CN110484970B - Resourceful treatment method for high-magnesium phosphate tailings - Google Patents
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Abstract
The invention provides a resource treatment method of high-magnesium phosphate tailings, which comprises the steps of firstly separating silicon slag in the high-magnesium phosphate tailings by hydrochloric acid acidolysis, then standing at a low temperature to separate phosphorus in the high-magnesium phosphate tailings in a calcium chlorophosphate form, then separating calcium and magnesium in the high-magnesium phosphate tailings by sulfuric acid acidification, and finally obtaining calcium sulfate whiskers and magnesium chloride whiskers by step-by-step concentration treatment.
Description
Technical Field
The invention relates to the technical field of waste resource utilization, in particular to a resource treatment method of high-magnesium phosphate tailings.
Background
The phosphorus tailings mainly come from tailings left after ore dressing and concentrate extraction, and belong to mining solid wastes in industrial solid wastes. The minerals mainly comprise dolomite, fluorine phosphorus ash and quartz, the CaO content of the dolomite is about 30.0-34.0 percent, and P is2O5The content is about 4-8.5%, and the content of MgO is about 12-18%.
As the exploitation of phosphate rock increases, the amount of phosphate tailings also rises rapidly. 30-40 million phosphate tailings can be generated after every 100 million phosphate ores are selected. At present, the comprehensive utilization rate of the phosphorus tailings is only 18%, and most phosphorus tailings are discharged to a tailing pond or are stockpiled to a tailing yard after being dehydrated. The comprehensive utilization approaches mainly comprise novel medicament re-flotation, recrystallization re-flotation, cement preparation, building brick preparation, microcrystalline glass preparation, phosphorus-magnesium fertilizer preparation and the like. However, the development of efficient collectors and inhibitors used in the flotation process is difficult, and the influence of the reagents on the environment is large. Although the development of building material products and fertilizers enables the phosphorite tailings to be utilized in a large quantity, the additional value is low, and resources are not reasonably utilized.
Disclosure of Invention
In view of the above, the invention aims to provide a resource treatment method for high-magnesium phosphate tailings, so as to solve the problems of low resource utilization rate and low product added value of the existing phosphate tailings.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a resource treatment method of high-magnesium phosphate tailings comprises the following steps:
1) mixing the high-magnesium phosphate tailings with hydrochloric acid, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out suction filtration to obtain acidolysis solution A and silicon slag;
2) standing the acidolysis solution A under an ice bath condition, and performing solid-liquid separation to obtain calcium chlorophosphate and acidolysis solution B;
3) dropwise adding sulfuric acid with a certain concentration into the acidolysis solution B at normal temperature, heating for reacting for a period of time, aging, and performing suction filtration to obtain an acidizing solution C and calcium sulfate precipitate;
4) after washing the calcium sulfate precipitate, standing a washing solution to obtain calcium sulfate whiskers;
5) concentrating the acidizing fluid C, and performing suction filtration to obtain calcium sulfate whiskers and a concentrated solution D;
6) and concentrating the concentrated solution D, and performing suction filtration to obtain the magnesium chloride whisker.
Optionally, the concentration of the hydrochloric acid in the step 1) is 8.80-12.07mol/L, and the mass ratio of the hydrochloric acid to the high-magnesium phosphorus tailings is (2.0-2.8): 1.
Optionally, the acidolysis reaction in the step 1) is carried out at a temperature of 20-60 ℃ for 20-60 min.
Optionally, the ice bath temperature of the ice bath in the step 2) is-10 ℃ to 0 ℃, and the standing time is 10 to 24 hours.
Optionally, the concentration of the sulfuric acid in the step 3) is less than or equal to 10%, and the addition amount of the sulfuric acid is 1-1.5 times of the mass amount of calcium in the acidolysis solution B.
Optionally, the reaction temperature of the heating reaction in the step 3) is 70-95 ℃, and the reaction time is 10-40 min.
Optionally, the aging time of the aging in the step 3) is 8-16 h.
Optionally, the standing time of the standing in the step 4) is 6-12 h.
Optionally, the concentration temperature of the concentration in the step 5) is 80-100 ℃, and the volume ratio of the concentrated solution D to the acidified solution C is 0.4-0.6.
Optionally, the concentration temperature of the concentration in the step 6) is 80-118 ℃.
