CN112645367A - Method for preparing calcium sulfate, magnesium oxide and potassium calcium magnesium nitrate from calcium magnesium-containing leaching solution - Google Patents
Method for preparing calcium sulfate, magnesium oxide and potassium calcium magnesium nitrate from calcium magnesium-containing leaching solution Download PDFInfo
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- C05—FERTILISERS; MANUFACTURE THEREOF
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Abstract
The invention discloses a method for preparing calcium sulfate, magnesium oxide and potassium-calcium-magnesium nitrate from calcium-magnesium-containing leaching solution, which comprises the following steps: simultaneously adding a potassium sulfate solution and a calcium magnesium ammonium nitrate concentrated solution into a reaction tank for decalcification reaction, and then adding an alkaline substance for neutralization reaction to obtain a calcium sulfate slurry; filtering the calcium sulfate slurry to obtain decalcified filtrate and calcium sulfate; adding an alkaline substance into the decalcified filtrate to carry out a demagging reaction to prepare a magnesium hydroxide precipitate; filtering the magnesium hydroxide precipitate, calcining a magnesium hydroxide filter cake, and crushing to obtain magnesium oxide; and (4) concentrating and granulating the demagging filtrate to obtain potassium calcium magnesium nitrate. The calcium and magnesium compounds prepared by the method are respectively calcium sulfate, magnesium oxide and potassium nitrate calcium magnesium, so that 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 produced potassium nitrate calcium magnesium is easy to be absorbed by fruit trees in agriculture and forestry.
Description
Technical Field
The invention relates to preparation of calcium-magnesium ionic compounds, in particular to a method for preparing calcium sulfate, magnesium oxide and potassium-calcium-magnesium nitrate from calcium-magnesium-containing leaching solution.
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 magnesium-containing calcium carbonate mixture has low utilization value, a large limitation on application range, high actual 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 sulfate, magnesium oxide and potassium-calcium-magnesium nitrate by using a calcium-magnesium-containing leaching solution; the calcium and magnesium compounds prepared by the method are respectively calcium carbonate, magnesium oxide and potassium nitrate calcium magnesium, the separation of calcium and magnesium ions is realized, the additional value of potassium is improved, 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 sulfate, magnesium oxide and 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 and decalcifying the calcium sulfate slurry to obtain a decalcified filtrate and a calcium sulfate filter cake;
adding an alkaline substance into the decalcified filtrate to carry out a demagging reaction to prepare a magnesium hydroxide precipitate;
filtering the magnesium hydroxide precipitation solution to obtain a magnesium-removed filtrate and a magnesium hydroxide filter cake;
concentrating and granulating the demagging filtrate to obtain potassium calcium magnesium nitrate;
adding water into the magnesium hydroxide filter cake for washing to obtain magnesium hydroxide, and drying and calcining the magnesium hydroxide to obtain magnesium oxide;
and adding water into the calcium sulfate filter cake for washing to obtain calcium 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 the weight percentages are as follows: p2O5More than or equal to 34.5 percent and less than or equal to 0.85 percent of MgO; 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.
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 magnesium hydroxide precipitation solution is prepared, the alkaline substance added to the decalcified filtrate is ammonia gas, the reaction temperature of the demagging reaction is controlled to be 10-50 ℃, and the reaction time is controlled to be 1-3 hours.
In one embodiment, in the method, the demagging filtrate is subjected to concentration and granulation, and the method further includes the following steps:
feeding the demagging filtrate into a preheater for preheating treatment;
sending the magnesium-removed filtrate subjected to preheating treatment into a heat exchanger, and then sending into a forced circulation type evaporator for evaporation treatment to obtain slurry;
and separating the slurry subjected to the evaporation treatment by a flash separator, and then sending the slurry into a granulator for granulation treatment.
