CN110872105A - Method for efficiently leaching calcium and magnesium ions in phosphorite - Google Patents
Method for efficiently leaching calcium and magnesium ions in phosphorite Download PDFInfo
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- CN110872105A CN110872105A CN201811010170.2A CN201811010170A CN110872105A CN 110872105 A CN110872105 A CN 110872105A CN 201811010170 A CN201811010170 A CN 201811010170A CN 110872105 A CN110872105 A CN 110872105A
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- 238000002386 leaching Methods 0.000 title claims abstract description 270
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 113
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 101
- 239000002367 phosphate rock Substances 0.000 title claims abstract description 94
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 85
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011575 calcium Substances 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 162
- 239000007788 liquid Substances 0.000 claims abstract description 139
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 60
- 239000007787 solid Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 64
- -1 ammonium ions Chemical class 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 41
- 229910019142 PO4 Inorganic materials 0.000 claims description 40
- 239000010452 phosphate Substances 0.000 claims description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 description 25
- 239000011777 magnesium Substances 0.000 description 23
- 229910052749 magnesium Inorganic materials 0.000 description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 22
- 239000012141 concentrate Substances 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000003337 fertilizer Substances 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for efficiently leaching calcium and magnesium ions in phosphorite, which comprises the steps of fully mixing a first phosphorite solid-liquid mixture containing magnesium hydroxide and calcium hydroxide with a first ammonium ion solution to form a first solid-liquid reaction system; controlling the pH value of the solution in the first solid-liquid reaction system to be 9-11, carrying out solid-liquid separation on the first solid-liquid reaction system after reacting for a first leaching time to obtain a solution containing soluble calcium ions and a second phosphorite solid with a first preset leaching rate; fully mixing the second phosphorite solid with a second ammonium ion solution to form a second solid-liquid reaction system; controlling the pH value of the solution in the second solid-liquid reaction system to be 6.0-7.5, and carrying out solid-liquid separation on the second solid-liquid reaction system after the second leaching time of the reaction to obtain a solution containing soluble magnesium ions and a third phosphorite solid with a second preset leaching rate. The method can obtain calcium ion solution and magnesium ion solution with better purity in the leaching time.
Description
Technical Field
The invention relates to the technical field of fertilizers, in particular to a method for efficiently leaching calcium and magnesium ions in phosphorite.
Background
Phosphorite is a non-renewable resource, although the phosphorite resource in China is relatively rich, the grade of the phosphorite is low, most of the phosphorite can be used for producing phosphoric acid, high-concentration phosphate fertilizer and the like only after being subjected to mineral separation and enrichment, the actual utilization rate of the phosphorite in China is low due to more impurities in the phosphorite, the phosphorus demand in China is particularly large, and the phosphorite resource in China is gradually exhausted after being exploited and utilized for many years. Especially, calcium in phosphorite can be used for calcium fertilizer, but the leaching rate of calcium ions in the existing method for leaching calcium ions is lower. Magnesium in phosphorite can be used for magnesium fertilizer, but the magnesium ion leaching rate in the existing magnesium ion leaching method is low, impurities are more, and the leaching process is uncontrollable.
CN201710909154.6 discloses a method for improving the leaching efficiency of calcium in phosphorite, and a product and application thereof, wherein the method comprises the following steps: adjusting and controlling the pH value of an aqueous solution system containing phosphorite solid particles to be 7.2-8.2 and the ammonium ion concentration to be 0.5-3 mol/L to carry out leaching reaction for 0.5-5 hours. However, the method in this patent has a low leaching rate for leaching calcium ions and is easy to leach magnesium ions.
CN201510226236.1 discloses a method for extracting phosphate concentrate and co-producing calcium carbonate and magnesium oxide from phosphate tailings, which comprises the steps of calcining the phosphate tailings at high temperature, adding hot water into the calcined material for digestion treatment, then adding an ammonium nitrate solution for stirring, leaching calcium at a certain temperature to obtain a calcium-containing leachate and leaching residues, leaching magnesium from the leaching residues by using an ammonium sulfate solution to obtain phosphate concentrate and a magnesium-containing leachate, precipitating the calcium-containing leachate by using an ammonium carbonate solution to obtain calcium carbonate, precipitating the magnesium-containing leachate by using an ammonium carbonate solution to obtain magnesium carbonate, and calcining the magnesium carbonate to obtain magnesium oxide. The leaching rate of the method in this patent for leaching calcium and magnesium ions is not high.
CN201710818988.6 discloses a method for improving the leaching efficiency of magnesium in phosphorite and application thereof, wherein the method comprises the following steps: adding an ammonium solution into a phosphorus material to be leached with magnesium, and adjusting and controlling the pH value of the solution to be 6.5-7.2 and the ammonium ion concentration to be 0.5-3 mol/L to carry out leaching reaction; wherein the reaction time of the leaching reaction is 0.5-5 hours; separating to obtain solid phase matter after leaching reaction. The method only discloses conditions for improving the magnesium leaching efficiency in phosphorite, but does not relate to the matching of various conditions of a magnesium ion leaching process so as to enable the process to be automatic, particularly when one factor is changed during magnesium ion leaching each time, proper parameters or reaction conditions of other factors cannot be obtained, an operator needs to repeatedly test, the method is time-consuming and inconvenient, and the magnesium ion leaching reaction is not intelligent.
