CN114059989A - Dissolving mining method of low-grade solid sylvite ore - Google Patents
Dissolving mining method of low-grade solid sylvite ore Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 60
- 238000005065 mining Methods 0.000 title claims abstract description 46
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 30
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 30
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 157
- 239000012267 brine Substances 0.000 claims abstract description 156
- 239000011734 sodium Substances 0.000 claims abstract description 54
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 51
- 150000003109 potassium Chemical class 0.000 claims abstract description 35
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 31
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011591 potassium Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 21
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims description 41
- 239000011148 porous material Substances 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000033558 biomineral tissue development Effects 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 3
- 230000002262 irrigation Effects 0.000 claims 1
- 238000003973 irrigation Methods 0.000 claims 1
- 239000013505 freshwater Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 235000010755 mineral Nutrition 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 238000013459 approach Methods 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract 2
- 235000002639 sodium chloride Nutrition 0.000 description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009933 burial Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/29—Obtaining a slurry of minerals, e.g. by using nozzles
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- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
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Abstract
The invention belongs to the technical field of mineral exploitation, and particularly relates to a solution mining method of low-grade solid sylvite ore. According to the invention, unsaturated high-sodium high-salinity brine containing potassium, which cannot be developed and utilized under the current technical and economic conditions, is poured into a brine goaf of low-grade solid potassium salt ore containing soluble potassium, and as the concentration of sodium ions in the brine approaches or reaches a saturated state, the concentration of potassium ions far does not reach the saturated state, the sodium ions are not dissolved any more, and the potassium ions can be dissolved all the time until the potassium ions are approximately balanced with the concentration of potassium ions in the solid; in addition, the solid potassium ions in the low-grade solid sylvite mining area have strong activity and high solubility, are easily dissolved out of the stratum by the unsaturated potassium-containing high-sodium type high-salinity brine, and the content of the potassium ions in the brine is increased, so that the brine is easy to exploit. The solution mining method of the invention does not need to use fresh water, solves the problem of serious shortage of underground fresh water in mining areas, and simultaneously can solve the problem that the high-sodium type brine containing potassium can not be developed under the current economic and technical conditions.
Description
Technical Field
The invention belongs to the technical field of mineral exploitation, and particularly relates to a solution mining method of low-grade solid sylvite ore.
Background
With the large exploitation of the shallow brine resources of the firewood basin, the contradiction between the gradual reduction of the potassium salt resources and the fact that the water-rich property of most shallow salt inter-crystal brine cannot meet the exploitation requirements of enterprises is aggravated, and the fact that the potassium resources are in short is substantial, how to develop and utilize low-grade solid potassium salt ores to improve the current situation of the shortage of the potassium resources is a problem which needs to be solved urgently at present.
Since 2008, the amount of potassium-containing high-sodium potassium salt resources found in the west of the firewood basin reaches 8 hundred million tons, and the amount of brine reaches 4000 hundred million tons. In foreign countries, research on the development and utilization of similar high-sodium brine containing potassium is blank. In China, since 2014, Chinese geological academy, Qingkale company and the like extract brine in big wave beaches and black north concave lands to carry out indoor and salt field evaporation experiments, and the sodium salt has long crystallization route, large entrainment loss amount on potassium salt and unsatisfactory experiment result, so that the resource amount of the type cannot be exploited and utilized.