In one embodiment, the demagging filtrate 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, the method further comprises the following processing steps when water is added to the magnesium hydroxide filter cake for washing:
adding water into the washed magnesium hydroxide filter cake for repulping treatment to obtain repulped liquid; the temperature of the repulping process is 40-80 ℃, and the repulping time is 0.5-1.5 hours;
and filtering and washing the repulping liquid to obtain a magnesium hydroxide filter cake, and drying and crushing the magnesium hydroxide filter cake to obtain the magnesium hydroxide.
In one embodiment, in the method, the number of times of washing the calcium sulfate filter cake is two; washing the calcium sulfate filter cake after adding water for the first time to obtain a primary washing solution containing nitrate, and sending the primary washing solution to the potassium sulfate solution preparation container 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 the method for preparing calcium sulfate, magnesium oxide and potassium-calcium-magnesium nitrate by using the leaching solution containing calcium and magnesium, potassium sulfate solution is adopted to react with the concentrated solution containing calcium-magnesium nitrate, alkaline substances are added to carry out neutralization reaction to obtain calcium sulfate solution, and the calcium sulfate solution is filtered to obtain decalcified filtrate and calcium sulfate; adding an alkaline substance into the decalcified filtrate to obtain a magnesium hydroxide precipitate, and filtering to obtain a demagging filtrate and magnesium hydroxide; calcining the magnesium hydroxide to obtain magnesium oxide; and continuously concentrating and granulating the demagging filtrate to obtain potassium nitrate calcium magnesium.
The calcium and magnesium compounds prepared by the method are respectively calcium sulfate, magnesium oxide and potassium nitrate calcium magnesium, so that the separation of calcium and magnesium ions is realized, the additional value of potassium is improved, and the preparation method has the advantages of simple process flow, low cost, high conversion rate and stable and reliable quality; the produced potassium nitrate calcium magnesium is easy to be absorbed by fruit trees in agriculture and forestry, thus greatly widening the application range.
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 process flow diagram for preparing calcium sulfate, magnesium oxide and potassium nitrate calcium magnesium from the leaching solution containing calcium and magnesium;
FIG. 3 shows the steps of preparing calcium sulfate, magnesium oxide and potassium calcium magnesium 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 sulfate, magnesium oxide and potassium-calcium-magnesium nitrate from calcium-magnesium-containing leaching solution provided by the invention has the following implementation principle:
in the method for preparing calcium sulfate, magnesium oxide and potassium-calcium-magnesium nitrate by using the leaching solution containing calcium and magnesium, a potassium sulfate solution is adopted to react with a concentrated solution of calcium-magnesium ammonium nitrate, an alkaline substance is added to carry out a neutralization reaction to obtain a calcium sulfate slurry, and the calcium sulfate slurry is filtered to obtain a decalcification filtrate and calcium sulfate; adding an alkaline substance into the decalcified filtrate to obtain a magnesium hydroxide precipitate, and filtering to obtain a demagging filtrate and a magnesium hydroxide filter cake; and continuously concentrating and granulating the demagging filtrate to obtain potassium nitrate calcium magnesium. And (3) repulping, washing and drying the magnesium hydroxide filter cake to obtain a magnesium hydroxide product, and calcining the magnesium hydroxide product at high temperature to obtain magnesium oxide.
The preparation scheme of the production process of the present invention is specifically described below.
As shown in fig. 3, the method for preparing calcium sulfate, magnesium hydroxide and potassium-calcium-magnesium nitrate from the leaching solution containing calcium and magnesium provided by the invention comprises the following steps:
s1, adding the potassium sulfate solution into a reaction tank containing the calcium magnesium ammonium nitrate concentrated solution, adding calcium hydroxide powder for neutralization reaction after full reaction, adding an alkaline substance for neutralization reaction, and controlling the slurry to be alkalescent to obtain the calcium sulfate slurry.