Compared with the prior art, the resource treatment method of the high-magnesium phosphate tailings has the following advantages:
1. according to the invention, firstly, the silicon slag in the high-magnesium phosphate tailings is separated through hydrochloric acid acidolysis, then the high-magnesium phosphate tailings are placed at a low temperature and left to stand, so that phosphorus in the high-magnesium phosphate tailings is separated out in the form of calcium chlorophosphate, then, calcium and magnesium in the high-magnesium phosphate tailings are separated out through sulfuric acid acidification, and finally, calcium sulfate whiskers and magnesium chloride whiskers are obtained through step-by-step concentration treatment.
2. The hydrochloric acid in the acidolysis reaction can be industrial hydrochloric acid, which belongs to industrial waste, thereby being beneficial to reducing the resource utilization cost of the high-magnesium phosphate tailings, being beneficial to reducing the burden and increasing the income of enterprises, and being beneficial to popularization and industrial application of the high-magnesium phosphate tailings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a process flow diagram of the resource treatment of the high-magnesium phosphate tailings of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
With reference to fig. 1, the method for recycling high-magnesium phosphate tailings of this embodiment specifically includes the following steps:
1) weighing 520mL of industrial hydrochloric acid with the mass fraction of 32% (10.34mol/L), placing the industrial hydrochloric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 30min at 60 ℃, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃ to obtain acidolysis solution A and silicon slag, wherein the silicon slag is washed three times by 100mL of distilled water, and primary water washing solution and acidolysis solution A are mixed;
2) pouring the acidolysis solution A into a dry beaker, placing in an ice bath at the temperature of-2 ℃, standing for 11h to ensure that white calcium chlorophosphate is completely separated out, preserving heat at the temperature of-2 ℃, filtering, and separating solid from liquid to obtain calcium chlorophosphate and acidolysis solution B;
3) weighing 133mL of 98% sulfuric acid, diluting until the concentration is less than or equal to 10%, dropwise adding the sulfuric acid into the acidolysis solution B, wherein the addition amount of the diluted sulfuric acid is 1 time of the mass amount of calcium in the acidolysis solution B, starting stirring, gradually generating white precipitate in the stirring process, heating to 85 ℃ after the addition of the sulfuric acid is finished, continuing reacting for 30min, aging for 12h, carrying out suction filtration to obtain an acidizing solution C and a calcium sulfate precipitate, wherein the calcium sulfate precipitate is washed with 300mL of distilled water for three times, and mixing a primary water washing solution with the acidizing solution C;
4) washing the calcium sulfate precipitate with 200mL of distilled water, and standing the washing solution for 10h to obtain calcium sulfate whiskers with a high length-diameter ratio;
5) placing the acidizing fluid C in a dry beaker, heating to 90 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the acidizing fluid C, stopping concentration when the volume of the concentrated fluid C is 0.5 times of the original volume, namely the volume ratio of the subsequently obtained concentrated fluid D to the acidizing fluid C is 0.5, and performing suction filtration to obtain calcium sulfate whiskers with high length-diameter ratio and the concentrated fluid D;
6) and (3) placing the concentrated solution D in a dry beaker, heating to 118 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the concentrated solution D, stopping heating when a crystal film is generated in the beaker, cooling to room temperature, performing suction filtration to obtain the magnesium chloride whiskers, wherein the magnesium chloride whiskers are washed with ethanol for three times and dried.
Example 2
With reference to fig. 1, the method for recycling high-magnesium phosphate tailings of this embodiment specifically includes the following steps:
1) weighing 520mL of industrial hydrochloric acid with the mass fraction of 32% (10.34mol/L), placing the industrial hydrochloric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 30min at 60 ℃, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃ to obtain acidolysis solution A and silicon slag, wherein the silicon slag is washed three times by 100mL of distilled water, and primary water washing solution and acidolysis solution A are mixed;
2) pouring the acidolysis solution A into a dry beaker, placing in an ice bath at the temperature of-2 ℃, standing for 11h to ensure that white calcium chlorophosphate is completely separated out, preserving heat at the temperature of-2 ℃, filtering, and separating solid from liquid to obtain calcium chlorophosphate and acidolysis solution B;
3) weighing 133mL of 98% sulfuric acid, diluting until the concentration is less than or equal to 10%, dropwise adding the sulfuric acid into the acidolysis solution B, wherein the addition amount of the diluted sulfuric acid is 1 time of the mass amount of calcium in the acidolysis solution B, starting stirring, gradually generating white precipitate in the stirring process, heating to 85 ℃ after the addition of the sulfuric acid is finished, continuing reacting for 30min, aging for 12h, carrying out suction filtration to obtain an acidizing solution C and a calcium sulfate precipitate, wherein the calcium sulfate precipitate is washed with 300mL of distilled water for three times, and mixing a primary water washing solution with the acidizing solution C;
4) washing the calcium sulfate precipitate with 200mL of distilled water, and standing the washing solution for 8h to obtain calcium sulfate whiskers with a high length-diameter ratio;
5) placing the acidizing fluid C in a dry beaker, heating to 90 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the acidizing fluid C, stopping concentration when the volume of the concentrated fluid C is 0.45 times of the original volume, namely the volume ratio of the subsequently obtained concentrated fluid D to the acidizing fluid C is 0.45, and performing suction filtration to obtain calcium sulfate whiskers with high length-diameter ratio and the concentrated fluid D;
6) and (3) placing the concentrated solution D in a dry beaker, heating to 102 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the concentrated solution D, stopping heating when a crystal film is generated in the beaker, cooling to room temperature, performing suction filtration to obtain the magnesium chloride whiskers, wherein the magnesium chloride whiskers are washed with ethanol for three times and dried.