The present commonly adopted mining technology of low-grade solid sylvite ore is a solution mining method using fresh water and old brine as solvent, i.e. adding halite or old brine into fresh water, raising the mineralization degree of solvent and then pouring it into rock salt layer to dissolve beneficial elements in solid such as K, Mg. The solution mining method has the advantages that beneficial elements such as K, Mg and the like are dissolved out under the condition of not damaging the crystal framework or the form of the rock salt layer, and the method has the defects that a large amount of fresh water resources are needed, and the method cannot be realized in areas lacking the fresh water resources. However, the low-grade solid sylvine ore cannot be mined by a solution mining process of adding rock salt and old brine into fresh water due to the fact that the west of the firewood basin has little rainfall, large evaporation capacity and serious shortage of fresh water resources.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for mining low-grade solid sylvite ore by dissolving unsaturated potassium-containing high-sodium type high-salinity brine, which does not need to use fresh water resources and is suitable for developing low-grade solid sylvite ore in areas lacking fresh water resources.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a solution mining method of low-grade solid sylvite ore, which comprises the following steps:
filling unsaturated high-sodium high-salinity brine containing potassium into a brine goaf of low-grade solid potassium salt ore for dissolving, and when K is contained in the dissolved brine+When the concentration of the brine is more than or equal to 5.436g/L, pumping the dissolved brine to a salt pan for evaporation separation; the mineralization degree of the unsaturated potassium-containing high-sodium high-mineralization brine is more than or equal to 150 g/L; k in the unsaturated potassium-containing high-sodium high-salinity brine+0.1～3g/L，Na+More than 50 g/L; k in the low-grade solid sylvite ore+0.53-1.5% of Na+The content is 15-25%.
Preferably, the unsaturated potassium-containing high-sodium type hypersalinity brine also comprises: mg (magnesium)2+＞5g/L，Li+＞1mg/L，Ca2+＞3.726g/L，SO4 2-＞1g/L，B2O3Is more than 118.2 mg/L; the specific gravity of the unsaturated potassium-containing high-sodium type high-salinity brine is more than 1.15g/cm3。
Preferably, the unsaturated potassium-containing high-sodium hypersalinity brine is gravel pore brine and/or structural fracture pore brine.
Preferably, the low-grade solid sylvite ore further comprises: mg (magnesium)2+1～4.55％，Li+1～20g/T，Ca2+0.1～0.44％，SO4 2-5～18.79％，B2O330-71.03 g/T, 5-10% water-insoluble substance.
Preferably, the filling is performed through a hose and a submersible pump, the diameter of the hose is larger than 150cm, and the lift of the submersible pump is larger than or equal to 50 m.
Preferably, the flow rate of the filled unsaturated potassium-containing high-sodium hypersalinity brine is more than or equal to 20m3/h。
Preferably, the unsaturated potassium-containing high-sodium hypersalinity brine is obtained by pumping out brine in a brine extraction well in the west of the firewood basin along a well wall pipe and a strainer pipe by using a submersible pump.
Preferably, the well depth of the brine extraction well is 500-1500 m.
Preferably, the casing tube has a diameter of >108mm and the strainer tube has a porosity of > 5%.
Preferably, the power of the submersible pump is more than 20kw/h, and the lift of the submersible pump is more than or equal to 50 m.
The invention provides a solution mining method of low-grade solid sylvite ore, which comprises the following steps: filling unsaturated high-sodium high-salinity brine containing potassium into a brine goaf of low-grade solid potassium salt ore for dissolving, and when K is contained in the dissolved brine+When the concentration of the brine is more than or equal to 5.436g/L, pumping the dissolved brine to a salt pan for evaporation separation; the mineralization degree of the unsaturated potassium-containing high-sodium high-mineralization brine is more than or equal to 150 g/L; k in the unsaturated potassium-containing high-sodium high-salinity brine+0.1～3g/L，Na+More than 50 g/L; k in the low-grade solid sylvite ore+0.53-1.5% of Na+The content is 15-25%. The invention fills the unsaturated high-sodium high-salinity brine containing potassium into the brine goaf of the low-grade solid sylvite ore containing soluble sylvite, because the Na in the unsaturated high-sodium high-salinity brine containing potassium+The concentration is near or has reached saturation, and K+The concentration is far from the saturation state (the liquid phase point is K)+，Na+//Cl--H2The O ternary system phase diagram is positioned at a NaCl saturation line and is positioned in a sodium chloride region consistent with the system point when the salt in the goaf is dissolved), and the system point is positioned in the sodium chloride regionNaCl reaches the equilibrium of dissolution, Na+No longer soluble, K+In this zone, K can be dissolved up to and in the solid+The concentration approaches equilibrium; in addition, due to solid K in low-grade solid sylvite ore area+Has strong activity and high solubility, is very easy to be dissolved out of the stratum by the unsaturated potassium-containing high-sodium type high-salinity brine, and improves the K in the brine+The content of the brine is easy to exploit, and a great amount of unsaturated potassium-containing high-sodium type high-salinity brine exists in the west of the firewood basin, but the brine is lack of fresh water resources, so that the solution mining method does not need to use fresh water for solution mining, solves the problem that underground fresh water is seriously lacked in an exploitation mining area, and can solve the problem that the potassium-containing high-sodium type brine cannot be developed and utilized under the current economic and technical conditions.
