CN112794354A - Method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate from calcium magnesium-containing leaching solution - Google Patents
Method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate from calcium magnesium-containing leaching solution Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 39
- 238000002386 leaching Methods 0.000 title claims abstract description 37
- SNNUUXJFRJODOJ-UHFFFAOYSA-N [Mg++].[K+].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Mg++].[K+].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SNNUUXJFRJODOJ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RPASNPADOARUAP-UHFFFAOYSA-N calcium magnesium tetranitrate Chemical compound [Mg++].[Ca++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O RPASNPADOARUAP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 13
- 239000011591 potassium Substances 0.000 title claims abstract description 13
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 title abstract description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 174
- 238000005406 washing Methods 0.000 claims abstract description 45
- 239000012065 filter cake Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 32
- 239000012452 mother liquor Substances 0.000 claims abstract description 31
- 239000011575 calcium Substances 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 20
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 18
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 18
- RBIDTZUOKZFXOO-UHFFFAOYSA-O [N+](=O)([O-])[O-].[NH4+].[Mg].[Ca] Chemical compound [N+](=O)([O-])[O-].[NH4+].[Mg].[Ca] RBIDTZUOKZFXOO-UHFFFAOYSA-O 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims description 39
- 230000008025 crystallization Effects 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 239000002367 phosphate rock Substances 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 8
- 239000004137 magnesium phosphate Substances 0.000 claims description 8
- 229960002261 magnesium phosphate Drugs 0.000 claims description 8
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 7
- 235000013399 edible fruits Nutrition 0.000 abstract description 5
- 229940043430 calcium compound Drugs 0.000 abstract description 4
- 150000002681 magnesium compounds Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 101
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229910009112 xH2O Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- -1 calcium-magnesium ionic compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FOGVNFMUZXDMTR-UHFFFAOYSA-N [Mg].Cl Chemical compound [Mg].Cl FOGVNFMUZXDMTR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
- C01D9/08—Preparation by double decomposition
- C01D9/12—Preparation by double decomposition with nitrates or magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/38—Magnesium nitrates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate by using calcium-magnesium-containing leaching solution, which comprises the following steps: adding a potassium sulfate solution into the calcium magnesium ammonium nitrate concentrated solution for reaction to obtain calcium sulfate slurry; filtering the calcium sulfate slurry to obtain a filtrate and a calcium sulfate filter cake; sequentially concentrating, crystallizing and centrifugally separating the filtrate to obtain crystallized mother liquor, and concentrating and granulating the crystallized mother liquor to obtain magnesium potassium nitrate/calcium magnesium potassium nitrate; washing the calcium sulfate filter cake with water to obtain a solution containing nitrate and calcium sulfate; calcium sulfate is made into calcium sulfate slurry and then reacts with ammonium carbonate solution to obtain calcium carbonate. The calcium and magnesium compounds prepared by the method are respectively calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate, so that the separation of calcium and magnesium ions is realized, and the preparation process is simple in flow, low in cost, high in conversion rate and stable and reliable in quality; the produced magnesium potassium nitrate/calcium potassium nitrate/magnesium calcium nitrate is easy to be absorbed by fruit trees in agriculture and forestry, and the application range of the magnesium potassium nitrate/calcium potassium nitrate/magnesium calcium nitrate is greatly widened.
Description
Technical Field
The invention relates to preparation of calcium-magnesium ionic compounds, in particular to a method for preparing calcium carbonate and potassium-magnesium nitrate/potassium-calcium-magnesium nitrate by using calcium-magnesium containing leaching liquid.
Background
In the enterprises of processing phosphate rock and chemical fertilizer, the by-products of chemical ore dressing contain calcium and magnesium ionic compounds, which are indispensable elements of agricultural and forestry fruit trees and are beneficial to the growth of agricultural and forestry fruit trees.
