CN114059989B - Solution mining method of low-grade solid potassium salt ore - Google Patents
Solution mining method of low-grade solid potassium salt ore Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000005065 mining Methods 0.000 title claims abstract description 29
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 title abstract description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 153
- 239000012267 brine Substances 0.000 claims abstract description 150
- 239000011734 sodium Substances 0.000 claims abstract description 61
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 50
- 150000003109 potassium Chemical class 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 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 claims description 18
- 230000033558 biomineral tissue development Effects 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 abstract description 25
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 24
- 239000011591 potassium Substances 0.000 abstract description 23
- 239000013505 freshwater Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 7
- 239000011707 mineral Substances 0.000 abstract description 7
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 abstract 2
- 235000002639 sodium chloride Nutrition 0.000 description 63
- 238000004090 dissolution Methods 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 239000011780 sodium chloride Substances 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010446 mirabilite Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000009933 burial Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 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
- 238000010586 diagram Methods 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- -1 Na + Chemical compound 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000003804 effect on potassium Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase 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
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 238000003860 storage Methods 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- 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)
- Seasonings (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of mineral exploitation, and particularly relates to a solution exploitation method of low-grade solid potassium salt ores. According to the invention, unsaturated potassium-containing high-sodium high-mineralization brine 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 ores containing soluble potassium, and the concentration of sodium ions in the brine is close to or reaches a saturated state, but the concentration of potassium ions is far from the saturated state, so that the sodium ions are not dissolved any more, and the concentration of potassium ions can be dissolved until the concentration of potassium ions in the brine is close to the balance with that of the potassium ions in the solid; in addition, the solid potassium ions in the low-grade solid potassium salt mining area have strong activity and high solubility, are easily dissolved out of the stratum by unsaturated potassium-containing high-sodium type hypersalinity brine, and improve the content of potassium ions in the brine so as to be easy to be mined. The solution mining method of the invention does not need to use fresh water, solves the problem of serious lack of underground fresh water in mining areas, and can solve the problem that potassium-containing high-sodium brine cannot 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 exploitation method of low-grade solid potassium salt ores.
Background
Along with the large-scale exploitation of shallow brine resources of the Qaidam basin, the contradiction between the gradual reduction of potassium salt resources and the fact that the water enrichment of most shallow salt intergranular brine cannot meet the exploitation requirements of enterprises is aggravated, the fact that the potassium resources are in essence short has become true, and how to develop and utilize low-grade solid potassium salt ores to improve the current shortage situation of the potassium resources is a problem which needs to be solved at present.
In 2008, the amount of potassium-containing high-sodium potassium salt resources found in the western part of the Qidamu basin reaches 8 hundred million tons, and the amount of brine reaches 4000 hundred million tons. In abroad, the research on the development and utilization of similar potassium-containing high-sodium brine is blank. In China, since 2014, china geology academy of sciences, green potassium company and the like draw brine in the great wave beach and the North and south concave land to carry out indoor and salt pan evaporation experiments, and the salt is large in entrainment loss quantity of potassium salt due to long crystallization route of sodium salt, so that experimental results are not ideal, and the type of resource quantity cannot be exploited and utilized.
The exploitation technology of low-grade solid potassium salt mine is a solution exploitation method which takes fresh water and old brine as solvents, namely, stone salt or old brine is added into the fresh water, the mineralization degree of the solvents is improved, then the solvents are poured into a rock salt layer, and beneficial elements such as K, mg in the solids are dissolved. The method has the advantages that the beneficial elements such as K, mg are dissolved under the condition of not damaging the rock salt layer crystal skeleton or morphology, 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. And because the Western rainfall of the Qidamu basin is small, the evaporation capacity is large, fresh water resources are seriously lacking, and a solution mining process of adding stone salt and old brine into the fresh water cannot be adopted to mine low-grade solid potash salt ores.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for dissolving and collecting low-grade solid potash salt ores, which adopts unsaturated potassium-containing high-sodium high-mineralization brine to dissolve and collect the low-grade solid potash salt ores, does not need to use fresh water resources, and is suitable for developing the low-grade solid potash salt ores in areas lacking fresh water resources.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a solution mining method of low-grade solid potassium salt ores, which comprises the following steps:
Filling unsaturated potassium-containing high-sodium high-mineralization brine into a brine goaf of low-grade solid potash salt ores, dissolving, and pumping the dissolved brine into a salt field for evaporation separation when K + in the dissolved brine is more than or equal to 5.436 g/L; the mineralization degree of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than or equal to 150g/L; k +0.1～3g/L,Na+ in the unsaturated potassium-containing high-sodium hypersalinity brine is more than 50g/L; the content of K + in the low-grade solid kalium ore is 0.53-1.5%, and the content of Na + is 15-25%.