Example 3
With reference to fig. 1, the method for recycling high-magnesium phosphate tailings of this embodiment specifically includes the following steps:
1) weighing 493mL of industrial hydrochloric acid with the mass fraction of 34% (10.76mol/L), placing the industrial hydrochloric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 35min at 35 ℃, carrying out acidolysis reaction, carrying out heat preservation and suction filtration at 60 ℃ after the acidolysis reaction is finished, obtaining acidolysis solution A and silicon slag, wherein the silicon slag is washed three times by 100mL of distilled water, and the primary water washing solution and the acidolysis solution A are mixed;
2) pouring the acidolysis solution A into a dry beaker, placing in an ice bath at-11 ℃, standing for 5.5h to ensure that white calcium chlorophosphate is completely separated out, preserving heat at-11 ℃, and filtering to separate solid from liquid to obtain calcium chlorophosphate and acidolysis solution B;
3) weighing 172mL of 98% sulfuric acid, diluting until the concentration is less than or equal to 10%, dropwise adding the sulfuric acid into the acidolysis solution B, wherein the addition amount of the diluted sulfuric acid is 1.20 times of the mass amount of calcium in the acidolysis solution B, starting stirring, gradually generating white precipitate in the stirring process, heating to 90 ℃ after the addition of the sulfuric acid is finished, continuing to react for 20min, aging for 9h, and carrying out suction filtration to obtain an acidizing solution C and a calcium sulfate precipitate, wherein the calcium sulfate precipitate is washed with 300mL of distilled water for three times, and mixing a primary water washing solution with the acidizing solution C;
4) washing the calcium sulfate precipitate with 200mL of distilled water, and standing the washing solution for 7h to obtain calcium sulfate whiskers with a high length-diameter ratio;
5) placing the acidizing fluid C in a dry beaker, heating to 90 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the acidizing fluid C, stopping concentration when the volume of the concentrated fluid C is 0.6 times of the original volume, namely the volume ratio of the subsequently obtained concentrated fluid D to the acidizing fluid C is 0.6, and performing suction filtration to obtain calcium sulfate whiskers with high length-diameter ratio and the concentrated fluid D;
6) and (3) placing the concentrated solution D in a dry beaker, heating to 90 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the concentrated solution D, stopping heating when a crystal film is generated in the beaker, cooling to room temperature, performing suction filtration to obtain the magnesium chloride whiskers, wherein the magnesium chloride whiskers are washed with ethanol for three times and dried.