Therefore, the method for preparing the compound containing calcium and magnesium ions from the leaching solution containing calcium and magnesium of the by-product of chemical mineral separation is also one or more types of fertilizer products which are mainly researched, developed and produced by various phosphorus ore and fertilizer processing enterprises. However, in the existing method, calcium and magnesium ions of the compound containing calcium and magnesium prepared from the leaching solution containing calcium and magnesium are not separated as shown in fig. 1, so that the obtained mixture containing magnesium and calcium carbonate has low utilization value, a large limitation on application range, high practical production difficulty, high production cost, low filtrate conversion rate and unstable product content; therefore, the magnesium-containing calcium carbonate produced at present can not be absorbed by the fruit trees in agriculture and forestry.
In view of the above, the present invention is to provide a method for preparing calcium and magnesium compounds with separated calcium and magnesium ions.
Disclosure of Invention
Based on the problems, the invention aims to provide a method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate by using calcium-containing magnesium leaching solution; the calcium and magnesium compounds prepared by the method are respectively calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate, the separation of calcium and magnesium ions is realized, and the preparation process is simple, low in cost, high in conversion rate and stable and reliable in quality.
The technical scheme of the invention is as follows:
a method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate from calcium magnesium-containing leaching solution comprises the following steps:
simultaneously adding a potassium sulfate solution and a calcium magnesium ammonium nitrate concentrated solution into a reaction tank, and after full decalcification reaction, adding an alkaline substance for neutralization reaction to obtain a calcium sulfate slurry;
filtering the calcium sulfate slurry to obtain a filtrate and a calcium sulfate filter cake;
sequentially carrying out concentration crystallization and centrifugal separation on the filtrate to obtain a crystallization mother liquor, and carrying out concentration granulation treatment on the crystallization mother liquor to obtain potassium magnesium nitrate/potassium calcium magnesium nitrate;
adding water to the calcium sulfate filter cake for washing to obtain a solution containing nitrate and calcium sulfate;
converting the calcium sulfate into a calcium sulfate solution, placing the calcium sulfate solution into a reaction tank, adding a prepared ammonium carbonate solution, and reacting to obtain a calcium carbonate precipitation solution; then filtering and washing the calcium carbonate precipitation solution to obtain filtrate, low-concentration ammonium sulfate washing liquor and calcium carbonate; and concentrating the filtrate to obtain ammonium sulfate.
In one embodiment, the method comprises the following steps:
taking middle-low grade phosphorite as a raw material, sequentially carrying out crushing, calcining, digesting, leaching, filter pressing, separating and other processes, and discharging decalcified magnesium leaching solution and low-magnesium phosphate concentrate from a filter press; wherein, according to the mass percentage, the low-magnesium phosphate concentrate contains P2O5More than or equal to 34.5 percent and MgO less than or equal to 0.85 percent; the above-mentionedIn the leaching process, an ammonium nitrate solution is required to be added;
and pumping the decalcified magnesium leaching solution to a two-effect countercurrent evaporation device for concentration treatment to obtain the calcium magnesium ammonium nitrate concentrated solution.
In one embodiment, the potassium sulfate solution is preferably added into the concentrated solution containing calcium magnesium ammonium nitrate for reaction at the reaction temperature of 20-110 ℃ for 3-6 hours; the alkaline substance is calcium hydroxide or ammonia water, and the pH value of the slurry is controlled to be 6.5-7.5.
In one embodiment, in the method, when the filtrate is subjected to concentration and crystallization treatment, the filtrate is concentrated at 100-135 ℃ to remove part of water; then cooling to room temperature, precipitating potassium nitrate crystals, and controlling the crystallization time to be 4-8 hours to obtain a potassium nitrate crystal solution; the potassium nitrate crystal solution is washed and dried to obtain potassium nitrate.
In one embodiment, in the method, the crystallization mother liquor is subjected to concentration and granulation treatment, and the method further includes the following steps:
feeding the crystallization mother liquor into a preheater for preheating treatment;
sending the crystallization mother liquor after preheating treatment into a heat exchanger, and then sending into a forced circulation evaporator for evaporation treatment;
and the steam after the evaporation treatment is separated by a flash separator and then sent into a granulator for granulation treatment.
In one embodiment, the crystallization mother liquor is preferably sent to a preheater for preheating treatment, wherein the preheating treatment temperature is controlled to be 105-115 ℃ and the preheating time is 5-15 s.