Preferably, the unsaturated potassium-containing high sodium type hypersalinity brine also contains ：Mg2+＞5g/L,Li+＞1mg/L,Ca2+＞3.726g/L,SO4 2-＞1g/L,B2O3＞118.2mg/L; the specific gravity of the unsaturated potassium-containing high sodium type hypersalinity brine is more than 1.15g/cm 3.
Preferably, the unsaturated potassium-containing high sodium hypersalinity brine is gravel pore brine and/or structural fracture pore brine.
Preferably, the low-grade solid potash salt ore also contains ：Mg2+1～4.55％,Li+1～20g/T,Ca2+0.1～0.44％,SO4 2-5～18.79％,B2O330～71.03g/T,% to 10% of water insoluble matters.
Preferably, the filling is performed through a hose and a submersible pump, the diameter of the hose is more than 150cm, and the lift of the submersible pump is more than or equal to 50m.
Preferably, the flow rate of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than or equal to 20m 3/h.
Preferably, the unsaturated potassium-containing high sodium type hypersalinity brine is obtained by pumping brine in a brine collecting well at the west of the Qidamu basin along a well wall pipe and a water filtering pipe by using a submersible pump.
Preferably, the well depth of the brine production well is 500-1500 m.
Preferably, the diameter of the casing is >108mm and the porosity of the filter tube is >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 50m.
The invention provides a solution mining method of low-grade solid potassium salt ores, which comprises the following steps: filling unsaturated potassium-containing high-sodium high-mineralization brine into a brine goaf of low-grade solid potash salt ores, dissolving, and pumping the dissolved brine into a salt field for evaporation separation when K + in the dissolved brine is more than or equal to 5.436 g/L; the mineralization degree of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than or equal to 150g/L; k +0.1～3g/L,Na+ in the unsaturated potassium-containing high-sodium hypersalinity brine is more than 50g/L; the content of K + in the low-grade solid kalium ore is 0.53-1.5%, and the content of Na + is 15-25%. According to the invention, unsaturated potassium-containing high-sodium high-mineralization brine is poured into a brine goaf of a low-grade solid potassium salt mine containing soluble potassium salt, because the concentration of Na + in the unsaturated potassium-containing high-sodium high-mineralization brine is close to or reaches a saturated state, but the concentration of K + is far less than the saturated state (the liquidus point is close to the NaCl saturation line in a K +,Na+//Cl--H2 O ternary system phase diagram and is consistent with the system point in a sodium chloride region when the goaf salt is dissolved), naCl reaches dissolution balance in the region, na + is not dissolved any more, and K + can be dissolved in the region until the concentration of K + in the solid is close to the balance; in addition, because the solid K + in the low-grade solid potassium salt mining area has strong activity and large solubility, is extremely easy to be dissolved out of a stratum by the unsaturated potassium-containing high-sodium type hypersalinity brine, improves the content of K + in the brine and is easy to be mined, and a huge amount of unsaturated potassium-containing high-sodium type hypersalinity brine exists at the west of the Qidamu basin but lacks fresh water resources, the solution mining method does not need to use fresh water for solution mining, solves the problem of serious lack of underground fresh water in the 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, because the main component in the salt rock layer is NaCl crystal and the main component in the brine is NaCl, the brine is not easy to dissolve the salt rock layer in a large amount, the rock salt layer structure is not damaged, collapse is not easy to occur, collapse accidents in exploitation can be prevented, the aim of safe exploitation is achieved, and the exploitation cost can be reduced.
Drawings
FIG. 1 is a diagram of a sample of low grade solid potash salt ore salt used in example 1;
fig. 2 is a diagram of a dissolution test of a low-grade solid potash mineral salt sample in example 1.
