CN104860287A - Method for preparing magnesium ammonium phosphate and magnesium ammonium nitrate with phosphate tailings - Google Patents
Method for preparing magnesium ammonium phosphate and magnesium ammonium nitrate with phosphate tailings Download PDFInfo
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Abstract
The invention discloses a method for preparing magnesium ammonium phosphate and magnesium ammonium nitrate with phosphate tailings. The method comprises the steps of using nitric acid for carrying out acidolysis on phosphate tailings, filtering and washing reaction feed liquid to obtain acidolysis liquid and acidolysis residues, preheating the acidolysis liquid, adding an ammonium sulfate solution into the acidolysis liquid, stirring the mixture for some time for reaction under a certain temperature and then filtering the mixture to obtain gypsum and a decalcifying solution, adding ammonia water into the decalcifying solution for neutralization and filtering the mixture to obtain a neutralization solution and residues, pelletizing the residues to obtain magnesium ammonium phosphate, and pelletizing the neutralization solution after concentrating the neutralization solution to obtain magnesium ammonium nitrate. With the method, phosphate tailings can be treated in a large-scale mode, the problem that phosphate tailings piles up in bulk is effectively solved, and the obtained products, namely magnesium ammonium phosphate and magnesium ammonium nitrate, contain active magnesium, and have good fertilizer efficiency.
Description
Technical field
The present invention relates to the recovery and utilization technology field of phosphorus mine tailing, specifically, relate to a kind of method utilizing phosphorus mine tailing to prepare magnesium ammonium phosphate and ammonium nitrate magnesium.
Background technology
The solid waste of failing to be used of discharging when phosphorus mine tailing is phosphate rock floating concentrate.The grade of China's Rock Phosphate (72Min BPL) raw ore is all not high, causes sulphur dioxide of phosphor chemical industry and all outwards will discharge a large amount of phosphorus mine tailings when phosphate rock floating concentrate, often produces 3 tons of phosphorus ores, discharge 1 ton of phosphorus mine tailing, the bulk deposition of phosphorus mine tailing, not only takies a large amount of soils, but also can bring environmental pollution.Along with the development of China's phosphorus chemical industry and the continuous increase of social demand, the demand of phosphorus product is also along with increase, and the accumulation problem of phosphorus mine tailing is more and more serious.Phosphorus mine tailing is when being corroded, and in mine tailing during some transportable element generation chemical transport, will cause serious pollution to air and water and soil, serious meeting causes land deterioration, and vegetation is destroyed, and threatens the safety of people and animals.China at present by the land area of phosphorus tailings pollution up to 1,000,000 mu.
Because the phosphorus ore moiety of various places is different, the component difference of various places phosphorus mine tailing is larger, the main component of Guizhou province phosphorus mine tailing is rhombspar (accounting for about 80% of phosphorus mine tailing), secondly also containing a small amount of phosphatic rock (accounting for about 15% of phosphorus mine tailing).At present, the utilization of China to phosphorus mine tailing is mainly reflected in the following aspects: first, by phosphorus mine tailing as the raw material preparing material of construction, material of construction is as cement, gas concrete and devitrified glass etc., although above-mentioned several approach can consume a part of phosphorus mine tailing, alleviate the situation of phosphorus mine tailing bulk deposition to a certain extent, but phosphorus mine tailing is not utilized fully, cause the waste of part useful element in phosphorus mine tailing; The second, phosphorus mine tailing is carried out secondary flotation, and the method utilizes further to the phosphorus in phosphorus mine tailing, effectively can reduce the phosphorus content in phosphorus mine tailing, but still on the low side to the utilization ratio of phosphorus in phosphorus mine tailing, and fundamentally can not solve the present situation of phosphorus mine tailing bulk deposition; 3rd, adopt Mixed phosphoric acid and sulfuric acid to divide phosphorus decomposing mine tailing to prepare phosphorus fertiliser containing magnesium, although this kind of method can solve the Utilizing question of part phosphorite tailings, it will consume a large amount of sulfuric acid and phosphoric acid goes to prepare phosphorus fertiliser containing magnesium, and the economic benefit obtained is bad.
Application number is 201410595486.8, denomination of invention is a kind of method preparing high purity magnesium hydrate, phosphor tail slag is extracted after mixing by a certain percentage with industrial nitric acid and phosphate fertilizer plant's acid-bearing wastewater, filter out the extraction liquid after acid non-soluble substance and carry out one section of neutralization, after filtering, filtrate carries out obtaining magnesium hydroxide products with filtering separation post-drying in two sections.The waste water of this technology utilization phosphate fertilizer plant, reduces acid consumption, reduce production cost, and obtained magnesium hydroxide purity is higher.But this kind of method has only recycled the magnesium in phosphorus mine tailing, makes full use of other useful elements in phosphorus mine tailing, cause the waste as phosphorus and calcium of useful element in phosphorus mine tailing.