Furthermore, the unsaturated potassium-containing high-sodium type high-salinity brine is used for water dissolution mining of the low-grade solid potassium salt ore, because the main component in the salt rock stratum is NaCl crystals and the main component in the brine is also NaCl, the brine is not easy to dissolve a large amount of salt rock stratum, the structure of the salt rock stratum is not easy to damage, collapse is not easy to generate, collapse accidents in mining can be prevented, the purpose of safe mining is achieved, and the mining cost can be reduced.
Drawings
FIG. 1 is a diagram of a sample of a low-grade solid sylvite salt used in example 1;
FIG. 2 is a graph of a dissolution test of a low-grade solid sylvite salt sample in example 1.
Detailed Description
The invention provides a solution mining method of low-grade solid sylvite ore, which comprises the following steps:
filling unsaturated high-sodium high-salinity brine containing potassium into a brine goaf of low-grade solid potassium salt ore for dissolving, and when K is contained in the dissolved brine+When the concentration of the brine is more than or equal to 5.436g/L, pumping the dissolved brine to a salt pan for evaporation separation; the mineralization degree of the unsaturated potassium-containing high-sodium high-mineralization brine is more than or equal to 150 g/L; k in the unsaturated potassium-containing high-sodium high-salinity brine+0.1～3g/L，Na+More than 50 g/L; k in the low-grade solid sylvite ore+0.53-1.5% of Na+The content is 15～25％。
The invention pours the unsaturated high-sodium bittern into the goaf of low-grade solid sylvite ore for dissolving.
In the invention, the mineralization degree of the unsaturated potassium-containing high-sodium type high-mineralization brine is more than or equal to 150g/L, preferably 150-300 g/L, and K in the unsaturated potassium-containing high-sodium type high-mineralization brine+0.1～3g/L，Na+More than 50g/L, the unsaturated potassium-containing high-sodium type high-salinity brine also comprises: mg (magnesium)2+Preferably > 5g/L, Li+Preferably > 1mg/L, Ca2+Preferably > 3.726g/L, SO4 2-Preferably > 1g/L, B2O3Preferably > 118.2 mg/L.
In the invention, the specific gravity of the unsaturated potassium-containing high-sodium hypersalinity brine is preferably more than 1.15g/cm3(ii) a The water level burial depth of the unsaturated potassium-containing high-sodium type high-salinity brine is preferably 25-50 m.
In the present invention, the unsaturated potassium-containing high-sodium hypersalinity brine is preferably a gravel pore brine and/or a tectonic fracture pore brine, more preferably a gravel pore brine; the unsaturated potassium-containing high-sodium hypersalinity brine is preferably unsaturated potassium-containing high-sodium hypersalinity brine in the west of a faaida basin.
Unsaturated potassium-containing high-sodium hypersalinity brine in the west of the firewood basin exists in the gravel layer and is supported in a particle mode, so that collapse cannot occur even if a large amount of brine is extracted. The brine has low grade, large resource amount and high mineralization degree, and has large loss amount of potassium due to long stone salt crystallization route during exploitation, so that the brine can not be exploited and utilized independently under the prior art conditions. The amount of brine estimated in the survey and evaluation report of solid-liquid phase potassium salt resources since the late era of the Chaaida basin reaches several billion tons, and the brine cannot be developed and utilized.