Detailed Description
The invention provides a solution mining method of low-grade solid potassium salt ores, which comprises the following steps:
Filling unsaturated potassium-containing high-sodium high-mineralization brine into a brine goaf of low-grade solid potash salt ores, dissolving, and pumping the dissolved brine into a salt field for evaporation separation when K + in the dissolved brine is more than or equal to 5.436 g/L; the mineralization degree of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than or equal to 150g/L; k +0.1～3g/L,Na+ in the unsaturated potassium-containing high-sodium hypersalinity brine is more than 50g/L; the content of K + in the low-grade solid kalium ore is 0.53-1.5%, and the content of Na + is 15-25%.
The invention fills the unsaturated potassium-containing high sodium type high mineralization brine into the brine goaf of the low-grade solid potash salt ore for dissolution.
In the invention, the mineralization degree of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than or equal to 150g/L, preferably 150-300 g/L, wherein K +0.1～3g/L,Na+ in the unsaturated potassium-containing high-sodium type hypersalinity brine is more than 50g/L, and the unsaturated potassium-containing high-sodium type hypersalinity brine also comprises: mg 2+ is preferably > 5g/L, li + is preferably > 1Mg/L, ca 2+ is preferably > 3.726g/L, SO 4 2- is preferably > 1g/L, and B 2O3 is preferably > 118.2Mg/L.
In the invention, the specific gravity of the unsaturated potassium-containing high sodium type hypersalinity brine is preferably more than 1.15g/cm 3; the water level burial depth of the unsaturated potassium-containing high-sodium hypersalinity brine is preferably 25-50 m.
In the present invention, the unsaturated potassium-containing high sodium hypersalinity brine is preferably gravel pore brine and/or structural fracture pore brine, more preferably gravel pore brine; the unsaturated potassium-containing high sodium type hypersalinity brine is preferably unsaturated potassium-containing high sodium type hypersalinity brine at the west of the Qidamu basin.
Unsaturated potassium-containing high sodium type hypersalinity brine in the western part of the firewood basin exists in the gravel layer and is supported in a particle shape, so that collapse does not occur even if the brine is extracted in a large amount. The brine has low grade, large resource amount and high mineralization degree, and the loss of potassium is large due to long stone salt crystallization route during exploitation, so that the brine cannot be independently exploited under the prior art. The estimated halogen water amount reaches hundreds of billions tons in the solid-liquid phase potassium salt resource investigation and evaluation report of the late period of the Qidamu basin, and the method cannot be developed and utilized.
In the invention, the unsaturated potassium-containing high sodium type hypersalinity brine is preferably obtained by pumping brine in a brine collecting well at the west of a Qidamu basin along a well wall pipe and a water filtering pipe by using a submersible pump; the well depth of the brine production well is preferably 500-1500 m; the diameter of the well wall pipe is preferably >108mm, and the porosity of the water filtering pipe is preferably >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 50m.
The well depth of the brine production well is determined according to the burial depth and thickness of the brine-containing layer; the lengths of the well wall pipe and the water filtering pipe are determined according to the burial depth and the length of the halogen-containing layer.
In the invention, K +0.53～1.5％,Na+ -25% in the low-grade solid potash salt ore, mg 2+ in the low-grade solid potash salt ore is preferably 1-4.55%, li + is preferably 1-20 g/T, ca 2+ is preferably 0.1-0.44%, SO 4 2- is preferably 5-18.79%, B 2O3 is preferably 30-71.03 g/T, water insoluble matter is preferably 5-10%, and mineralization degree of the low-grade solid potash salt ore is more than or equal to 150g/L, preferably 150-300 g/L.
Solid potash ores in the western region of the Qidamu basin are not easily mined directly due to large burial depths and lack of underground (fresh) water. The salt inter-crystal brine in the mining area in the western salt pan of the Qidamu basin is weak in water enrichment, the single-well water quantity is less than 200m 3/d, the water level is rapidly and greatly reduced during production, the current water level is reduced to about 140m, and the resource is rapidly exhausted. A large number of statistics prove that the water level of a soluble sylvite mining area can be rapidly and greatly reduced after mining, a large number of holes and even karst cave can be formed in a brine goaf, so that the goaf of a salt pan is frequently collapsed, accidents are frequent, and normal mining cannot be performed.
The resource amount reaches tens of millions of tons, and K +、Mg2+、Li+ and the like are extremely easy to dissolve in unsaturated brine to increase the content of the brine, and Na +、Ca2+ and the like are difficult to dissolve in the brine.