CN201510226308.2 discloses a treatment method for improving the quality of middle-low grade phosphorite and recovering calcium and magnesium, which comprises the steps of firstly, sufficiently decomposing and removing calcium and magnesium carbonate through calcination and digestion treatment, then, sufficiently leaching magnesium element by adopting a composite leaching mode of ammonium nitrate solution and nitric acid solution and further leaching treatment of ammonium sulfate, and further separating the magnesium element from the solution in an ionic state. The method disclosed in this patent also does not involve matching of the various conditions of the magnesium ion leaching process to enable automation of the process.
Disclosure of Invention
In view of the above, the invention provides a method for obtaining calcium ion solution and magnesium ion solution with high purity from phosphate ore. The specific technical scheme is as follows.
A method for efficiently leaching calcium and magnesium ions from phosphate ore, the method comprising:
fully mixing a first phosphorite solid-liquid mixture containing magnesium hydroxide and calcium hydroxide with a first ammonium ion solution to form a first solid-liquid reaction system;
controlling the pH value of the solution in the first solid-liquid reaction system to be 9-11 to carry out calcium ion leaching reaction, and carrying out solid-liquid separation on the first solid-liquid reaction system after the first leaching time of the reaction to obtain a soluble calcium ion-containing solution with a first preset leaching rate and a second phosphorite solid;
fully mixing the second phosphorite solid with a second ammonium ion solution to form a second solid-liquid reaction system;
controlling the pH value of the solution in the second solid-liquid reaction system to be 6.0-7.5 to carry out magnesium ion leaching reaction, and carrying out solid-liquid separation on the second solid-liquid reaction system after the second leaching time of the reaction to obtain a solution containing soluble magnesium ions and a third phosphorite solid with a second preset leaching rate.
Preferably, the solid-liquid ratio in the first phosphorite solid-liquid mixture is 1 to (1.2-1.8), when the mass ratio of the first phosphorite solid-liquid mixture to the first ammonium ion aqueous solution is a first preset mass ratio, the mass concentration of ammonium ions in the first ammonium ion aqueous solution is a first preset concentration, and the average particle size of solid particles in the first phosphorite solid-liquid mixture is a first preset particle size, the first leaching time is determined according to the first leaching temperature of the calcium ion leaching reaction, so that the first leaching time is 5-20 minutes.
Preferably, when the first preset mass ratio is 1 to (0.5-3), the first preset concentration is 30-35%, and the first preset particle size is 0.2-4 mm;
the primary leaching time satisfies the following relation:
T1＝45-(0.8-1.1)*C1
wherein T is1For the primary leach time, T1In units of minutes, C1Is the primary leaching temperature, C1In degrees Celsius, C1The range of values is 20-40.
Preferably, when the first preset mass ratio is 1: 1, the first preset concentration is 30%, and the first preset particle size is 0.2-1 mm;
the primary leaching time satisfies the following relation:
T1＝45-1*C1。
preferably, when the mass ratio of the second solid phosphorite to the second ammonium ion aqueous solution is a second preset mass ratio, the mass concentration of ammonium ions in the second ammonium ion aqueous solution is a second preset concentration, and the average particle size of solid particles in the second solid phosphorite is a second preset particle size, the secondary leaching time is determined according to the secondary leaching temperature of the magnesium ion leaching reaction, so that the secondary leaching time is 25-40 minutes.
Preferably, when the second preset mass ratio is 1 to (0.5-2), the second preset concentration is 30-35%, and the second preset particle size is 0.2-1 mm;
the secondary leaching time satisfies the following relation:
T2＝(0.8-1.2)*C2-35；
wherein T is2For the secondary leaching time, T2In units of minutes, C2Is the secondary leaching temperature, C2In degrees Celsius, C2The numerical range of (A) is 60 to 90.
Preferably, the second preset mass ratio is 1: 1, the second preset concentration is 30%, and the second preset particle size is 0.2-1 mm;
the secondary leaching time satisfies the following relation: t is2＝1*C2-35。
Preferably, the method further comprises an ammonium ion supply step, wherein the ammonium ion supply step supplies ammonium ions to the first solid-liquid reaction, the molar quantity of the supplied ammonium ions is a first supply ammonium ion quantity, and the ratio of the first supply ammonium ion quantity to the molar quantity of ammonia gas volatilized from the reaction system in the calcium ion leaching reaction of the first solid-liquid reaction system is 0.1-1.
Preferably, the ammonium ion supplying step further supplies ammonium ions to the second solid-liquid reaction, and the molar amount of the supplied ammonium ions is a second supply ammonium ion amount, and the ratio of the second supply ammonium ion amount to the molar amount of ammonia gas volatilized from the reaction system when the second solid-liquid reaction system is subjected to the magnesium ion leaching reaction is 0.1 to 1.5.
Preferably, in the ammonium ion supplementing step, the ammonium ions are derived from ammonia gas volatilized from the reaction system in the calcium ion leaching reaction of the first solid-liquid reaction system, and/or derived from ammonia gas volatilized from the reaction system in the magnesium ion leaching reaction of the second solid-liquid reaction system.
The invention has the beneficial effects that: the method for efficiently leaching calcium and magnesium ions in phosphorite provided by the invention can obtain calcium ion solution and magnesium ion solution with better purity in leaching time, and fully utilize calcium and magnesium in phosphorite; the controllable leaching time for leaching calcium ions and magnesium ions can be realized under different primary leaching temperatures and secondary leaching temperatures.