In the step, potassium sulfate (K) is prepared2SO4) Solution: pumping a primary washing solution obtained after the calcium sulfate filter cake of the previous batch is washed for the first time to a potassium sulfate dissolving tank, metering potassium sulfate according to calculation, conveying the potassium sulfate to the dissolving tank through a bucket elevator, stirring and dissolving the potassium sulfate by a stirrer, conveying the solution to a reaction tank in a decalcification working section, and mixing the solution with calcium magnesium ammonium nitrate (Ca (NO)3)2﹒Mg(NO3)2﹒xH2O﹒NH4NO3) And (3) reacting the concentrated solution, wherein the reaction temperature is 20-110 ℃, the reaction time is 3-6 hours, the reaction temperature is preferably 60 ℃, and the reaction time is preferably 5 hours. 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, the concentrated solution of calcium magnesium ammonium nitrate is used as a reaction raw material and is prepared by the following steps:
firstly, taking middle-low grade phosphorite as a raw material, and sequentially crushing the middle-low grade phosphorite by a crusher to obtain 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 macadam 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 sent 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 discharged from the filter press after being washed by water and dried by air to obtain filter cakes; at the moment, the filter cake discharged by 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 34.5 percent and MgO less than or equal to 0.85 percent;
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 remove calcium, and obtaining a decalcified filtrate and a calcium sulfate filter cake.
In the step, pumping the calcium sulfate slurry into a filter for filtering treatment to obtain decalcified filtrate and a calcium sulfate filter cake; and the decalcified filtrate and the calcium sulfate filter cake are correspondingly treated by two process flows; the processing of the filtrate shifts to step S3; and adding water into the calcium sulfate filter cake for washing twice, drying and crushing the calcium sulfate filter cake obtained after washing to obtain a calcium sulfate product.
S3, after filtering, adding an alkaline substance into the decalcified filtrate to carry out a demagging reaction, and obtaining a magnesium hydroxide precipitate after the reaction;
in the step, an alkaline substance is added into the decalcified filtrate to carry out a demagging reaction, so as to prepare a magnesium hydroxide precipitation solution. Wherein the alkaline substance is one or more of ammonia gas, sodium hydroxide, potassium hydroxide, etc.; the ammonia gas is selected in the embodiment, so that the operation is convenient, the conveying cost is low, and the like. And (3) directly introducing ammonia gas into the decalcified filtrate, and performing a demagging reaction for 1-3 hours at the temperature of 10-50 ℃.
S4, filtering the magnesium hydroxide precipitate to obtain a magnesium-removed filtrate and a magnesium hydroxide filter cake; and (4) concentrating and granulating the demagging filtrate to obtain potassium calcium magnesium nitrate.
In the step, the demagging filtrate is concentrated and granulated,
the method is realized by adopting the following steps:
firstly, feeding the demagging filtrate into a preheater for preheating treatment, wherein the preheating treatment temperature is controlled to be 105-115 ℃, and the preheating time is 5-15 s;
then, feeding the magnesium-removed filtrate subjected to preheating treatment into a heat exchanger, feeding the magnesium-removed filtrate subjected to heat exchange into a forced circulation type evaporator, and evaporating the magnesium-removed filtrate at the temperature of 140-165 ℃ to remove part of water to obtain slurry; wherein, the condensed fluid generated by the concentration of the magnesium-removing filtrate can be used for a water washing filter after being collected;
then, separating the slurry obtained after the evaporation treatment by a flash separator, and then sending the slurry into a granulator for granulation treatment; wherein, the temperature of the concentrated solution after magnesium removal is subjected to heat exchange with the feed liquid to be evaporated through a heat exchanger is reduced to the optimal granulation temperature of 100-120 ℃, and the concentrated solution 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 potassium nitrate calcium magnesium.
And S5, adding water into the magnesium hydroxide filter cake to wash to obtain magnesium hydroxide, and drying and calcining to obtain magnesium oxide.
In the step, when water is added into the magnesium hydroxide filter cake for washing, the method also comprises the following processing steps:
adding water into the washed magnesium hydroxide filter cake for repulping treatment to obtain repulped liquid; the temperature of the repulping process is 40-80 ℃, and the repulping time is 0.5-1.5 hours;
filtering and washing the repulping liquid to obtain a magnesium hydroxide filter cake, and drying and crushing the magnesium hydroxide filter cake to obtain magnesium hydroxide; (wherein, the drying air inlet temperature is 200-240 ℃, the drying air outlet temperature is 115-140 ℃, the time is 0.15-1h, the ambient atmosphere is normal temperature, the equipment is a QGS-5 powerful crushing dryer, the particle size is less than 10 μm during crushing, and the like.