The potassium magnesium salt mining area in the salt pan is provided with a huge rock salt layer, is rich in low-grade solid potassium, magnesium and the like, has a resource amount of tens of millions of tons, is extremely easy to dissolve in unsaturated brine to increase the content of the brine, and is difficult to dissolve in the brine such as Na +、Ca2+ and the like.
In the invention, the filling is preferably performed through a hose and a submersible pump, the diameter of the hose is preferably more than 150cm, the lift of the submersible pump is preferably more than or equal to 50m, and the flow of the unsaturated potassium-containing high sodium type hypersalinity brine is preferably more than or equal to 20m 3/h.
The length of the hose is adjusted according to the distance from a brine collecting well of unsaturated potassium-containing high-sodium high-mineralization brine to a brine goaf of low-grade solid potash salt ores.
When K + in the dissolved brine is more than or equal to 5.436g/L, the method pumps the dissolved brine into a salt pan for evaporation separation.
The process of pumping the dissolved brine into a salt pan is not particularly limited, and the process well known in the art can be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
A piece of solid salt sample (low-grade solid potassium salt mine) at a new collapse fracture position of 10m underground in a great wave beach mining area is selected, 11.36kg is taken as a whole, the upper layer is white salt which is dehydrated by a large amount of mirabilite, the lower layer is mud-containing salt, the texture is hard, the salt is cut into 4 parts, one part of salt is put into a plastic bucket with a cover, the salt is taken as brine (the brine with chloride type water chemical property, the mineralization degree is 288.0g/L, the density is 1.187g/mL, and the salt is characterized by potassium, high sodium, high magnesium and unsaturation), the salt is put into a room for standing and dissolving for 62 days, and the brine for dissolving and taking potassium is obtained.
Example 2
Selecting a block of solid salt sample (low-grade solid potassium salt mine) at the new collapse fracture position of 10m underground in a great wave beach mining area, 11.36kg, wherein the upper layer is white salt obtained by a large amount of water loss of mirabilite, the lower layer is mud-containing salt, the texture is hard, cutting the salt into 4 parts, one part of the brine is put into a plastic bucket with a cover, wherein the plastic bucket is provided with fracture pore brine (the chemical property of water is chloride, 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 the Nanlingshan region, the plastic bucket is covered and sealed to prevent evaporation, and the plastic bucket is placed indoors for standing and dissolving ores for 62 days, so that brine for dissolving potassium is obtained.
Comparative example 1
A piece of solid salt sample (low-grade solid potassium salt mine) at a new collapse fracture position of 10m underground in a great wave beach mining area is selected, 11.36kg is taken, the upper layer is white salt obtained by a large amount of water loss of mirabilite, the lower layer is mud-containing salt, the texture is hard, the salt is cut into 4 parts, one part of salt is put into a plastic bucket with a cover, the salt is put into the plastic bucket, the brine is filled with the 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, the characteristics of high potassium, high magnesium, high sulfate and saturation are achieved, the cover is sealed to prevent evaporation, and the salt is placed indoors for standing and dissolving the salt for 62 days, so that brine for dissolving potassium is obtained.
And (3) testing:
A piece of solid salt sample (low-grade solid potassium salt mine) at a new collapse fracture position of 10m underground in a great wave beach mining area is selected, 11.36kg is taken as a whole, the upper layer is white salt with a large amount of dehydrated mirabilite, the lower layer is mud-containing salt, the texture is hard, the salt sample is cut into 4 parts, one part of salt sample (01B-S) is taken and crushed and uniformly mixed, and the mixture is dried for 24 hours at the constant temperature of 30 ℃ for chemical analysis, and the result is shown in Table 1. The solid salt sample mainly comprises Na 2SO4、NaCl、MgCl2、MgSO4、KCl、CaSO4, and the surface has obvious mirabilite loss.
TABLE 1 content of solid salt like Each component used in examples 1 to 2 and comparative example 1
Sampling for five times from 21 days of 2021, 6 and 21 days to 5 days of 9 and 5 days, observing and taking brine analysis samples at time intervals of 3 days, 7 days, 14 days, 30 days and 62 days respectively, and observing contents: the environmental temperature, humidity, halogen temperature and water loss are fully stirred before sample collection, and the sample is collected and analyzed after standing and clarification for 2 hours. The water-soluble test was terminated until there was no sign of an increase in the concentration of K +、Mg2+ in the brine, and the sample record is shown in table 2.