In the invention, the unsaturated potassium-containing high-sodium hypersalinity brine is preferably obtained by pumping out the brine in a brine-extracting well at the west part of a firewood basin along a well wall pipe and a strainer pipe by using a submersible pump; the well depth of the brine extraction well is preferably 500-1500 m; the casing tube preferably has a diameter of >108mm, the strainer preferably has a porosity of > 5%; the power of the submersible pump is preferably more than 20kw/h, and the lift of the submersible pump is preferably more than or equal to 50 m.
The well depth of the brine extraction well is determined according to the buried depth and the thickness of a brine-containing layer; the lengths of the casing pipe and the strainer pipe are determined according to the buried depth and the length of the halogen-containing layer.
In the invention, K in the low-grade solid sylvite ore+0.53～1.5％，Na+15-25% of Mg in the low-grade solid sylvite ore2+Preferably 1 to 4.55%, Li+Preferably 1 to 20g/T, Ca2+Preferably 0.1-0.44%, SO4 2-Preferably 5 to 18.79%, B2O3Preferably 30-71.03 g/T, preferably 5-10% of water-insoluble substances, and the mineralization degree of the low-grade solid sylvite ore is not less than 150g/L, preferably 150-300 g/L.
Solid sylvite ores in the west of the faaida basin are not easily mined directly due to the large burial depth and lack of underground (fresh) water. The salt intercrystalline brine in the mining area in the salt pan in the west of the firewood basin has weak water-rich property, and the water quantity of a single well is less than 200m3And d, the water level is rapidly and greatly reduced during production, and the water level is reduced to about 140m at present, so that the resource is rapidly exhausted. A large amount of statistics proves that the water level of a soluble sylvite mining area can be rapidly and greatly reduced after mining, a large amount of pores or even karst caves can be formed in a brine goaf, and the salt field goaf can be frequently collapsed, frequently occurs in accidents and cannot be normally mined.
The resource amount reaches ten million tons, and K+、Mg2+、Li+Is extremely soluble in unsaturated brine to increase the content of Na in brine+、Ca2+Etc. are difficult to dissolve in such brines.
The potassium magnesium salt mining area in the salt pan has a huge rock salt layer which is rich in low-grade solid potassium, magnesium and the like, the resource amount reaches ten million tons, and K is+、Mg2+、Li+Is extremely soluble in unsaturated brine to increase the content of Na in brine+、Ca2+Etc. are difficult to dissolve in such brines.
In the present invention, the pouring is preferably by softeningA pipe and a submersible pump, the diameter of the hose is optimized>150cm, the lift of the submersible pump is preferably more than or equal to 50m, and the flow rate of the filled unsaturated potassium-containing high-sodium type hypersalinity brine is preferably more than or equal to 20m3/h。
The length of the hose is adjusted according to the distance from the brine collecting well of the unsaturated potassium-containing high-sodium type high-salinity brine to the brine collecting space area of the low-grade solid sylvite ore.
When K is contained in the dissolved brine+When the concentration of the brine is more than or equal to 5.436g/L, the dissolved brine is pumped to a salt pan for evaporation and separation.
The process of pumping the dissolved brine into the salt pan is not particularly limited, and the process known in the field can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Selecting one solid salt sample (low-grade solid sylvine) at a new collapse fracture position 10m underground of a stormy beach mining area, wherein the total weight is 11.36kg, the upper layer is white salt formed by a large amount of dehydrated mirabilite, the lower layer is mud salt and hard in texture, cutting the solid salt sample into 4 parts, putting one part of the solid salt sample into a plastic bucket with a cover and a cover, wherein the plastic bucket is filled with gravel pore brine (the water chemistry property is chloride type brine, the mineralization degree is 288.0g/L, the density is 1.187g/mL, and the characteristics of potassium content, high sodium content, high magnesium content and unsaturation), sealing the cover to prevent evaporation, and standing the plastic bucket indoors to dissolve ores for 62 days to obtain brine with dissolved potassium.