In sum, develop a kind of technology fully useful element in phosphorus mine tailing can being carried out recycling, there is important economic implications and environment protection significance.
Summary of the invention
In view of this, the object of this invention is to provide a kind of method utilizing phosphorus mine tailing to prepare magnesium ammonium phosphate and ammonium nitrate magnesium, to solve phosphorus mine tailing bulk deposition, cause a large amount of soil occupied, bring environmental pollution, cause land deterioration, vegetation is destroyed, and threatens the safety of people and animals and the technical problem existed.
For solving the problems of the technologies described above, the present inventor, for the characteristic of phosphorus mine tailing, carries out deep development research to the comprehensive Utilization Ways of phosphorus mine tailing, through long-term research and constantly test, draws following technical scheme:
Utilize phosphorus mine tailing to prepare a method for magnesium ammonium phosphate and ammonium nitrate magnesium, comprise the following steps:
(1) acidolysis: first nitric acid is joined in reactive tank, temperature is regulated to be keep constant temperature after 50 ~ 60 DEG C, and after rotating speed is adjusted to 200 ~ 300r/min, add phosphorus mine tailing, then with the speed of 10 ~ 20r/min, rotating speed is increased to 450 ~ 550r/min, the mass ratio of nitric acid and phosphorus mine tailing is (2 ~ 3): 1, after reaction 1 ~ 3h, obtains reaction feed liquid;
(2) filter, wash: reaction feed liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtain residue and washing lotion;
(3) decalcification: first acid hydrolysis solution being preheated to temperature is 50 ~ 60 DEG C, the rotating speed of agitator is adjusted to 550 ~ 650r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 15 ~ 25g/L, in the process adding ammoniumsulphate soln, with the speed of 10 ~ 20r/min, rotating speed is increased to 700 ~ 900r/min, and temperature is increased to 70 ~ 80 DEG C, after reaction 100 ~ 150min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is washed, then dry, obtain gypsum, and washings is turned back in decalcification operation,
(4) neutralize: ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.2 ~ 6.5, and regulate temperature of reaction to be 70 ~ 90 DEG C, after the rotating speed stirring reaction 30 ~ 80min of 500 ~ 700r/min, stop heating and stir, reaction feed liquid being filtered, obtains neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate;
(5) granulation: adopted by neutralizer the temperature evaporation concentration of 100 ~ 150 DEG C to be after the fused solution of 94 ~ 97% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
In described phosphorus mine tailing, calcium oxide content is 30 ~ 45%, and content of magnesia is 11 ~ 20%, and the content of Vanadium Pentoxide in FLAKES is 5 ~ 12%.
Preferably, in described phosphorus mine tailing, phosphorus pentoxide content is 5.5 ~ 6.6%, calcium oxide content is 33.4 ~ 35.9%, content of magnesia is 17.6 ~ 18.9%.
The concentration of described salpeter solution is 50 ~ 60%.
The concentration of described ammoniacal liquor is 25 ~ 28%.
The concentration of described ammonium sulfate is 30 ~ 40%.
In described step (1), adopt ammoniacal liquor be used for absorption reaction generate carbon dioxide, obtain sal volatile.
In described step (2), washing lotion is returned in hydrolysis procedure.
In described step (3), first acid hydrolysis solution being preheated to temperature is 55 DEG C, the rotating speed of agitator is adjusted to 600r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 20g/L, in the process adding ammoniumsulphate soln, with the speed of 15r/min, rotating speed is increased to 800r/min, and temperature is increased to 75 DEG C, after reaction 120min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is washed, then dries, obtain gypsum, and washings is turned back in decalcification operation.
In described step (3), washing point is carried out for four times, first three time adopts cold water washing, the washings that first time washs turns back in decalcification operation, second time and third time adopt countercurrent washing, secondary washings is used for third time washing, adopts for the 4th time the hot water of 60 DEG C to carry out countercurrent washing.
In described step (4), ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.3, and regulate temperature of reaction to be 80 DEG C, after the rotating speed stirring reaction 60min of 600r/min, stop heating and stir, reaction feed liquid is filtered, obtain neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate.
In described step (5), adopted by neutralizer the temperature evaporation concentration of 120 DEG C to be after the fused solution of 96% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
Beneficial effect of the present invention is:
1, the present invention is with phosphorus mine tailing for main raw material prepares magnesium ammonium phosphate and ammonium nitrate magnesium, effectively recycles the phosphorus in phosphorus mine tailing, calcium and magnesium, has good economic benefit.Meanwhile, the method can carry out mass disposal to phosphorus mine tailing, efficiently solves phosphorus mine tailing bulk deposition and a large amount of soils brought are occupied and the problem such as environmental pollution.