Table 2 sample recording tables of examples 1 to 2 and comparative example 1
During each sampling, the liquid is sucked by a disposable plastic dropper, the sample is slowly dripped into a small beaker, the sample with certain mass (generally 20.0 g) is accurately weighed, and the sample is transferred into a 250mL volumetric flask for constant volume; after the solid is uniformly mixed, a sample with a certain mass (generally 20.0 g) 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+ is detected by an inductively coupled plasma emission spectrometry; cl -、B2O3 is detected by a capacity method; rb +、Cs+、Br-、I-、NO3- is detected spectrophotometrically; density was measured by the pycnometer method. The sample analysis is completed by the Qinghai province Qaidam comprehensive geological mineral exploration hospital test center, and the detection quality meets the relevant requirements of DZ/T0130-2006 of geological mineral laboratory test quality management Specification. The results of the measurements are shown in Table 3 and the following Table 3.
Table 3 the brine component content amounts for each stage in examples 1-2 and comparative example 1
Table 3 shows the component content of brine in each stage of examples 1 to 2 and comparative example 1
As can be seen from Table 3 and subsequent Table 3, the effect of dissolving K +、Mg2+、SO4 2-、Li+ in the brine with gravel pores was remarkable, and the concentration increase rate of each ion was K +33.10％、Mg2+93.40％、SO4 2-1921％、Li+28.14％、Na+ 5.35.35% at the 43 rd day of the test. By calculating the dissolution amount, SO 4 2- is mainly derived from MgSO 4 in the solid phase, which shows that the presence of high Na + has good inhibition effect on the dissolution of mirabilite. The Ca 2+ in the brine is obviously reduced, which is caused by the reaction of the dissolved SO 4 2- with the dissolved SO to generate CaSO 4, SO that Ca 2+ in the brine can be effectively removed, and the change of other ions is not great. After dissolution of the ore, the brine is converted from chloride form to magnesium sulfate subtype.
As can be seen from Table 3 and subsequent Table 3, the effect of dissolving K +、Mg2+、SO4 2-、Na+ with the structural fissure pore brine is relatively obvious, and the concentration increase rate of K + is 24.90% and the concentration increase rate of Mg 2+621％,SO4 2-2511％,Na+ 11.54.54% are at the 43 th day of the test. The concentration of Ca 2+、Sr2+ is obviously reduced, and a large amount of Ca 2+、Sr2+ in brine reacts with SO 4 2- to generate insoluble precipitate, SO that the concentration of Ca 2+、Sr2+ is effectively reduced. After dissolution of the ore, the brine is converted from chloride form to magnesium sulfate subtype.
According to the invention, the high-potassium and high-magnesium saturated intergranular brine is selected to carry out a dissolution test in the same step, and as a comparison test, as can be seen from table 3 and subsequent table 3, when the high-potassium and high-magnesium saturated intergranular brine is dissolved, other ions such as K + are not dissolved except a small amount of Mg 2+、SO4 2-.
As can be seen from table 3 and subsequent table 3, the increase rate of K + volume concentration of the gravel pore brine was 33.10% and Na + was only 5.35% at the maximum dissolution amount; the improvement rate of K + and Na + of the structural fracture pore brine is 24.90% and 11.54%. The dissolving effect of the gravel pore brine is obviously better than that of the structural fracture pore brine. The inter-crystalline brine has reached saturation and has no sign of dissolving potassium in the solid ore.
From Table 3 and subsequent Table 3, the effect of dissolving K + was taken as a measure of the dissolution effect, and from the point of view of the dissolution effect of the gravel pore brine and the structural fracture pore brine, the increase of the K + concentration in the two groups of experiments was 0.60g/L and 0.69g/L respectively from the time of dissolution to day 7; at 14 days, the concentration is 0.65g/L and 0.81g/L respectively; at day 43, the concentration is 1.35g/L and 1.16g/L respectively; when the mineral dissolution is carried out in 74 days, although the concentration of K + is slightly improved, the concentration of Na + and the concentration of Cl - are reduced, the concentration of K + caused by precipitation of sodium chloride in brine is improved due to the reduction of the ambient temperature, the mineralization degree is almost unchanged, the concentration of potassium ions and the concentration of 43 days do not obviously increase, and each ion of the inter-crystalline brine does not obviously change in the mineral dissolution process. Therefore, the ore dissolution time can be completed within 45 days at room temperature, and the ore dissolution time can be prolonged in consideration of the low underground halogen temperature (10 ℃).
