon chain length of the aliphatic amine is C 10 ~C 22 The carbon chain length of aliphatic sulfate is C 10 ~C 20 .

[0025] will include carbon chain length C 10 ~C 22 The fatty amine with carbon chain length C 10 ~C 20 The collector is obtained by mixing the components of aliphatic sulfates of the present invention. The aliphatic amine as the cationic part and the aliphatic sulfate as the anionic part neutralize the anionic and cationic properties, thereby reducing the electrostatic repulsion between the collector molecules and the critical micelle concentration of the collector, thereby improving the flotation collection effect of the collector on minerals. The preferred aliphatic amine with the above carbon chain length helps to improve the hydrophobicity of the surface of the collector molecules after adsorption on the surface of potassium chloride crystals. The preferred aliphatic sulfate with the above carbon chain length helps to obtain a more stable adsorption layer and a higher adsorption layer density for the collector, thereby increasing the adsorption amount of the collector at the bubble / flotation liquid phase interface. When the above collector is used for potassium chloride positive flotation, even without adding other auxiliary agents such as frothers and inhibitors, the flotation yield of potassium chloride is very high, while the cost is greatly reduced. The collector has excellent low-temperature resistance. In particular, when the flotation liquid phase temperature is low (below 5°C), the collector still has good potassium chloride collection ability, and the obtained potassium chloride product has a high purity.

[0026] In one embodiment of the present application, the fatty amine comprises a first fatty amine and a second fatty amine, and the carbon chain length of the first fatty amine is C 10 ~C 17 , the carbon chain length of the second fatty amine is C 18 ~C 22 , preferably the first fatty amine is dodecylamine and / or hexadecylamine, and preferably the second fatty amine is octadecylamine and / or eicosylamine.

[0027] The synergistic effect of the first fatty amine and the second fatty amine of the above two carbon chain lengths is more conducive to reducing the turbidity of the collector in the saturated potassium chloride solution, thereby further improving the dispersion state of the collector in the saturated potassium chloride solution. Furthermore, the first fatty amine and the second fatty amine of the above categories are preferably more conducive to exerting the synergistic effect of the two.

[0028] In one embodiment of the present application, the molar ratio of the first fatty amine to the second fatty amine is 1:4 to 1:2.

[0029] The preferred carbon chain length is C 18 ~C 22 The amount of the second fatty amine is greater than the carbon chain length C 10 ~C 17 The amount of the first fatty amine is more conducive to the synergistic effect of the two. It is particularly preferred to limit the molar ratio of the two to the above range, which is conducive to obtaining a collector with better flotation effect.

[0030] In order to further enhance the synergistic effect of fatty amine and fatty sulfate, it is preferred that the carbon chain length of the fatty sulfate is C 12 ~C 16 Preferably, the aliphatic sulfate is selected from any one or more of sodium lauryl sulfate, potassium lauryl sulfate, sodium hexadecyl sulfate, and potassium hexadecyl sulfate.

[0031] In some embodiments of the present application, the collector composition preferably includes 20% dodecylamine, 60% octadecylamine and 20% sodium lauryl sulfate, calculated in molar percentage, so that the synergistic effect of the components is further optimized, thereby making the flotation effect of the collector better.

[0032] In another typical embodiment of the present application, a collector is provided, which is prepared by mixing a collector composition, and the collector composition is the above-mentioned collector composition.

[0033] will include carbon chain length C 10 ~C 22 The fatty amine with carbon chain length C 10 ~C 20The collector is obtained by mixing the components of aliphatic sulfates of the present invention. The aliphatic amine as the cationic part and the aliphatic sulfate as the anionic part neutralize the anionic and cationic properties, thereby reducing the electrostatic repulsion between the collector molecules and the critical micelle concentration of the collector, thereby improving the flotation collection effect of the collector on minerals. The preferred aliphatic amine with the above carbon chain length helps to improve the hydrophobicity of the surface of the collector molecules after adsorption on the surface of potassium chloride crystals. The preferred aliphatic sulfate with the above carbon chain length helps to obtain a more stable adsorption layer and a higher adsorption layer density for the collector, thereby increasing the adsorption amount of the collector at the bubble / flotation liquid phase interface. When the above collector is used for potassium chloride positive flotation, even without adding other auxiliary agents such as frothers and inhibitors, the flotation yield of potassium chloride is very high, while the cost is greatly reduced. The collector has excellent low-temperature resistance. In particular, when the flotation liquid phase temperature is low (below 5°C), the collector still has good potassium chloride collection ability, and the obtained potassium chloride product has a high purity.