Example 2
Selecting one solid salt sample (low-grade solid sylvine ore) at a new collapse fracture position 10m underground in a stormy beach mining area, wherein the total weight is 11.36kg, the upper layer is white salt formed by a large amount of dehydrated mirabilite, the lower layer is muddy salt and hard in texture, cutting the mixture into 4 parts, taking one part of the mixture, putting the other part of the mixture into a plastic bucket with a cover and filled with structural crack pore brine (the water chemistry property is chloride type, the mineralization degree is 293.5g/L, the density is 1.190g/mL, and the unsaturated brine containing potassium, low magnesium, high sodium and high calcium) in a southern wing mountain area, sealing the cover to prevent evaporation, and placing the bucket indoors for standing and dissolving the ore for 62 days to obtain brine for dissolving the potassium.
Comparative example 1
Selecting one solid salt sample (low-grade solid sylvine) at a new collapse fracture part of 10m underground of a stormy beach mining area, wherein the total weight is 11.36kg, the upper layer is white salt formed by a large amount of dehydrated mirabilite, the lower layer is muddy salt with hard texture, cutting the mixture into 4 parts, taking one part of the mixture, putting the other part of the mixture into a plastic bucket with a cover, wherein the plastic bucket is filled with intercrystalline brine (the water chemistry property of which is magnesium sulfate subtype brine, the mineralization degree is 376.4g/L, the density is 1.270g/mL, and the characteristics of high potassium, high magnesium, high sulfate radical and saturation), sealing the cover to prevent evaporation, and placing the plastic bucket indoors for standing and dissolving ores for 62 days to obtain brine for dissolving potassium.
And (3) testing:
selecting one solid salt sample (low-grade solid sylvine) at a new collapse fracture position 10m underground of a stormy beach mining area, wherein the total weight is 11.36kg, the upper layer is white salt formed by a large amount of dehydrated mirabilite, the lower layer is mud-containing salt and is hard in texture, cutting the salt sample into 4 parts, crushing one salt sample (01B-S), uniformly mixing, keeping the constant temperature of 30 ℃ and drying for 24 hours, and carrying out chemical analysis, wherein the results are shown in table 1. The solid salt sample is mainly composed of Na2SO4、NaCl、MgCl2、MgSO4、KCl、CaSO4The obvious sodium sulfate exists on the surface.
TABLE 1 table of contents of respective components of solid salt samples used in examples 1 to 2 and comparative example 1
Sampling five times from 6 and 21 days to 9 and 5 days in 2021, observing and taking brine analysis samples at time intervals of 3 days, 7 days, 14 days, 30 days and 62 days respectively, and observing the contents: the environmental temperature, the humidity, the brine temperature and the water loss are fully stirred before sampling and analyzing samples, and the samples are sampled and analyzed after standing and clarifying for 2 hours. Water solubilization test to K in brine+、Mg2+The test was terminated when there was no sign of an increase in concentration and the sampling was recorded as shown in table 2.
TABLE 2 sampling record tables of examples 1 to 2 and comparative example 1
When sampling, the liquid is absorbed by a disposable plastic dropper, slowly dropped into a small beaker, accurately weighed with a certain mass (generally 20.0g), and moved into a 250mL volumetric flask for constant volume; after the solid is mixed uniformly, a sample with a certain mass (generally 20.0g) is directly weighed, dissolved and transferred into a 250mL volumetric flask for constant volume. The detection method comprises the following steps: k+、Na+、Ca2+、Mg2+、SO4 2-、Li+、Sr2+Detecting by using an inductively coupled plasma emission spectrometry; cl-、B2O3Detecting by a volumetric method; rb+、Cs+、Br-、I-、NO3-Detecting by spectrophotometry; the density was measured by the pycnometer method. The sample analysis is completed by a test center of a comprehensive geological mineral exploration institute of faaida in Qinghai province, and the detection quality meets the relevant requirements of 'geological mineral laboratory test quality management Specification' DZ/T0130-2006. The results of the measurements are shown in Table 3 and Table 3 below.