In one embodiment, the evaporation treatment temperature is preferably controlled to be 140-165 ℃; the granulation temperature is controlled to be 100-120 ℃.
In one embodiment, in the method, the number of times of washing the calcium sulfate filter cake is two; adding water into the calcium sulfate filter cake for the first time, and then washing with water to obtain a primary washing solution containing nitrate, wherein the primary washing solution is conveyed into the potassium sulfate solution preparation container and is used for preparing the potassium sulfate solution; and after the calcium sulfate filter cake is washed by water for the second time, a secondary washing solution containing nitrate and the calcium sulfate are obtained, and the secondary washing solution is used as the primary washing solution of the next batch of calcium sulfate filter cake.
In one embodiment, the step of converting the calcium sulfate into a calcium sulfate solution comprises:
and sending the calcium sulfate into a breaker to be broken up, then sending the calcium sulfate into a calcium sulfate container tank, and then adding the low-concentration ammonium sulfate washing liquor into the container tank to be mixed to obtain the calcium sulfate solution.
In one embodiment, the method comprises the following steps:
firstly, according to a stoichiometric formula, metering ammonium bicarbonate and then sending the ammonium bicarbonate to a dissolving tank; then, adding the low-concentration ammonium sulfate washing liquor for dissolving to obtain an ammonium bicarbonate solution; and finally, pumping the ammonium bicarbonate solution into a jet absorber, and introducing ammonia gas for absorption and conversion to obtain the ammonium carbonate solution.
In the method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate by using the leaching solution containing calcium and magnesium, potassium sulfate solution is adopted to react with calcium magnesium ammonium nitrate concentrated solution to obtain calcium sulfate solution, and the calcium sulfate solution is filtered to obtain filtrate and calcium sulfate filter cake slightly soluble in water; on one hand, after concentrating, crystallizing and centrifugally separating the filtrate, concentrating and granulating crystallized mother liquor to obtain magnesium potassium nitrate/calcium magnesium potassium nitrate; on the other hand, the calcium sulfate filter cake is washed by water for multiple times, the obtained washing liquid reacts with the prepared ammonium carbonate solution, and the solubility of calcium carbonate is far lower than that of calcium sulfate, so that a calcium carbonate precipitation solution is obtained by the reaction, and calcium carbonate is obtained after filtering and drying.
The calcium and magnesium compounds prepared by the method are respectively calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate, so that the separation of calcium and magnesium ions is realized, and the preparation process is simple in flow, low in cost, high in conversion rate and stable and reliable in quality; the produced magnesium potassium nitrate/calcium potassium nitrate/magnesium calcium nitrate is easy to be absorbed by fruit trees in agriculture and forestry, and the application range of the magnesium potassium nitrate/calcium potassium nitrate/magnesium calcium nitrate is greatly widened.
Drawings
FIG. 1 is a flow chart of a process for preparing magnesium-containing calcium carbonate from a leaching solution containing calcium and magnesium;
FIG. 2 is a flow chart of the process for preparing calcium carbonate and magnesium potassium nitrate/magnesium calcium nitrate from the leaching solution containing calcium and magnesium;
FIG. 3 shows the steps of preparing calcium carbonate and magnesium potassium nitrate/magnesium calcium nitrate from the leaching solution containing calcium and magnesium.
Detailed Description
The preferred embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 2, the method for preparing calcium carbonate and magnesium potassium nitrate/magnesium calcium nitrate from calcium and magnesium containing leaching solution provided by the invention has the following implementation principle:
reacting a potassium sulfate solution with a calcium magnesium ammonium nitrate concentrated solution to obtain a calcium sulfate solution, and filtering to obtain a filtrate and a calcium sulfate filter cake slightly soluble in water; on one hand, after concentrating, crystallizing and centrifugally separating the filtrate, concentrating and granulating crystallized mother liquor to obtain magnesium potassium nitrate/calcium magnesium potassium nitrate; on the other hand, the calcium sulfate filter cake is washed by water for multiple times, the obtained washing liquid reacts with the prepared ammonium carbonate solution, and the solubility of calcium carbonate is far lower than that of calcium sulfate, so that a calcium carbonate precipitation solution is obtained by the reaction, and calcium carbonate is obtained after filtering and drying.