Example 4
With reference to fig. 1, the method for recycling high-magnesium phosphate tailings of this embodiment specifically includes the following steps:
1) weighing 450mL of industrial hydrochloric acid with the mass fraction of 37% (11.43mol/L), placing the industrial hydrochloric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 55min at 20 ℃, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃ to obtain acidolysis solution A and silicon slag, wherein the silicon slag is washed three times by 100mL of distilled water, and primary water washing solution and acidolysis solution A are mixed;
2) pouring the acidolysis solution A into a dry beaker, placing in an ice bath at 0 ℃, standing for 15h to completely separate out white calcium chlorophosphate, and then carrying out heat preservation and filtration at 0 ℃ to separate solid from liquid to obtain calcium chlorophosphate and acidolysis solution B;
3) weighing 185mL of 98% sulfuric acid, diluting until the concentration is less than or equal to 10%, dropwise adding the sulfuric acid into the acidolysis solution B, wherein the addition amount of the diluted sulfuric acid is 1.21 times of the mass amount of calcium in the acidolysis solution B, starting stirring, gradually generating white precipitate in the stirring process, heating to 70 ℃ after the addition of the sulfuric acid is finished, continuing to react for 45min, aging for 12h, and carrying out suction filtration to obtain an acidizing solution C and a calcium sulfate precipitate, wherein the calcium sulfate precipitate is washed with 300mL of distilled water for three times, and mixing a primary water washing solution with the acidizing solution C;
4) washing the calcium sulfate precipitate with 200mL of distilled water, and standing the washing solution for 7.5h to obtain calcium sulfate whiskers with a high length-diameter ratio;
5) placing the acidizing fluid C in a dry beaker, heating to 100 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the acidizing fluid C, stopping concentrating when the volume of the concentrated fluid C is 0.5 times of the original volume, namely when the volume ratio of the subsequently obtained concentrated fluid D to the acidizing fluid C is 0.5, and performing suction filtration to obtain calcium sulfate whiskers with high length-diameter ratio and the concentrated fluid D;
6) and (3) placing the concentrated solution D in a dry beaker, heating to 80 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the concentrated solution D, stopping heating when a crystal film is generated in the beaker, cooling to room temperature, performing suction filtration to obtain the magnesium chloride whiskers, wherein the magnesium chloride whiskers are washed with ethanol for three times and dried.
Example 5
With reference to fig. 1, the method for recycling high-magnesium phosphate tailings of this embodiment specifically includes the following steps:
1) weighing 560mL of industrial hydrochloric acid with the mass fraction of 27% (9.71mol/L), placing the industrial hydrochloric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, after the high-magnesium phosphorus tailing is added, opening condensed water, starting stirring, refluxing for 60min at 55 ℃, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃ to obtain acidolysis solution A and silicon slag, wherein the silicon slag is washed three times by 100mL of distilled water, and primary water washing solution and acidolysis solution A are mixed;
2) pouring the acidolysis solution A into a dry beaker, placing in an ice bath at-3 ℃, standing for 11h to ensure that white calcium chlorophosphate is completely separated out, preserving heat at-3 ℃, filtering, and separating solid from liquid to obtain calcium chlorophosphate and acidolysis solution B;
3) weighing 200mL of 98% sulfuric acid, diluting until the concentration is less than or equal to 10%, dropwise adding the sulfuric acid into the acidolysis solution B, wherein the addition amount of the diluted sulfuric acid is 1.38 times of the mass amount of calcium in the acidolysis solution B, starting stirring, gradually generating white precipitate in the stirring process, heating to 85 ℃ after the addition of the sulfuric acid is finished, continuing to react for 25min, aging for 14h, and carrying out suction filtration to obtain an acidizing fluid C and a calcium sulfate precipitate, wherein the calcium sulfate precipitate is washed with 300mL of distilled water for three times, and mixing a primary water washing solution with the acidizing fluid C;
4) washing the calcium sulfate precipitate with 200mL of distilled water, and standing the washing solution for 12h to obtain calcium sulfate whiskers with a high length-diameter ratio;
5) placing the acidizing fluid C in a dry beaker, heating to 95 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the acidizing fluid C, stopping concentrating when the volume of the concentrated fluid C is 0.53 times of the original volume, namely when the volume ratio of the subsequently obtained concentrated fluid D to the acidizing fluid C is 0.53, and performing suction filtration to obtain calcium sulfate whiskers with high length-diameter ratio and the concentrated fluid D;
6) and (3) placing the concentrated solution D in a dry beaker, heating to 112 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the concentrated solution D, stopping heating when a crystal film is generated in the beaker, cooling to room temperature, performing suction filtration to obtain the magnesium chloride whiskers, wherein the magnesium chloride whiskers are washed with ethanol for three times and dried.