[0034] In another typical embodiment of the present application, an application of a collector is provided, comprising: adding carnallite to water to prepare a saturated mother liquor, and adding a collector to the saturated mother liquor for flotation, wherein the collector is the above-mentioned collector.

[0035] Since the solubility of magnesium chloride in carnallites is much greater than that of potassium chloride and sodium chloride, and there is a common ion effect between potassium chloride, sodium chloride and magnesium chloride, the solubility of potassium chloride and sodium chloride decreases sharply with the increase of magnesium chloride concentration. When potassium chloride reaches saturation in the mother liquor, carnallites continue to dissolve, and saturated potassium chloride and sodium chloride are precipitated as crystals. Therefore, carnallites are first made into saturated mother liquor to reduce the common ion effect between potassium chloride, sodium chloride and magnesium chloride as much as possible. Then, the above collector is added to the saturated mother liquor. The collector selectively changes the surface properties of potassium chloride, i.e., the surface hydrophobicity of potassium chloride becomes stronger, thereby causing potassium chloride to combine with foam and rise to the surface of the saturated mother liquor, while sodium chloride remains in the saturated mother liquor.

[0036] In some embodiments of the present application, the above application further includes filtering the foam obtained by flotation to obtain a filter cake, and washing, dehydrating and drying the filter cake to obtain potassium chloride. Preferably, the above collector is controlled to be an aqueous solution with a mass concentration of 0.25-1.25%, such as 0.25%, 0.50%, 0.75%, 1.00% or 1.25%, so that the effective ingredients in the collector solution have a suitable concentration, thereby more efficiently performing the flotation of potassium chloride.

[0037] Since sodium chloride particles are small, they tend to adhere to the foam during flotation. Therefore, in order to remove the sodium chloride in the foam, the filter cake needs to be washed to remove the sodium chloride adhered to the foam. Distilled water can be used for washing.

[0038] The potassium content in existing conventional carnallites is 10 to 20 wt%, such as 10 wt%, 10.23 wt%, 12.39 wt%, 15.22 wt%, 16 wt%, 18 wt% or 20 wt%. In order to float out potassium chloride in the carnallites as much as possible without causing unnecessary waste of the collector, the mass ratio of the collector to the carnallites is preferably 3:1600 to 1:320, such as 3:1600, 4:1600 or 5:1600.

[0039] In one embodiment of the present application, the mass ratio of the above-mentioned carnallite to water is 1.2 to 2.5:1, such as 1.2:1, 1.5:1, 1.8:1, 2.0:1, 2.2:1, 2.5:1, preferably 2:1.

[0040] Based on the common ion effect between potassium chloride, sodium chloride and magnesium chloride, it can be seen that during the flotation process of potassium chloride, it is necessary to ensure that the magnesium chloride in carnallites can be completely dissolved in water as much as possible, thereby ensuring a higher magnesium chloride concentration in the saturated mother liquor and further ensuring a higher potassium chloride yield. Therefore, it is preferred to control the mass ratio of carnallites to water within the above range.

[0041] The beneficial effects of the present application will be further illustrated below with reference to embodiments.

[0042] Example 1

[0043] according to Figure 1 The simplified process diagram shown in FIG. 1 is used for flotation of potassium chloride. Specifically,

[0044] Preparation of carnallite saturated mother liquor: Weigh 400 g of carnallite ore (potassium content in the ore is 15.22 wt%) into a 1000 mL beaker, add distilled water (about 50% of the ore weight) for hydrolysis, and continue stirring for 6 h.

[0045] Preparation method of the collector: accurately weigh dodecylamine (0.0361 g, 0.0732 g, 0.1085 g, 0.1446 g) and octadecylamine (0.1576 g, 0.3152 g, 0.4728 g, 0.6304 g) and place them in a 100 mL beaker, add 90 mL of distilled water, and seal. Heat and stir at 75°C for 4 hours until melted, add 3 mL of 36% concentrated hydrochloric acid for acidification to prepare a hydrochloric acid amine cationic collector, continue stirring for 30 minutes, add a certain amount of sodium dodecyl sulfate (0.0562 g, 0.1124 g, 0.1686 g, 0.2248 g) to the solution, continue stirring for 2 hours, transfer the solution to a 100 mL volumetric flask, and dilute to 100 mL with distilled water. After the obtained collector is evenly mixed, seal and store for later use, wherein the above four groups of masses of dodecylamine, octadecylamine and sodium dodecyl sulfate correspond to the four mass concentrations of the collector, 0.25%, 0.5%, 0.75% and 1%, respectively.