Drawings
FIG. 1 is a flow chart of the method for efficiently leaching calcium and magnesium ions in phosphorite provided by the invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Referring to fig. 1, the present invention provides a method for efficiently leaching calcium and magnesium ions from phosphate ore, which includes steps S100, S200, S300 and S400. The detailed procedure is as follows.
Step S100, fully mixing a first phosphorite solid-liquid mixture containing magnesium hydroxide and calcium hydroxide with a first ammonium ion solution to form a first solid-liquid reaction system. It is understood that the first ammonium ion solution is derived from ammonium nitrate. The first phosphorite solid-liquid mixture is obtained by wet ball milling of phosphorite, and comprises first phosphorite solid and liquid, wherein the first phosphorite solid contains 20-30% by mass of phosphorus pentoxide, 41-55% by mass of calcium oxide, 5-13% by mass of magnesium oxide, 0.2-0.9% by mass of iron oxide and 0.4-0.8% by mass of aluminum oxide.
And S200, controlling the pH value of the solution in the first solid-liquid reaction system to be 9-11 to carry out calcium ion leaching reaction, and carrying out solid-liquid separation on the first solid-liquid reaction system after the first leaching time of the reaction to obtain a solution containing soluble calcium ions and a second phosphorite solid with a first preset leaching rate. Wherein the calcium ion leaching reaction is carried out in a first solid-liquid reaction system, and the first preset leaching rate refers to the mole percentage of calcium in the liquid containing soluble calcium ions and calcium in the first phosphorite solid-liquid mixture.
The calcium content in the second solid phosphorite after calcium leaching is obviously lower than that in the first phosphorite solid-liquid mixture before calcium leaching, preferably, after calcium ions are leached by adopting the method, the percentage of the calcium ions in the obtained soluble calcium ion liquid in the first phosphorite solid-liquid mixture before calcium leaching is more than 75%, namely the first preset leaching rate is more than 75%. More preferably, more than 80% (first predetermined leaching rate) of calcium ions can be leached. In the method, the ammonium ions and the calcium hydroxide react to generate the calcium ions and the ammonium hydroxide, the pH value of a reaction system needs to be controlled very strictly, namely, the condition of the method can ensure that the calcium ion leaching effect is better, the magnesium hydroxide in the solid-liquid mixture of the first phosphorite cannot be leached out, and the calcium ion-containing solution with better purity is obtained.
And step S300, fully mixing the second phosphorite solid with the second ammonium ion solution to form a second solid-liquid reaction system for magnesium ion leaching reaction. The second phosphate solid contained magnesium hydroxide. It is to be understood that the molar concentrations of the ammonium ions in the ammonium ion solutions in step S200 and step S300 may be the same or different, and are set according to the respective reaction efficiencies. It will be appreciated that the second phosphate ore solid obtained by solid-liquid separation may contain a small amount of liquid, and thus the second phosphate ore solid according to the present invention includes a second phosphate ore solid containing a small amount of liquid.
And S400, controlling the pH value of the solution in the second solid-liquid reaction system to be 6.0-7.5, and performing solid-liquid separation on the second solid-liquid reaction system after the second leaching time to obtain a solution containing soluble magnesium ions and a third phosphorite solid with a second preset leaching rate. Wherein the magnesium ion leaching reaction occurs in a second solid-liquid reaction system, and the second preset leaching rate refers to the mole percentage of magnesium ions in the liquid containing soluble magnesium ions and the second solid phosphate ore. In the absence of leaching magnesium ions in the primary solid-liquid system, the second predetermined leaching rate is the mole percentage of magnesium ions in the liquid containing soluble magnesium ions to magnesium ions in the primary phosphate ore solid-liquid mixture.
It will be appreciated that the first phosphate ore solid-liquid mixture contains a large amount of calcium and magnesium, which has a great application prospect in the preparation of phosphate concentrate, such as calcium fertilizer, calcium carbonate, magnesium fertilizer or calcium-magnesium fertilizer, so that the phosphate ore concentrate is prepared while leaching the calcium and magnesium from the phosphate ore to obtain calcium and magnesium with high purity.
The method for efficiently leaching calcium and magnesium ions in phosphorite provided by the invention is divided into a calcium ion leaching reaction step and a magnesium ion leaching reaction step, and the pH values of the two leaching reactions are strictly controlled. The calcium ion solution with higher purity can be leached in the calcium ion leaching reaction step, if magnesium ions stay in the liquid simultaneously after magnesium ions and calcium ions are leached out simultaneously, the liquid containing the magnesium ions has influence on the subsequent application of the calcium ions, for example, when the leached calcium ion-containing solution is used for the subsequent preparation of calcium carbonate, the magnesium ions contained in the calcium ion-containing solution influence the purity of the calcium carbonate product. In order to prevent the magnesium ions in the solid-liquid mixture of the first phosphorite from being leached, the method controls the pH value of the solution in the first solid-liquid reaction system to be 9-11 to carry out calcium ion leaching reaction, and at the pH value, the magnesium ions cannot be easily leached. More preferably, under continuous trial and experiment of the applicant of the present invention, it is found that calcium ion leaching reaction is carried out by controlling the pH of the solution in the first solid-liquid reaction system to 10-10.5, and calcium ion solution with higher purity can be obtained. After the calcium ion leaching reaction step is finished, magnesium ion leaching reaction is carried out, and the pH value of the second solid-liquid reaction system is controlled to be 6.0-7.5.