Example 6
With reference to fig. 1, the method for recycling high-magnesium phosphate tailings of this embodiment specifically includes the following steps:
1) 537mL of industrial hydrochloric acid with the mass fraction of 31.6% (10.06mol/L) is measured and placed in a clean three-neck flask, 261.8g of high-magnesium phosphorus tailing powder is weighed, the high-magnesium phosphorus tailing is gradually added into the three-neck flask, condensed water is opened after the addition of the high-magnesium phosphorus tailing is finished, stirring is started, the mixture is refluxed for 30min at 60 ℃, acidolysis reaction is carried out, after the acidolysis reaction is finished, heat preservation and suction filtration are carried out at 60 ℃, acidolysis solution A and silicon slag are obtained, wherein the silicon slag is washed three times by 100mL of distilled water, and primary water washing solution and the acidolysis solution A are mixed;
2) pouring the acidolysis solution A into a dry beaker, placing in an ice bath at 0 ℃, standing for 12h to completely separate out white calcium chlorophosphate, and then carrying out heat preservation and filtration at 0 ℃ to separate solid from liquid to obtain calcium chlorophosphate and acidolysis solution B;
3) measuring 213mL of 98% sulfuric acid, diluting until the concentration is less than or equal to 10%, dropwise adding the diluted sulfuric acid into the acidolysis solution B, wherein the addition amount of the diluted sulfuric acid is 1.38 times of the mass amount of calcium in the acidolysis solution B, starting stirring, gradually generating white precipitate in the stirring process, heating to 80 ℃ after the addition of the sulfuric acid is finished, continuing to react for 28min, aging for 16h, and carrying out suction filtration to obtain an acidizing fluid C and a calcium sulfate precipitate, wherein the calcium sulfate precipitate is washed with 300mL of distilled water for three times, and mixing a primary water washing solution with the acidizing fluid C;
4) washing the calcium sulfate precipitate with 200mL of distilled water, and standing the washing solution for 9h to obtain calcium sulfate whiskers with a high length-diameter ratio;
5) placing the acidizing fluid C in a dry beaker, heating to 85 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the acidizing fluid C, stopping concentrating when the volume of the concentrated fluid C is 0.55 times of the original volume, namely when the volume ratio of the subsequently obtained concentrated fluid D to the acidizing fluid C is 0.55, and performing suction filtration to obtain calcium sulfate whiskers with high length-diameter ratio and the concentrated fluid D;
6) and (3) placing the concentrated solution D in a dry beaker, heating to 107 ℃, continuously stirring in the heating process to continuously evaporate and concentrate the concentrated solution D, stopping heating when a crystal film is generated in the beaker, cooling to room temperature, performing suction filtration to obtain the magnesium chloride whiskers, wherein the magnesium chloride whiskers are washed with ethanol for three times and dried.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A resource treatment method of high-magnesium phosphate tailings is characterized by comprising the following steps:
1) mixing the high-magnesium phosphate tailings with hydrochloric acid, carrying out acidolysis reaction, and after the acidolysis reaction is finished, carrying out suction filtration to obtain acidolysis solution A and silicon slag;
2) standing the acidolysis solution A under an ice bath condition, and performing solid-liquid separation to obtain calcium chlorophosphate and acidolysis solution B;
3) dropwise adding sulfuric acid with a certain concentration into the acidolysis solution B at normal temperature, heating for reacting for a period of time, aging, and performing suction filtration to obtain an acidizing solution C and calcium sulfate precipitate;
4) after washing the calcium sulfate precipitate, standing a washing solution to obtain calcium sulfate whiskers;
5) concentrating the acidizing fluid C, and performing suction filtration to obtain calcium sulfate whiskers and a concentrated solution D;
6) concentrating the concentrated solution D, and performing suction filtration to obtain magnesium chloride whiskers;
the concentration of the hydrochloric acid in the step 1) is 8.80-12.07mol/L, and the mass ratio of the hydrochloric acid to the high-magnesium phosphate tailings is (2.0-2.8) to 1;
the ice bath temperature of the ice bath in the step 2) is-10 ℃ to 0 ℃, and the standing time is 10 to 24 hours;
the concentration of the sulfuric acid in the step 3) is less than or equal to 10%, and the addition amount of the sulfuric acid is 1-1.5 times of the mass amount of calcium in the acidolysis solution B;
the concentration temperature of the concentration in the step 5) is 80-100 ℃, and the volume ratio of the concentrated solution D to the acidizing solution C is 0.4-0.6;
the concentration temperature of the concentration in the step 6) is 80-118 ℃.
2. The resource treatment method of the high-magnesium phosphate tailings in the claim 1, wherein the acidolysis reaction in the step 1) is performed at a temperature of 20-60 ℃ for 20-60 min.
3. The resource treatment method of the high-magnesium phosphate tailings according to claim 1, wherein the reaction temperature of the heating reaction in the step 3) is 70-95 ℃, and the reaction time is 10-40 min.
4. The resource treatment method of the high-magnesium phosphate tailings in claim 1, wherein the aging time for the aging in the step 3) is 8-16 h.
5. The resource treatment method of the high-magnesium phosphate tailings according to claim 1, wherein the standing time of the standing in the step 4) is 6-12 h.
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