The preparation scheme of the production process of the present invention is specifically described below.
As shown in figure 3, the method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate by using the calcium-magnesium-containing leaching solution provided by the invention comprises the following process steps:
s1, adding the potassium sulfate solution and the calcium magnesium ammonium nitrate concentrated solution into the reaction tank at the same time, and fully decalcifying; the alkaline substance is calcium hydroxide or ammonia water, and the pH value of the slurry is controlled to be 6.5-7.5, so that calcium sulfate slurry is obtained.
In the step, potassium sulfate (K) is prepared2SO4) Solution: pumping the first washing solution obtained after the first washing of the last batch of calcium sulfate filter cake to a potassium sulfate dissolving tank, metering potassium sulfate according to a proportion, and passing throughThe mixture is conveyed to a dissolving tank by a bucket elevator, stirred and dissolved by a stirrer and then conveyed to a reaction tank in a decalcification section to react with calcium magnesium ammonium nitrate (Ca (NO)3)2﹒Mg(NO3)2﹒xH2O﹒NH4NO3) Reacting the concentrated solution at the reaction temperature of 20-110 ℃ for 3-6 hours, wherein the corresponding chemical reaction process is as follows:
2K2SO4+Ca(NO3)2﹒Mg(NO3)2﹒xH2O﹒NH4NO3→CaSO4↓+4KNO3+
Mg(NO3)2﹒xH2O+NH4NO3
at this point, calcium sulfate (CaSO) was produced4) As a sparingly water-soluble compound, appearing as a precipitate; therefore, the reaction system obtained after the reaction is a slurry.
After the decalcification reaction, adding an alkaline substance into the reaction system for neutralization reaction; wherein the alkaline substance is calcium hydroxide or ammonia water, and the slurry is controlled to be alkalescent, namely the pH value is 6.5-7.5; in one embodiment, the alkaline material is preferably calcium hydroxide and the pH of the slurry is 7.0.
In addition, in the step, calcium magnesium ammonium nitrate concentrated solution is used as a reaction raw material, medium and low grade phosphorite is used as a raw material, the low magnesium phosphate concentrate and decalcified magnesium leaching solution are prepared after the processes of crushing, calcining, digesting, leaching, filter pressing, separating and the like are sequentially carried out, and the decalcified magnesium leaching solution is discharged from a filter press; pumping the decalcified magnesium leaching solution to a two-effect countercurrent evaporation device for concentration treatment to obtain the calcium magnesium ammonium nitrate concentrated solution; wherein, the low-magnesium phosphate concentrate contains P according to the mass percentage2O5Not less than 34.5 wt% and not more than 0.85 wt% of MgO.
The preparation process comprises the following steps:
firstly, taking middle-low grade phosphorite as a raw material, namely a byproduct generated in chemical ore dressing, and crushing the middle-low grade phosphorite by a crusher in sequence, namely crushing the middle-low grade phosphorite into ore particles with the particle size not more than 4.5 mm; the phosphorite is selected mainly because the phosphorite contains a certain amount of calcium and magnesium elements, can be optimized through a corresponding process and is used for preparing a compound fertilizer containing calcium and magnesium ions;
secondly, feeding the crushed stone into a calcining kiln, calcining for 1.5-4 hours at 900-1100 ℃, and then cooling to obtain calcined ore;
secondly, performing wet ball milling on the calcined ore until the particle size is not more than 1.0mm, and performing digestion treatment to obtain phosphorus ore pulp;
then, the phosphorite pulp is sent to a leaching tank, ammonium nitrate salt is added into the leaching tank for reaction, and leaching treatment is carried out to obtain leaching solution; wherein the leaching temperature is 75-90 ℃, the reaction time is 1.5-5 h, and the reaction pH is controlled to be 4.0-6.5; in other embodiments, the ammonium nitrate salt can also adopt nitrate and ammonium salt solution which is easy to dissolve in water;
then, the obtained leaching slurry is conveyed to a filter press for filter pressing treatment, filtrate discharged from the filter press is decalcified magnesium leaching solution, and filter cakes in the filter press are washed by adding water and dried in the air, and then discharged from the filter press to obtain filter cakes; at the moment, the filter cake obtained by unloading the filter press is the low-magnesium phosphate concentrate; wherein, the low-magnesium phosphate concentrate contains P according to the mass percentage2O5More than or equal to 34.5wt percent and less than or equal to 0.85wt percent of MgO;
and finally, pumping the decalcified magnesium leaching solution to a two-effect countercurrent evaporation device for concentration treatment to obtain a calcium magnesium ammonium nitrate concentrated solution with the mass percentage concentration of more than or equal to 25%. Of course, if a nitrate solution is used for leaching, a calcium magnesium nitrate concentrated solution is obtained; if an ammonium salt solution, such as an ammonium chloride solution, is used for leaching, a concentrated solution of ammonium, calcium and magnesium hydrochloride is obtained.