It is understood that the second solid phosphate ore also includes iron ions and aluminum ions, as well as other components. In order to obtain a magnesium ion solution with higher purity in the magnesium ion leaching reaction, if the magnesium ions in the phosphorite are leached out simultaneously with the iron ions and the aluminum ions, the iron ions and the aluminum ions stay in the liquid simultaneously, and then the liquid containing the iron ions and the aluminum ions has influence on the subsequent application of the magnesium ions, for example, when the leached magnesium ion-containing solution is used for preparing magnesium carbonate or calcium magnesium fertilizer subsequently, the iron ions and the aluminum ions contained in the leached magnesium ion-containing solution influence the product purity of the magnesium carbonate or calcium magnesium fertilizer. In order to prevent impurities such as iron ions, aluminum ions and the like in the second solid phosphorite from being leached, the pH value of the solution in the second solid-liquid reaction system is controlled to be 6.0-7.5 in the magnesium ion leaching reaction to carry out the magnesium ion leaching reaction, and at the pH value, the impurities such as the iron ions, the aluminum ions and the like cannot be easily leached out. More preferably, under the continuous trial and experiment of the applicant of the present invention, the magnesium ion leaching reaction is carried out by controlling the solution in the second solid-liquid reaction system to 6.0-7.5, so that the magnesium ion solution with higher purity can be obtained.
It can be understood that the second solid phosphorite is rich in phosphorus, and the phosphorus in the second solid phosphorite cannot be dissolved out while magnesium ions are leached, so that the phosphorus content in the third solid phosphorite after magnesium leaching is prevented from being reduced. The pH value of the magnesium ion leaching reaction is set to be 6.0-7.5, so that phosphorus in the phosphorite can be effectively prevented from being dissolved out, if the pH value is lower than 6.0, the phosphorus in the phosphorite is easily dissolved out, if the pH value is higher than 7.5, other impurities in the phosphorite are easily dissolved out, and if the pH value is too high, the efficiency of dissolving and leaching magnesium ions from the second solid phosphorite is greatly reduced, even the magnesium ions are not dissolved. Preferably, the pH is set between 6.5 and 6.8.
In a further embodiment, the solid-to-liquid ratio of the first phosphorite solid-to-liquid mixture is 1 to (1.2-1.8), that is, the solid-to-liquid ratio of the first phosphorite solid to the liquid in the first phosphorite solid-to-liquid mixture is 1 to (1.2-1.8). When the mass ratio of the first phosphorite solid-liquid mixture to the first ammonium ion aqueous solution is a first preset mass ratio, the mass concentration of ammonium ions in the first ammonium ion aqueous solution is a first preset concentration, and the average particle size of solid particles of the first phosphorite solid-liquid mixture is a first preset particle size, the primary leaching time is determined according to the primary leaching temperature of the calcium ion leaching reaction, so that the primary leaching time is 5-20 minutes. Wherein the primary leaching temperature is the average temperature before the end of the primary leaching time under the condition of meeting the leaching pH. Preferably, the difference between the maximum temperature and the minimum temperature in the primary leach time is less than 5 ℃. Wherein the average particle size of the solid particles of the first phosphorite solid-liquid mixture is the average particle size of the first phosphorite solid. It will be appreciated that the primary leach time and primary leach temperature of the calcium leaching reaction have a significant effect on the primary leach temperature, which is suitable to enable rapid leaching of calcium ions from the primary phosphate ore, when other conditions are preset values in the leaching reaction.
The method provided by the invention can control the primary leaching time by controlling the primary leaching temperature for leaching calcium ions, so that the primary leaching time of the calcium ion leaching process in the phosphorite is controllable, and the reaction for leaching the calcium ions by the phosphorite is more automatic and intelligent.
For example, when the primary leach time needs to be controlled at 15 minutes, the process of the present invention can be adjusted in real time by detecting the primary leach temperature to allow control of the primary leach time for the calcium ions. When the time of other procedures in the preparation process of the phosphate concentrate is accelerated, and other conditions are fixed or within a preset range, the leaching speed can be accelerated by controlling the primary leaching temperature, and then the calcium ion leaching process can be matched with other procedures.
It can be understood that the method of the invention can obtain calcium ion solution with higher purity, and can control the primary leaching time to be 5-20 minutes, so as to ensure the leaching efficiency of the calcium ion leaching by the solid-liquid mixture of the primary phosphorite.
In a further embodiment, when the first preset mass ratio is 1 to (0.5-2), the first preset concentration is 30-35%, and the first preset particle size is 0.2-4 mm;
the primary leaching time satisfies the following relation:
T1＝45-(0.8-1.1)*C1
wherein T is1For the primary leach time, T1In units of minutes, C1Is the primary leaching temperature, C1In degrees Celsius, C1The range of values is 20-40.
It will be appreciated that in order to be able to control the primary leach time (T)1Minutes) and ensures the leaching efficiency of calcium ions, and the relationship between the primary leaching temperature and the primary leaching time is controlled by the relational expression so as to realize the controllable and adjustable calcium ion leaching process and further improve the process efficiency of the phosphate concentrate.
In a further embodiment, when the first predetermined mass ratio is 1: 1, the first predetermined concentration is 30%, and the first predetermined particle size is 0.2-1 mm;
the primary leaching time satisfies the following relation:
T1＝45-1*C1。
the particle size of the solid particles in the primary phosphate ore solid-liquid mixture influences the surface contact area of the solid particles and the primary ammonium ion solution, and further influences the leaching reaction rate of calcium ions. The leaching effect is better by adopting the grain size range. The relationship between the primary leaching time and the primary leaching temperature can be satisfied by strictly controlling the conditions of the calcium ion leaching reaction, such as the above-mentioned primary predetermined mass ratio, primary predetermined concentration, and primary predetermined particle size.