Further, calcining the magnesium hydroxide (wherein the calcining temperature is 700 ℃, the ambient temperature is normal temperature, and the calcining time is 0.5-1.5h) to obtain the magnesium oxide. The specific chemical reaction is as follows:
Mg(OH)2→MgO+H2O
s6, after filtering and decalcifying treatment, adding water into the obtained calcium sulfate filter cake for washing to obtain a solution containing calcium ions and calcium sulfate.
The number of times of washing the calcium sulfate filter cake with water was two. And washing the calcium sulfate filter cake on the filter 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 calcium nitrate/potassium calcium magnesium nitrate in the next batch. After the calcium sulfate filter cake is washed by 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.
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 (9)
1. A method for preparing calcium sulfate, magnesium oxide and potassium-calcium-magnesium nitrate from calcium-magnesium containing 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 for decalcification reaction, and after full reaction, adding an alkaline substance for neutralization reaction to obtain a calcium sulfate slurry;
filtering the calcium sulfate slurry to obtain a decalcified filtrate and a calcium sulfate filter cake;
adding an alkaline substance into the decalcified filtrate to carry out a demagging reaction to prepare a magnesium hydroxide precipitate;
filtering the magnesium hydroxide precipitation solution to obtain a magnesium-removed filtrate and a magnesium hydroxide filter cake; concentrating and granulating the demagging filtrate to obtain potassium calcium magnesium nitrate;
adding water into the magnesium hydroxide filter cake for washing to obtain magnesium hydroxide, and drying and calcining the magnesium hydroxide to obtain magnesium oxide;
and adding water into the calcium sulfate filter cake for washing to obtain calcium 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, the weight percentage isThe ratio is as follows: p2O5More than or equal to 34.5 percent and less than or equal to 0.85 percent of MgO; in the leaching treatment process, an ammonium nitrate solution is required to be added;
and pumping the low-magnesium phosphate concentrate 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 the alkaline substance added to the decalcified filtrate is ammonia gas when preparing the magnesium hydroxide precipitate, and the reaction temperature of the decalcified filtrate is controlled to be 10-50 ℃ and the reaction time is controlled to be 1-3 hours.
5. The method according to claim 1, wherein the de-magnesiated filtrate is subjected to a concentration granulation process, further comprising the steps of:
feeding the demagging filtrate into a preheater for preheating treatment;
sending the magnesium-removed filtrate subjected to preheating treatment into a heat exchanger, and then sending into a forced circulation type evaporator for evaporation treatment to obtain slurry;
and separating the slurry subjected to the evaporation treatment by a flash separator, and then sending the slurry into a granulator for granulation treatment.
6. The method as claimed in claim 5, wherein the demagging filtrate is sent to 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 6, 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 step of adding water to the magnesium hydroxide filter cake for washing further comprises the following steps:
adding water into the washed magnesium hydroxide filter cake for repulping treatment to obtain repulped liquid; the temperature of the repulping process is 40-80 ℃, and the repulping time is 0.5-1.5 hours;
and filtering and washing the repulping liquid to obtain a magnesium hydroxide filter cake, and drying and crushing the magnesium hydroxide filter cake to obtain the magnesium hydroxide.
9. The method of claim 1, wherein the calcium sulfate filter cake is washed twice; washing the calcium sulfate filter cake after adding water for the first time to obtain a primary washing solution containing nitrate, and sending the primary washing solution to the potassium sulfate solution preparation container 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.
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| CN115159579A (en) * | 2022-08-01 | 2022-10-11 | 贵州金瑞新材料有限责任公司 | Method for deeply separating calcium and magnesium impurities in manganese sulfate |
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