S2, filtering the calcium sulfate slurry to obtain filtrate and a calcium sulfate filter cake.
In the step, pumping the calcium sulfate slurry into a filter for filtering treatment to obtain filtrate and a calcium sulfate filter cake; the filtrate and the calcium sulfate filter cake are correspondingly treated by two process flows; the processing of the filtrate shifts to step S3; the process of treating the calcium sulfate filter cake proceeds to step S4.
S3, filtering the calcium sulfate slurry, sequentially carrying out concentration crystallization and centrifugal separation on the obtained filtrate to obtain a crystallization mother liquor, and carrying out concentration granulation on the crystallization mother liquor to obtain the magnesium potassium nitrate/magnesium calcium nitrate.
In the step, the concentration, crystallization and centrifugal separation treatment of the filtrate are realized by adopting the following modes:
firstly, pumping filtrate from a filtering and washing process to a concentration system by a pump, performing concentration treatment at 100-135 ℃, and removing partial water to obtain concentrated solution;
then, after the concentrated solution is cooled to the room temperature, controlling the crystallization time for 4-8 hours to obtain a crystallization slurry, and carrying out centrifugal separation treatment on the crystallization slurry to obtain potassium nitrate and a crystallization mother solution;
and finally, after the separated potassium nitrate crystals are washed by water for a plurality of times in a water system tank, the potassium nitrate crystals are conveyed to a centrifugal machine for centrifugal treatment to obtain crystallization mother liquor and potassium nitrate crystal filter cakes, the potassium nitrate filter cakes obtained by the centrifugal treatment are dried to obtain potassium nitrate, and meanwhile, the crystallization mother liquor discharged by the centrifugal machine is collected for the next concentration and granulation process.
The concentration and granulation of the crystallization mother liquor are realized by adopting the following modes:
firstly, feeding crystallization mother liquor into a preheater for preheating treatment; the heat treatment temperature is controlled to be 105-115 ℃, and the preheating time is 5-15 s;
then, feeding the crystallization mother liquor subjected to preheating treatment into a heat exchanger, feeding the crystallization mother liquor subjected to heat exchange into a forced circulation type evaporator, and carrying out evaporation treatment on the crystallization mother liquor at the temperature of 140-165 ℃ to remove part of water to obtain concentrated crystallization mother liquor; wherein, the condensate generated by the concentration of the crystallization mother liquor can be used for a water washing filter after being collected;
then, separating the steam of the evaporated crystallization mother liquor by a flash separator, and then sending the steam into a granulator for granulation; after heat exchange is carried out on the crystallization mother liquor and the feed liquid to be evaporated through a heat exchanger, the temperature of the crystallization mother liquor is reduced to the optimal granulation temperature of 100-120 ℃, and the crystallization mother liquor is sent to a granulator for granulation to obtain granular substances;
and finally, feeding the granular substances into a cooling device for cooling treatment, and then feeding the granular substances obtained by cooling into a sieving machine with the sieving mesh number or the pore size of 1.0-4.0mm for sieving treatment to obtain the magnesium potassium nitrate/calcium magnesium potassium nitrate.