Reference may be made specifically to the following specific example 1.
The primary leach time and primary leach temperature for the above examples are illustrated by the specific example 1 and experimental data below: t is1＝45-1*C1The calcium ion leaching process can be completed within T minutes. And can ensure the purity of the calcium ion solution.
Example 1
In example 1, a first solid-liquid phosphate rock mixture and a first ammonium ion aqueous solution are thoroughly mixed to form a first solid-liquid reaction system. Wherein the mass ratio of the first phosphorite solid-liquid mixture to the first ammonium ion aqueous solution is 1: 1, and the first phosphorite solid-liquid mixtureThe solid-liquid ratio in the material is 1: 1.4, the mass concentration of ammonium ions in the first ammonium ion aqueous solution is 30 percent, and the particle size of the first phosphorite solid-liquid mixture is 0.2-1 mm. Controlling the pH value of the solution in the first solid-liquid reaction system to be 9-11 to carry out calcium ion leaching reaction, carrying out solid-liquid separation on the first solid-liquid reaction system after leaching to respectively obtain a liquid containing soluble calcium ions and a second solid phosphorite after calcium leaching, detecting the percentage of the calcium ions in the liquid containing the soluble calcium ions in the solid phosphorite containing calcium hydroxide before leaching, namely when the first preset leaching rate is 80%, stopping the leaching reaction, and recording the first leaching time T when the calcium ions reach the first preset leaching rate1. The primary leaching temperatures listed in table 1 below were varied and the primary predetermined leaching rates were measured after completion of the leaching calcium ion reactions. See table 1 for details.
TABLE 1
As can be seen from Table 1 above, when the primary leach temperature and the primary leach time are in a sufficient relationship T1＝45-1*C1The time of the calcium ion leaching process can be controlled within the range of 5-20 minutes, so that the process flow is improved. It can be understood that when the calcium ion leaching process needs to be completed in a shorter time to match with other phosphate concentrate processes, the leaching temperature can be adjusted by the method of the above embodiment to control the calcium ion process time, thereby improving the efficiency of the whole phosphate concentrate process.
It will be appreciated from table 1 above that when the primary leach temperature is reduced to 20 degrees celsius, the primary leach time is significantly extended to achieve an 80% calcium ion leach, but the extended time has little effect on further improving the calcium ion leach rate and also increases energy consumption.
In a further embodiment, the secondary leaching time is determined based on the secondary leaching temperature of the magnesium ion leaching reaction when the mass ratio of the secondary solid phosphate ore to the secondary aqueous solution of ammonium ions is at a second predetermined mass ratio, the mass concentration of ammonium ions in the secondary aqueous solution of ammonium ions is at a second predetermined concentration, and the average particle size of the solid particles in the secondary solid phosphate ore is at a second predetermined particle size, such that the secondary leaching time is between 25 and 40 minutes. That is to say, the secondary leaching time is controlled by controlling the secondary leaching temperature of the magnesium ion leaching reaction, so that the secondary leaching time of the magnesium ion leaching process in the phosphorite is controllable, and the reaction of the phosphorite for leaching magnesium ions is more automatic and intelligent.
It will be appreciated that, for example, when the secondary leaching time is controlled to be 25 minutes in order to match the time of the calcium ion leaching process, in order to minimize the time difference from the calcium ion leaching process, the method of the present invention can be adjusted in real time by detecting the secondary leaching temperature, so that the secondary leaching time of magnesium ions can be controlled to match the calcium ion leaching process, thereby achieving the mutual connection of the treatment capacity of the calcium ion leaching process and the magnesium ion leaching process without wasting equipment resources. When the time of other procedures in the preparation process of the phosphate concentrate is reduced, and other conditions are constant or within a preset range, the leaching speed can be reduced by controlling the secondary leaching temperature, so that the magnesium ion leaching process can be matched with other procedures.
In a further embodiment, when the second preset mass ratio is 1 to (0.5-2), the second preset concentration is 30-35%, and the second preset particle size is 0.2-1 mm;
the secondary leaching time satisfies the following relation:
T2＝(0.8-1.2)*C2-35；
wherein T is2For the secondary leaching time, T2In units of minutes, C2Is the secondary leaching temperature, C2In degrees Celsius, C2The numerical range of (A) is 60 to 90.
It will be appreciated that in order to be able to control the time (T)2Minutes) and ensures the leaching efficiency of magnesium ions, and the relationship between the secondary leaching temperature and the secondary leaching time is controlled by the relational expression so as to realize the controllable and adjustable magnesium ion leaching processFurther improving the process efficiency of the phosphate concentrate.
In a further embodiment, when the second predetermined mass ratio is 1: 1, the second predetermined concentration is 30%, and the second predetermined particle size is 0.2-1 mm;
the secondary leaching time satisfies the following relation: t is2＝1*C2-35。
The secondary leaching time and the secondary leaching temperature can be made to satisfy the above-mentioned relation by strictly controlling the conditions of the calcium ion leaching reaction, such as the above-mentioned secondary predetermined mass ratio, secondary predetermined concentration and secondary predetermined particle size.
Reference may be made specifically to the following specific example 2.
The following will illustrate, by way of specific example 2 and experimental data, that the secondary leach temperature and the secondary leach time of the above examples satisfy the relationship: t is2＝1*C235 hours, the magnesium ion leaching process can be completed within 25-40 minutes. And the purity of the magnesium ion solution can be ensured.