[0046] The flotation method of potassium chloride is to place the saturated mother liquor of carnallite in the flotation tank and stir it for 5 minutes. Then, the four mass concentrations of collectors are added respectively. The mass ratio of collector to carnallite is 1:400. After stirring for 5 minutes, flotation begins. The temperature of the flotation process is controlled throughout. The flotation temperature is 23℃ or 5℃ respectively. The speed of the flotation machine impeller is 1600r / min and the air flow rate is 0.1m 3 / h, the action time is 10min. After the flotation process is completed, the mineral product is filtered, washed, and weighed to obtain potassium chloride product. The flotation results are as follows: Figure 2 shown.

[0047] from Figure 2 As can be seen from the figure, at 23°C, the collector's KCl capture efficiency was significantly higher than that of octadecylamine. Experimental results indicate that by mixing the three reagents in a specific ratio, the anionic and cationic charges of each reagent are neutralized, making it easier to form semi-micelles on the KCl surface, thereby enhancing the KCl capture efficiency. Compared with the simple octadecylamine collector, the KCl capture efficiency was significantly improved.

[0048] At low temperatures (5°C), the collector's flotation yield for KCl was significantly higher than that of octadecylamine, by an average of approximately 10%. This result demonstrates that the collector of the present application has a significantly higher solubility in a saturated KCl solution at low temperatures than pure octadecylamine, thereby improving the flotation yield of KCl at low temperatures.

[0049] Example 2

[0050] The difference from Example 1 is that the potassium content in the raw ore is 12.39wt%, and the flotation results are as follows: Figure 3 shown.

[0051] Example 3

[0052] The difference from Example 1 is that the potassium content in the raw ore is 10.23wt%, and the flotation results are as follows: Figure 4 shown.

[0053] Example 4

[0054] The difference from Example 1 is that, based on molar percentage, the collector composition includes 20% hexadecylamine, 60% eicosamine and 20% potassium hexadecyl sulfate.

[0055] Example 5

[0056] The difference from Example 1 is that, based on mole percentage, the collector composition includes 16% of dodecylamine, 64% of octadecylamine and 20% of sodium lauryl sulfate.

[0057] Example 6

[0058] The difference from Example 1 is that, based on molar percentage, the collector composition includes 26.67% of dodecylamine, 53.33% of octadecylamine and 20% of sodium lauryl sulfate.

[0059] Example 7

[0060] The difference from Example 1 is that, based on molar percentage, the collector composition includes 40% of dodecylamine, 40% of octadecylamine and 20% of sodium lauryl sulfate.

[0061] Example 8

[0062] The difference from Example 1 is that, based on molar percentage, the collector composition includes 18.75% of dodecylamine, 61.25% of octadecylamine and 25% of sodium lauryl sulfate.

[0063] Example 9

[0064] The difference from Example 1 is that, based on molar percentage, the collector composition includes 21.25% of dodecylamine, 58.75% of octadecylamine and 15% of sodium lauryl sulfate.

[0065] Example 10

[0066] The difference from Example 1 is that, based on molar percentage, the collector composition includes 22.5% of dodecylamine, 67.5% of octadecylamine and 10% of sodium lauryl sulfate.

[0067] Example 11

[0068] The difference from Example 1 is that the mass ratio of the collector to the carnallite is 3:1600.

[0069] Example 12

[0070] The difference from Example 1 is that the mass ratio of the collector to the carnallite is 1:320.

[0071] Example 13

[0072] The difference from Example 1 is that the mass ratio of the collector to the carnallite is 1:1600.

[0073] Comparative Example 1

[0074] The difference from Example 1 is that the collector is octadecylamine, and the flotation results are as follows: Figure 2 shown.

[0075] Comparative Example 2

[0076] The difference from Example 2 is that the collector is octadecylamine, and the flotation results are as follows: Figure 3 shown.

[0077] Comparative Example 3

[0078] The difference from Example 3 is that the collector is octadecylamine, and the flotation results are as follows: Figure 4 shown.

[0079] Comparative Example 4

[0080] The difference from Example 1 is that the collector is dodecylamine.

[0081] Comparative Example 5

[0082] The difference from Example 1 is that the collectors are octadecylamine and dodecylamine.

[0083] Comparative Example 6

[0084] The difference from Example 1 is that the collector is dodecylamine hydrochloride.