S4, filtering the calcium sulfate slurry, adding water into the obtained calcium sulfate filter cake, and washing to obtain a nitrate-containing solution and calcium sulfate.
Specifically, in this example, the number of times of washing the calcium sulfate filter cake with water is two. And (3) washing the calcium sulfate filter cake on the filter with water after adding water for the first time to obtain a primary washing solution containing nitrate, conveying the primary washing solution into a potassium sulfate solution preparation container for preparing a potassium sulfate solution, and taking the potassium sulfate solution as a reaction raw material for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate in the next batch. After the calcium sulfate filter cake is washed with water for the second time, a secondary washing solution containing nitrate and calcium sulfate are obtained, and the secondary washing solution is used as a primary washing solution of the next batch of calcium sulfate filter cake; by the operation, the nitrate can be utilized as much as possible, so that the loss of the nitrate in the manufacturing process is reduced, and the high-quality calcium sulfate powder material can be obtained.
S5, converting calcium sulfate into a calcium sulfate solution, placing the calcium sulfate solution into a reaction tank, adding a prepared ammonium carbonate solution, and reacting to obtain a calcium carbonate precipitation solution; and then filtering and washing the calcium carbonate precipitation solution to obtain the calcium carbonate.
The chemical reaction formula in this step is as follows:
CaSO4+(NH4)2CO3→CaCO3+(NH4)2SO4
the chemical mechanism by which this step can be carried out is: CaCO3BiCaSO4Is more difficult to dissolve in water, and the chemical reaction is favorable to generate calcium carbonate according to the equilibrium principle of the chemical reaction, so that the calcium carbonate can be obtained.
In this step, the step of converting calcium sulfate into a calcium sulfate solution is as follows:
and feeding the calcium sulfate into a breaker, breaking the calcium sulfate into powder, feeding the powder into a calcium sulfate container tank, and adding a nitrate-containing solution into the container tank to mix to obtain the calcium sulfate solution. The nitrate-containing solution mainly refers to a secondary washing solution obtained after the calcium sulfate filter cake is washed for the second time, or a primary washing solution obtained after the calcium sulfate filter cake is washed for the first time, and the selected washing solution is reasonable according to the design process/cost of process equipment.
In addition, in the step, the ammonium carbonate solution is prepared by the following steps:
firstly, weighing ammonium bicarbonate according to a stoichiometric formula, and sending the ammonium bicarbonate to a dissolving tank;
then, adding a solution containing nitrate for dissolving to obtain an ammonium bicarbonate solution; wherein, the nitrate-containing solution mainly refers to a secondary washing solution obtained after the calcium sulfate filter cake is washed for the second time, and can also be a primary washing solution obtained after the calcium sulfate filter cake is washed for the first time, and which washing solution is selected is reasonable according to the design flow/cost of process equipment;
and finally, pumping the ammonium bicarbonate solution into a spray absorber, and introducing ammonia gas to carry out absorption neutralization reaction to obtain the ammonium carbonate solution.
In the step, the ammonium carbonate solution is obtained by adopting a reaction mode of ammonium bicarbonate and ammonia gas, and the requirement of ammonium carbonate is met mainly in consideration of large-scale production; it is therefore desirable to achieve this by chemical synthesis. The reaction formula is as follows:
NH4HCO3+NH3→(NH4)2CO3
it should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A method for preparing calcium carbonate and magnesium potassium nitrate/magnesium calcium nitrate from calcium-containing magnesium leaching solution is characterized by comprising the following steps:
simultaneously adding a potassium sulfate solution and a calcium magnesium ammonium nitrate concentrated solution into a reaction tank, and after full decalcification reaction, adding an alkaline substance for neutralization reaction to obtain a calcium sulfate slurry;
filtering the calcium sulfate slurry to obtain a filtrate and a calcium sulfate filter cake;
sequentially carrying out concentration crystallization and centrifugal separation on the filtrate to obtain a crystallization mother liquor, and carrying out concentration granulation treatment on the crystallization mother liquor to obtain potassium magnesium nitrate/potassium calcium magnesium nitrate;
adding water to the calcium sulfate filter cake for washing to obtain a solution containing nitrate and calcium sulfate;
preparing the calcium sulfate into calcium sulfate slurry, placing the calcium sulfate slurry into a reaction tank, adding a prepared ammonium carbonate solution, and reacting to obtain a calcium carbonate precipitation solution; then filtering and washing the calcium carbonate precipitation solution to obtain filtrate, low-concentration ammonium sulfate washing liquor and calcium carbonate; and concentrating the filtrate to obtain ammonium sulfate.