Example 2
In example 2, a second solid phosphate rock was thoroughly mixed with a second aqueous ammonium ion solution to form a second solid-liquid reaction system. Wherein the mass ratio of the second solid phosphorite to the second ammonium ion aqueous solution is 1: 1, the mass concentration of ammonium ions in the second ammonium ion aqueous solution is 30%, and the particle size of the second solid phosphorite is 0.2-1 mm. Controlling the pH value of the solution in the second solid-liquid reaction system to be 6.0-7.5 to carry out magnesium ion leaching reaction, carrying out solid-liquid separation on the second solid-liquid reaction system after leaching to respectively obtain a liquid containing soluble magnesium ions and solid phosphorite after magnesium leaching, detecting the percentage of the magnesium ions in the liquid containing the soluble magnesium ions in the solid phosphorite containing magnesium hydroxide before leaching, namely when the second preset leaching rate is 90%, stopping the leaching reaction, and recording the second leaching time T when the leached magnesium ions reach the second preset leaching rate2. The secondary leaching times required after completion of the reaction for leaching magnesium ions at different secondary leaching temperatures are shown in Table 2 below, and secondary preset leaching rates were determined. See table 2 for details.
TABLE 2
As can be seen from Table 2 above, when the secondary leach temperature and the secondary leach time are in a sufficient relationship T2＝1*C235 h, namely, the time of the magnesium ion leaching process can be controlled within the range of 25-40 minutes, so as to improve the process flow. It will be appreciated that when the magnesium ion leaching process needs to be completed in a relatively short time to match other phosphate concentrate processes, the calcium ion process time can be controlled by the secondary leaching temperature according to the relationship in the above method, thereby improving the overall phosphate concentrate process efficiency.
It will be appreciated from table 2 above that when the secondary leach temperature is raised to 80 degrees celsius, the secondary leach time is significantly longer to achieve an 80% magnesium ion leach rate, but the longer time does not contribute much to further improving the magnesium ion leach rate. That is, the secondary leaching temperature of 60-75 ℃ is enough to saturate the magnesium ion leaching efficiency, and the continuous temperature rise not only has little effect but also increases the energy consumption, and also increases the dissolution of impurities such as iron ions, aluminum ions and the like, and influences the purity of the magnesium ion solution.
In a further embodiment, the method further comprises an ammonium ion supply step, wherein the ammonium ion supply step supplies ammonium ions to the first solid-liquid reaction, the molar quantity of the supplied ammonium ions is a first supply ammonium ion quantity, and the ratio of the first supply ammonium ion quantity to the molar quantity of ammonia gas volatilized from the reaction system when the first solid-liquid reaction system is subjected to the calcium ion leaching reaction is 0.1-1.
It can be understood that, while calcium ions are generated in the first solid-liquid reaction system, ammonium hydroxide, that is, ammonia water, which is easily decomposed into ammonia water and water, is generated, and the ammonia gas is easily volatilized, and in the first solid-liquid reaction system, if the ammonium ions are volatilized in the form of ammonia gas, the molar concentration of the first ammonium ions in the first solid-liquid reaction system is reduced, which is not favorable for the subsequent calcium leaching reaction. Therefore, the ammonium ion supply step is added to maintain the molar concentration of the first ammonium ions in the first solid-liquid reaction system in dynamic balance during the calcium ion leaching reaction, and particularly, the effect is better when the molar ratio of the ammonia gas volatilized from the first supply ammonium ion amount is 0.1-1, so that the calcium ion leaching speed is improved, and the calcium ion leaching can be completed in the first leaching time.
In a further embodiment, the ammonium ion replenishment step further supplies ammonium ions to the second solid-liquid reaction, and the molar amount of the ammonium ions supplied is a second replenishment ammonium ion amount, and the ratio of the second replenishment ammonium ion amount to the molar amount of ammonia gas volatilized from the reaction system at the time of the magnesium ion leaching reaction of the second solid-liquid reaction system is 0.1 to 1.5.
It can be understood that ammonia gas and water are generated while magnesium ions are generated in the second solid-liquid reaction system, the ammonia gas is volatile, and in the second solid-liquid reaction system, if the ammonium ions are volatilized in the form of ammonia gas, the molar concentration of the second ammonium ions in the second solid-liquid reaction system is reduced, so that the subsequent magnesium leaching reaction is not favorable. Therefore, by adding the ammonium ion supply step, the molar concentration of the second ammonium ions in the second solid-liquid reaction system maintains dynamic balance in the magnesium ion leaching reaction process, and further the magnesium ion leaching speed is increased, so that the magnesium ions can be leached within the second leaching time.
In a further embodiment, the ammonium ion supply step is performed by supplying ammonium ions from ammonia gas volatilized from the reaction system in the calcium ion leaching reaction of the first solid-liquid reaction system and/or from ammonia gas volatilized from the reaction system in the magnesium ion leaching reaction of the second solid-liquid reaction system. The ammonia gas generated after the calcium ion leaching reaction and the magnesium ion leaching reaction is recycled through the ammonium ion supply step, so that the material balance of ammonium ions is maintained, and the ammonium ion material is saved.
In a further embodiment, the temperature of the first solid-liquid reaction system is from 25 to 40 ℃. The reaction to leach calcium ions needs to be carried out at this temperature range. Too high temperature can cause the magnesium hydroxide in the phosphorite to react with ammonium ions, and further cause the calcium ion solution to contain a large amount of magnesium ions, and the leaching effect is poor. Preferably, the temperature of the calcium ion leaching reaction is 25-30 ℃.