[0085] Comparative Example 7

[0086] The difference from Example 1 is that the collector is octadecylamine hydrochloride.

[0087] The sodium tetraphenylborate method (GB / T 6549-2011) was used to determine the flotation yield and grade of potassium chloride obtained by collector flotation in Examples 1 to 3 and Comparative Examples 1 to 3, respectively. The test results when the mass concentration of the collector was 1 wt% are listed in Table 1.

[0088] Table 1

[0089]

[0090] The sodium tetraphenylborate method (GB / T 6549-2011) was used to determine the flotation yield and grade of potassium chloride obtained by collector flotation in Examples 4 to 13 and Comparative Examples 4 to 7, respectively. The flotation yield and grade of potassium chloride obtained by flotation at 5° C. when the mass concentration of the collector was 1 wt % are listed in Table 2.

[0091] Table 2

[0092]

[0093]

[0094] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0095] will include carbon chain length C 10 ~C 22 The fatty amine with carbon chain length C 10 ~C 20 The collector is obtained by mixing the components of aliphatic sulfates of the present invention. The aliphatic amine as the cationic part and the aliphatic sulfate as the anionic part neutralize the anionic and cationic properties, thereby reducing the electrostatic repulsion between the collector molecules and the critical micelle concentration of the collector, thereby improving the flotation collection effect of the collector on minerals. The preferred aliphatic amine with the above carbon chain length helps to improve the hydrophobicity of the surface of the collector molecules after adsorption on the surface of potassium chloride crystals. The preferred aliphatic sulfate with the above carbon chain length helps to obtain a more stable adsorption layer and a higher adsorption layer density for the collector, thereby increasing the adsorption amount of the collector at the bubble / flotation liquid phase interface. When the above collector is used for potassium chloride positive flotation, even without adding other auxiliary agents such as frothers and inhibitors, the flotation yield of potassium chloride is very high, while the cost is greatly reduced. The collector has excellent low-temperature resistance. In particular, when the flotation liquid phase temperature is low (below 5°C), the collector still has good potassium chloride collection ability, and the obtained potassium chloride product has a high purity.

[0096] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. An application of a collector, comprising: Carnallite is added to water to prepare a saturated mother liquor, and a collector is added to the saturated mother liquor for flotation, wherein the collector is prepared by mixing a collector composition. In terms of molar percentage, the collector composition comprises 75-85% of aliphatic amine and 15-25% of aliphatic sulfate, wherein the carbon chain length of the aliphatic amine is C 10 ~C 22 The carbon chain length of the aliphatic sulfate is C 10 ~C 20 .

2. The use according to claim 1, characterized in that In terms of molar percentage, the fatty amine includes a first fatty amine and a second fatty amine, wherein the carbon chain length of the first fatty amine is C 10 ~C 17 , the carbon chain length of the second fatty amine is C 18 ~C 22 .

3. The use according to claim 2, characterized in that The first fatty amine is dodecylamine and / or hexadecylamine.

4. The use according to claim 2, characterized in that The second fatty amine is octadecylamine and / or eicosylamine.

5. The use according to claim 2, characterized in that The molar ratio of the first fatty amine to the second fatty amine is 1:4 to 1:

2.

6. The use according to claim 1, characterized in that The carbon chain length of the aliphatic sulfate is C 12 ~C 16 .

7. The use according to claim 6, characterized in that The aliphatic sulfate is selected from any one or more of sodium lauryl sulfate, potassium lauryl sulfate, sodium hexadecyl sulfate, and potassium hexadecyl sulfate.

8. The use according to claim 1, characterized in that In terms of mole percentage, the collector composition includes 20% dodecylamine, 60% octadecylamine and 20% sodium lauryl sulfate.

9. The use according to claim 1, characterized in that The application further comprises filtering the foam obtained by flotation to obtain a filter cake, and washing, dehydrating and drying the filter cake to obtain potassium chloride.

10. The use according to claim 9, characterized in that The collector is an aqueous solution with a mass concentration of 0.25-1.25%.

11. The use according to claim 1, characterized in that The potassium content in the carnallite is 10-20 wt %.

12. The use according to claim 11, characterized in that The mass ratio of the collector to the carnallites is 3:1600 to 1:

320.

13. The use according to claim 1, characterized in that The mass ratio of the carnallite to the water is 1.2-2.5:

1.

14. The use according to claim 13, characterized in that The mass ratio of the carnallite to the water is 2:1.

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