When the potassium-containing high-sodium sand gravel pore brine and the structural fracture pore brine are adopted for dissolving ores, the dissolving effect on K +、Mg2+、Li+ in solid ores is obviously better than that of saturated intergranular brine, and the selectivity is better. However, the position where the brine with the fissure pores exists is far away from a developed salt pan, the underground water quantity is unstable, the water resource is small, and the factors such as stratum collapse and the like can be generated when the brine is extracted for a long time, so that the aim of long-term exploitation cannot be achieved; and because the salt inter-crystalline brine has the worst dissolution effect on solid salt, the water quantity is small, the KCl content is high, and the salt inter-crystalline brine is directly used for short-term or small-amount exploitation and cannot be exploited for a long time. The gravel pore brine exists around or at the bottom of the solid salt field, the pores of the gravel layer of the brine storage layer are supported by particles, the water quantity is large, long-term extraction is carried out, and the collapse of the stratum can not be generated. Thus potassium-containing high sodium sand gravel pore brine is the best solvent. In addition, sodium is not dissolved in a large amount in the dissolution process, sulfate radicals in the solid ores exist, so that the concentration of calcium ions is effectively reduced, the sulfate radical concentration is improved, the brine is converted from chloride type to sulfate type, and the quality of potassium mixed salt in the potassium extraction process of the brine after dissolution and extraction can be effectively improved. When the gravel pore brine is dissolved to the concentration of K + g/L, the brine reaches a saturated state, and the continuous ore dissolution is stopped. At this time, the volume concentration increase rate of K + is 33.10%, and the concentration increase rate of Na + is only 5.35%, so that the dissolution effect is good.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, according to which one can obtain other embodiments without inventiveness, these embodiments are all within the scope of the invention.
Claims (7)
1. A solution mining method of low-grade solid potash salt ore comprises the following steps:
Filling unsaturated potassium-containing high-sodium high-mineralization brine into a brine goaf of low-grade solid potash salt ores, dissolving, and pumping the dissolved brine into a salt field for evaporation separation when K + in the dissolved brine is more than or equal to 5.436 g/L; the method for obtaining the unsaturated potassium-containing high sodium type hypersalinity brine comprises the steps of pumping brine in a brine collecting well at the west of a Qidamu basin by using a submersible pump along a well wall pipe and a water filtering pipe; the mineralization degree of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than or equal to 150g/L;
The content of each component in the unsaturated potassium-containing high-sodium type hypersalinity brine is ：K+ 0.1～3g/L,Na+＞50g/L,Mg2+ ＞5g/L,Li+ ＞1mg/L,Ca2+ ＞3.726g/L,SO4 2-＞1g/L,B2O3＞118.2mg/L;, and the specific gravity of the unsaturated potassium-containing high-sodium type hypersalinity brine is more than 1.15g/cm 3;
The content of each component in the low-grade solid potash salt ore is ：K+ 0.53～1.5％,Na+ 15～25％,Mg2+ 1～4.55％,Li+ 1～20g/T,Ca2+ 0.1～0.44％,SO4 2- 5～18.79％,B2O3 30～71.03g/T, -10% of water insoluble matters.
2. The solution mining method according to claim 1, wherein the unsaturated potassium-containing high sodium hypersalinity brine is gravel pore brine and/or formation fracture pore brine.
3. The solution mining method according to claim 1, wherein the filling is performed through a hose and a submersible pump, the diameter of the hose is >150cm, and the lift of the submersible pump is not less than 50m.
4. The method for dissolving and collecting according to claim 1 or 3, wherein the flow rate of the unsaturated potassium-containing high-sodium high-mineralization brine is more than or equal to 20m 3/h.
5. The solution mining method according to claim 1, wherein the well depth of the brine mining well is 500-1500 m.
6. The solution mining method according to claim 1, wherein the diameter of the casing is >108mm and the porosity of the filter tube is >5%.
7. The solution mining method according to claim 1, wherein the power of the submersible pump is >20kw/h, and the lift of the submersible pump is not less than 50m.
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