The temperature of the second solid-liquid reaction system is 60-75 ℃. The effect of magnesium ion leaching reaction in the temperature range is better. Too low a temperature can lead to poor effect of dissolving magnesium ions by reaction of magnesium hydroxide and ammonium ions in the phosphorite and poor leaching effect. Too high a temperature will dissolve impurities from the solid phosphate rock and contaminate the magnesium ion solution.
In a further embodiment, the mass ratio of the first phosphorite solid-liquid mixture to the first ammonium ion solution is 1: (0.5-3); the mass ratio of the second solid phosphorite to the second ammonium ion solution is 1: 0.5-2. The above is the mass ratio at the mass concentration of 30% of the first ammonium ion solution and the second ammonium ion solution, and the applicant of the present invention has continuously tried and tested that the above mass ratio can make the leaching rate of calcium ions and magnesium ions higher.
Example 3
The invention is illustrated by the experimental data in example 3 below, in order to demonstrate the superiority of the leaching pH and primary leaching temperature in the leaching calcium ion reaction provided by the invention, in particular to obtain a calcium ion solution with high purity, that is to say a lower magnesium ion content during the leaching process.
In example 3, a first solid-liquid reaction system was formed by thoroughly mixing a first phosphorite solid-liquid mixture with a first ammonium ion aqueous solution, calcium ion leaching reaction was performed under different pH and temperature conditions under the same conditions, solid-liquid separation was performed on the first solid-liquid reaction system after leaching to obtain a liquid containing soluble calcium ions and a second solid phosphorite after calcium leaching, respectively, and the molar percentage of calcium ions in the liquid containing soluble calcium ions to the total amount of calcium ions and magnesium ions was examined. See table 3 for details.
TABLE 3
| Group of | pH value | Primary leach temperature, deg.C | Ca in a molar percentage of the total amount of Ca and Mg% |
| 1 | 7.5 | 25 | 60 |
| 2 | 8.2 | 25 | 67 |
| 3 | 8.8 | 25 | 70 |
| 4 | 9 | 25 | 90 |
| 5 | 9.5 | 25 | 93 |
| 6 | 9.8 | 25 | 94 |
| 7 | 10 | 25 | 99 |
| 8 | 10.5 | 25 | 95 |
| 9 | 10.8 | 25 | 91 |
| 10 | 11 | 25 | 92 |
| 11 | 10 | 28 | 98 |
| 12 | 10 | 30 | 95 |
| 13 | 10 | 32 | 92 |
| 14 | 10 | 35 | 92 |
| 15 | 10 | 37 | 91 |
| 16 | 10 | 40 | 92 |
| 17 | 10 | 45 | 80 |
| 18 | 10 | 50 | 71 |
| 19 | 10 | 60 | 58 |
| 20 | 10 | 80 | 52 |
As can be seen from the above data from group 1 to group 10 in Table 3, when the pH was controlled within the range of 9 to 11, the content of calcium was significantly large, up to 99%, and the magnesium ion impurities were very small. From the 11 th to 20 th data, it can be seen that the calcium content is significantly greater, up to 98%, when the temperature is controlled in the range of 25-40 ℃.
Example 4
The experimental data set forth below in example 4 illustrate the superiority of the leaching pH and secondary leaching temperature in the leaching magnesium ion reaction provided by the present invention, particularly to obtain magnesium ion solutions with high purity, i.e., less iron and other impurities in the leaching process.
In example 4, a second solid-liquid reaction system was formed by thoroughly mixing a second solid phosphate ore with a second ammonium ion aqueous solution, under the same conditions, a magnesium ion leaching reaction was performed under different pH values and temperature conditions, after leaching, the second solid-liquid reaction system was subjected to solid-liquid separation to obtain a liquid containing soluble magnesium ions and a third solid phosphate ore after magnesium leaching, respectively, and the mole percentage of magnesium ions in the liquid containing soluble magnesium ions to magnesium in the second solid phosphate ore before magnesium leaching, that is, the leaching rate of magnesium ions, was measured. And detecting the mass percentage of the phosphorus component dissolved in the solution in the phosphorite, namely the dissolution rate of the phosphorus. See table 4 for details.