TABLE 3 brine component content in each stage in examples 1-2 and comparative example 1
TABLE 3 brine component content in each stage of examples 1 to 2 and comparative example 1
As can be seen from Table 3 and Table 3, K is extracted from the brine in the pores of gravel+、Mg2+、SO4 2-、Li+The effect is obvious, and the increasing rate of the concentration of each ion is K on the 43 th day of the test+33.10％、Mg2+93.40％、SO4 2-1921％、Li+28.14％、Na+5.35 percent. Obtained by calculating the amount of dissolved, SO4 2-Mainly from MgSO in the solid phase4Indicating high Na+The existence of the sodium sulfate has good inhibition effect on the dissolution of the sodium sulfate. Ca in brine2+With a significant reduction in dissolved SO4 2-Reacts therewith to form CaSO4As a result, Ca in the brine can be effectively removed2+And the other ions do not change much. The brine is converted from chloride type to magnesium sulfate subtype after dissolving the ore.
As can be seen from Table 3 and Table 3, K was extracted with tectonic fissure pores+、Mg2+、SO4 2-、Na+The effect of (A) is obvious, and at the 43 th day of the test, K+Concentration increase rate 24.90%, Mg2+621％，SO4 2-2511％，Na+11.54 percent. And Ca2+、Sr2+The concentration of the brine is obviously reduced, and a large amount of Ca is originally contained in the brine2+、Sr2+With SO4 2-Insoluble precipitate is generated by the reaction, thereby effectively reducing Ca2+、Sr2+And (4) concentration. The brine is converted from chloride type to magnesium sulfate subtype after dissolving the ore.
The invention selects the saturated intercrystalline brine with high potassium and high magnesium to synchronously carry out the ore dissolving test, as the comparative test, as can be seen from the table 3 and the table 3, when the saturated intercrystalline brine with high potassium and high magnesium is dissolved in water, except Mg2+、SO4 2-With little dissolution, K+The other ions do not dissolve in.
Watch with watch3 and continuing from Table 3, K for gravel pore brine up to maximum dissolution+The increase rate of volume concentration was 33.10% and Na+Only 5.35 percent of the total weight is increased; k for constructing crack pore brine+The improvement rate is 24.90 percent and Na+The improvement rate was 11.54%. The ore dissolving effect of the gravel pore brine is obviously better than that of the structural fracture pore brine. The intercrystalline brine is saturated and shows no sign of dissolving potassium in the solid ore.
As can be seen from Table 3 and Table 3 below, K is dissolved+The effect of (A) is used as a measurement standard of ore dissolving effect, and from the ore dissolving effect of gravel pore brine and tectonic fracture pore brine, K is measured in two groups of tests from the ore dissolving time to the 7 th day+The concentration increment is 0.60g/L and 0.69g/L respectively; 0.65g/L and 0.81g/L respectively at 14 days; 1.35g/L and 1.16g/L at 43 days respectively; when the ore is dissolved in 74 days, although K is+Slightly increased but Na+And Cl-The concentration is reduced, and K caused by the precipitation of sodium chloride in the brine due to the reduction of the environmental temperature is considered+The concentration is improved, the mineralization degree is almost unchanged, the concentration of potassium ions and the concentration of 43 days are not obviously increased, and the ions of the intercrystalline brine are not obviously changed in the ore dissolving process. Therefore, the dissolving mining time can be finished within about 45 days at room temperature, and the dissolving mining time is prolonged in consideration of the low underground brine temperature (10 ℃).