2. The method as claimed in claim 1, wherein the concentrated solution of calcium magnesium ammonium nitrate is obtained by the following steps:
taking middle-low grade phosphorite as a raw material, sequentially carrying out crushing, calcining, digesting, leaching, filter pressing, separating and other processes, and discharging decalcified magnesium leaching solution and low-magnesium phosphate concentrate from a filter press; wherein, according to the mass percentage, the low-magnesium phosphate concentrate contains P2O5More than or equal to 34.5 percent and MgO less than or equal to 0.85 percent; in the leaching treatment process, an ammonium nitrate solution is required to be added;
and pumping the decalcified magnesium leaching solution to a two-effect countercurrent evaporation device for concentration treatment to obtain the calcium magnesium ammonium nitrate concentrated solution.
3. The method according to claim 1, wherein the potassium sulfate solution is reacted with the calcium magnesium ammonium nitrate concentrated solution at a reaction temperature of 20-110 ℃ for 3-6 hours, and the alkaline substance is calcium hydroxide or ammonia water.
4. The method according to claim 1, wherein when the filtrate is subjected to concentration and crystallization, the filtrate is concentrated at 100-135 ℃ to remove part of water; and then cooling to room temperature to precipitate potassium nitrate crystals, and controlling the crystallization time to be 4-8 hours to prepare the potassium nitrate.
5. The method as claimed in claim 1, wherein the crystallization mother liquor is subjected to concentration and granulation treatment, and further comprising the steps of:
feeding the crystallization mother liquor into a preheater for preheating treatment;
sending the crystallization mother liquor after preheating treatment into a heat exchanger, and then sending into a forced circulation evaporator for evaporation treatment;
and the steam after the evaporation treatment is separated by a flash separator and then sent into a granulator for granulation treatment.
6. The method as claimed in claim 5, wherein the crystallization mother liquor is fed into a preheater for preheating treatment, and the preheating treatment temperature is controlled to be 105-115 ℃ and the preheating time is 5-15 s.
7. The method according to claim 5, wherein the evaporation treatment temperature is controlled to be 140-165 ℃; the granulation temperature is controlled to be 100-120 ℃.
8. The method of claim 1, wherein the calcium sulfate filter cake is washed twice; adding water into the calcium sulfate filter cake for the first time, and then washing with water to obtain a primary washing solution containing nitrate, wherein the primary washing solution is conveyed into the potassium sulfate solution preparation container and is used for preparing the potassium sulfate solution; and after the calcium sulfate filter cake is washed by water for the second time, a secondary washing solution containing nitrate and the calcium sulfate are obtained, and the secondary washing solution is used as the primary washing solution of the next batch of calcium sulfate filter cake.
9. The method according to claim 1, wherein the step of preparing the calcium sulfate into the calcium sulfate solution is as follows:
and sending the calcium sulfate into a breaker to be broken up, then sending the calcium sulfate into a calcium sulfate container tank, and then adding the low-concentration ammonium sulfate washing liquor into the container tank to be mixed to obtain the calcium sulfate solution.
10. The method according to claim 1, wherein the ammonium carbonate solution is prepared by the following steps:
firstly, according to a stoichiometric formula, metering ammonium bicarbonate and then sending the ammonium bicarbonate to a dissolving tank; then, adding the low-concentration ammonium sulfate washing liquor for dissolving to obtain an ammonium bicarbonate solution; and finally, pumping the ammonium bicarbonate solution into a jet absorber, and introducing ammonia gas for absorption and conversion to obtain the ammonium carbonate solution.
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