TABLE 4
| Group of | pH value | Second temperature, deg.C | Leaching rate of magnesium ions, percent | The dissolution rate of phosphorus% |
| 1 | 2.5 | 80 | 60 | 90 |
| 2 | 4.1 | 80 | 67 | 86 |
| 3 | 5.6 | 80 | 70 | 62 |
| 4 | 6.0 | 80 | 90 | ＜1 |
| 5 | 6.2 | 80 | 93 | 0 |
| 6 | 6.5 | 80 | 99 | 0 |
| 7 | 6.8 | 80 | 98 | 0 |
| 8 | 7.0 | 80 | 95 | 0 |
| 9 | 7.2 | 80 | 91 | 0 |
| 10 | 7.5 | 80 | 90 | 0 |
| 11 | 6.8 | 25 | 1 | - |
| 12 | 6.8 | 40 | 5 | - |
| 13 | 6.8 | 60 | 65 | - |
| 14 | 6.8 | 70 | 82 | - |
| 15 | 6.8 | 75 | 91 | - |
| 16 | 6.8 | 78 | 92 | - |
| 17 | 6.8 | 80 | 98 | - |
| 18 | 6.8 | 82 | 96 | - |
| 19 | 6.8 | 85 | 98 | - |
| 20 | 6.8 | 90 | 96 (containing iron ion impurities) | - |
As can be seen from the above data from group 1 to group 10 in Table 4, when the pH is controlled within the range of 6.0 to 7.5, the leaching rate of magnesium ions is high, up to 99%, and the total phosphorus dissolution rate of phosphate ore is low, and when the pH is less than 6.0, the phosphorus dissolution rate is high, which is not favorable for obtaining high-content phosphate concentrate. From the data of group 11 to group 20, it can be seen that when the temperature is controlled within the range of 75-85 ℃, the leaching rate of magnesium ions is high, and the maximum leaching rate reaches 98%, and when the temperature is higher than 85 ℃, the dissolved magnesium ion solution contains more impurities.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for efficiently leaching calcium and magnesium ions in phosphorite is characterized by comprising the following steps:
fully mixing a first phosphorite solid-liquid mixture containing magnesium hydroxide and calcium hydroxide with a first ammonium ion solution to form a first solid-liquid reaction system;
controlling the pH value of the solution in the first solid-liquid reaction system to be 9-11 to carry out calcium ion leaching reaction, and carrying out solid-liquid separation on the first solid-liquid reaction system after the first leaching time of the reaction to obtain a soluble calcium ion-containing solution with a first preset leaching rate and a second phosphorite solid;
fully mixing the second phosphorite solid with a second ammonium ion solution to form a second solid-liquid reaction system;
controlling the pH value of the solution in the second solid-liquid reaction system to be 6.0-7.5 to carry out magnesium ion leaching reaction, and carrying out solid-liquid separation on the second solid-liquid reaction system after the second leaching time of the reaction to obtain a solution containing soluble magnesium ions and a third phosphorite solid with a second preset leaching rate.
2. The method of claim 1, wherein the solid-to-liquid ratio of the first phosphate ore solid-liquid mixture is 1 to (1.2-1.8), and when the mass ratio of the first phosphate ore solid-liquid mixture to the first ammonium ion aqueous solution is a first predetermined mass ratio, the mass concentration of ammonium ions in the first ammonium ion aqueous solution is a first predetermined concentration, and the average particle size of solid particles in the first phosphate ore solid-liquid mixture is a first predetermined particle size, the first leaching time is determined according to the first leaching temperature of the calcium ion leaching reaction, such that the first leaching time is 5-20 minutes.
3. The method according to claim 2, wherein when the first predetermined mass ratio is 1: (0.5-3), the first predetermined concentration is 30-35%, and the first predetermined particle size is 0.2-4 mm;
the primary leaching time satisfies the following relation:
T1＝45-(0.8-1.1)*C1
wherein T is1For the primary leach time, T1In units of minutes, C1Is the primary leaching temperature, C1In degrees Celsius, C1The range of values is 20-40.
4. The method according to claim 3, wherein when the first predetermined mass ratio is 1: 1, the first predetermined concentration is 30%, and the first predetermined particle size is 0.2-1 mm;
the primary leaching time satisfies the following relation:
T1＝45-1*C1。
5. the method according to claim 1, characterized in that when the mass ratio of the second solid phosphate ore to the second aqueous solution of ammonium ions is a second predetermined mass ratio, the mass concentration of ammonium ions in the second aqueous solution of ammonium ions is a second predetermined concentration, and the average particle size of the solid particles in the second solid phosphate ore is a second predetermined particle size, the secondary leaching time is determined according to the secondary leaching temperature of the magnesium ion leaching reaction so that the secondary leaching time is 25-40 minutes.
6. The method according to claim 5, wherein when the second predetermined mass ratio is 1: (0.5-2), the second predetermined concentration is 30-35%, and the second predetermined particle size is 0.2-1 mm;
the secondary leaching time satisfies the following relation:
T2＝(0.8-1.2)*C2-35；
wherein T is2For the secondary leaching time, T2In units of minutes, C2Is the secondary leaching temperature, C2In degrees Celsius, C2The numerical range of (A) is 60 to 90.
7. The method according to claim 6, wherein the second predetermined mass ratio is 1: 1, the second predetermined concentration is 30%, and the second predetermined particle size is 0.2-1 mm;
the secondary leaching time satisfies the following relation: t is2＝1*C2-35。
8. The method according to any one of claims 1 to 7, further comprising an ammonium ion replenishment step of supplying ammonium ions to the first solid-liquid reaction in a molar amount corresponding to a first amount of ammonium ions to be replenished, wherein the ratio of the first amount of ammonium ions to the molar amount of ammonia gas volatilized from the reaction system at the time of the calcium ion leaching reaction of the first solid-liquid reaction system is 0.1 to 1.
9. The method according to claim 8, wherein the ammonium ion replenishment step further supplies ammonium ions to the second solid-liquid reaction, and the molar amount of the ammonium ions supplied is a second supply ammonium ion amount, and the ratio of the second supply ammonium ion amount to the molar amount of ammonia gas volatilized from the reaction system at the time of the magnesium ion leaching reaction in the second solid-liquid reaction system is 0.1 to 1.5.
10. The method according to claim 8, wherein the ammonium ion supply step is performed by supplying ammonium ions from ammonia gas volatilized from the reaction system in the calcium ion leaching reaction in the first solid-liquid reaction system and/or from ammonia gas volatilized from the reaction system in the magnesium ion leaching reaction in the second solid-liquid reaction system.
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