The invention adopts potassium-containing high-sodium type gravel pore brine and constructed crack pore brine to dissolve K in solid ore+、Mg2+、Li+The dissolving effect of the method is obviously better than that of saturated intercrystalline brine, and the selectivity is better. However, the existing part of the constructed fissure pore brine is far away from the salt field development, the underground water quantity is unstable, the water resource is small, and factors such as stratum collapse and the like can be generated by pumping brine for a long time, so that the long-term exploitation target cannot be achieved; and because the salt intercrystalline brine has the worst dissolving effect on solid salt, the water quantity is small, the KCl content is high, and the salt intercrystalline brine is directly used for short-term or small-quantity mining and cannot be used for long-term mining. The gravel pore brine exists around or at the bottom of the solid salt field, and the pores of the gravel layer at the brine storage layer are supported by particles, so that the water yield is high, and the collapse of the stratum can not be generated after long-term extraction.Therefore, potassium-containing high sodium type grit pore brine is the best solvent. And sodium is not dissolved by a large amount of mirabilite in the dissolving process, and sulfate radicals exist in the solid ore, so that the concentration of calcium ions is effectively reduced, the concentration of the sulfate radicals is improved, brine is converted from a chloride type to a sulfate type, and the quality of potassium mixed salt in the process of extracting potassium from brine after dissolving and mining can be effectively improved. When the gravel pore brine is dissolved to K+When the concentration is 5.436g/L, the brine is saturated, and the ore dissolution is stopped. At this time K+The increase in volume concentration was 33.10% compared with Na+The concentration increase rate is only 5.35%, and the dissolution effect is better.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A dissolving mining method of low-grade solid sylvite ore comprises the following steps:
filling unsaturated high-sodium high-salinity brine containing potassium into a brine goaf of low-grade solid potassium salt ore for dissolving, and when K is contained in the dissolved brine+When the concentration of the brine is more than or equal to 5.436g/L, pumping the dissolved brine to a salt pan for evaporation separation; the mineralization degree of the unsaturated potassium-containing high-sodium high-mineralization brine is more than or equal to 150 g/L; k in the unsaturated potassium-containing high-sodium high-salinity brine+0.1～3g/L，Na+More than 50 g/L; k in the low-grade solid sylvite ore+0.53-1.5% of Na+The content is 15-25%.
2. The solution mining method according to claim 1, wherein the unsaturated potassium-containing high-sodium type hypersalinity brine further comprises: mg (magnesium)2+＞5g/L，Li+＞1mg/L，Ca2+＞3.726g/L，SO4 2-＞1g/L，B2O3Is more than 118.2 mg/L; the specific gravity of the unsaturated potassium-containing high-sodium type high-salinity brine is more than 1.15g/cm3。
3. The solution mining method according to claim 1, wherein the unsaturated potassium-containing high-sodium hypersalinity brine is gravel pore brine and/or tectonic fracture pore brine.
4. The solution mining method according to claim 1, characterized in that the low-grade solid sylvite ore further comprises: mg (magnesium)2+1～4.55％，Li+1～20g/T，Ca2+0.1～0.44％，SO4 2-5～18.79％，B2O330-71.03 g/T, 5-10% water-insoluble substance.
5. The solution mining method according to claim 1, wherein the irrigation is performed by a hose and a submersible pump, the hose has a diameter of more than 150cm, and the head of the submersible pump is more than or equal to 50 m.
6. The solution mining method according to claim 1 or 5, wherein the flow rate of the filled unsaturated potassium-containing high-sodium hypersalinity brine is more than or equal to 20m3/h。
7. The solution mining method according to claim 1, wherein the unsaturated potassium-containing high-sodium hypersalinity brine is obtained by pumping out brine from a brine-producing well in the west of the fada basin along casing and strainer pipes with a submersible pump.
8. The solution mining method according to claim 7, wherein the well depth of the brine mining well is 500-1500 m.
9. The solution mining method according to claim 7, wherein the casing pipe has a diameter >108mm and the drainpipe has a porosity > 5%.
10. The solution mining method according to claim 7, wherein the power of the submersible pump is more than 20kw/h, and the head of the submersible pump is more than or equal to 50 m.
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