2, the present invention adopts and is slowly joined in nitric acid by phosphorus mine tailing, be conducive to the abundant dissolving in phosphorus mine tailing, and by the control of nitric acid and phosphorus mine tailing consumption and stirring velocity, the control of temperature of reaction, phosphorus is all dissolved in acid hydrolysis solution, and adopt ammonium sulfate by the calcium removing in acid hydrolysis solution, ensure that the magnesium ammonium phosphate of subsequent production and the quality of ammonium nitrate magnesium, acid hydrolysis solution being neutralized to pH value is 62 ~ 6.5, first for magnesium ammonium phosphate filtering separation is conducive to be gone out, phosphorus content in the magnesium ammonium phosphate prepared is improved greatly, the content of nitrogen and phosphorus is more than 40%, the content of moderate-element magnesium and calcium is about 15%, this magnesium ammonium phosphate nutritive element content enriches, and reasonable ratio, there is good fertilizer efficiency.In the ammonium nitrate magnesium obtained, nitrogen content is more than 25%, and nitric nitrogen is more than 14%, and the content of moderate-element magnesium is about 4%, is a kind of production of compound fertilizer raw material preferably.
3, the present invention in process of production, all recycles, greatly reduce production cost to waste residue and waste liquid, decreases outside sewage effluent and solid waste, has significant environment protection significance.
4, the filter residue after decalcification is carried out four washings by the present invention, and adopt first three cold water washing, 4th hot wash, first time following current washing, the mode of rear three countercurrent washings, can thoroughly wash in washing lotion by the phosphorus in filter residue and magnesium useful element, and washing lotion is recycled, effectively prevent the loss of useful element, improve the comprehensive utilization ratio to phosphorus mine tailing, reduce manufacturing cost further.
Effect of the present invention is verified below with experiment:
Experimental raw:
Phosphorus mine tailing, salpeter solution, ammoniacal liquor.Wherein, in phosphorus mine tailing, phosphorus pentoxide content is 5.64%, calcium oxide content is 33.87%, content of magnesia is 18.88%, iron oxide content is 0.26%, alumina content is 0.37%, Oil repellent is 0.52%; The concentration of salpeter solution is 55%; The purity of ammoniacal liquor is 25 ~ 28%, and the concentration of ammoniumsulphate soln is 34%.
Experimental installation:
Retort furnace, electronic thermostatic agitator, stirring arm, glass beaker, temperature adjustable electrically heated device, thermometer, filter flask, funnel and water-jet exhauster.
Experimental procedure:
1), get A, B, C and D tetra-volumes are the beaker of 1000mL, 975g salpeter solution is added successively in four beakers, 1035g salpeter solution, 1100g salpeter solution and 1250g salpeter solution, the rotating speed regulating agitator is 300r/min, then in four beakers, 500g phosphorus mine tailing is added respectively, feed time is 75min, to guarantee that foam does not overflow beaker in the process, and gradually rotating speed is increased to 500r/min, after material is warming up to 50 DEG C naturally, electric thermal power is regulated to make temperature remain on 50 DEG C, carry out filtering and washing after material reaction 60min, obtain acid hydrolysis solution and acidolysis slag, measure its chemical composition, as table 1:
Table 1
As can be seen from experimental result, along with the increase of nitric acid dosage, phosphorus residual in acidolysis slag reduces, and when nitric acid dosage reaches 1250g, phosphorus almost all enters into acid hydrolysis solution.In addition, sour consumption is lower, the more sad filter of slip of gained.The bubble produced due to phosphorus mine tailing is more, and the nitrogen oxide taken out of is more, thus will extend feed time.
2), the acid hydrolysis solution of above-mentioned acquisition is mixed, acid hydrolysis solution being preheated to temperature is 55 DEG C again, the rotating speed of agitator is adjusted to 600r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 15g/L, in the process adding ammoniumsulphate soln, rotating speed is increased to 800r/min, and keep constant temperature after temperature is increased to 70 DEG C, after reaction 120min, reaction feed liquid is carried out filtering and washing, obtain gypsum and decalcifying Fluid, detect the composition of decalcifying Fluid and gypsum, result is as follows:
Table 2
As can be seen from experimental result, also containing a small amount of calcium in decalcifying Fluid, but calcium is as moderate-element required in growing process, and a small amount of calcium exists, and the nutritive element of the ammonium phosphate fertiliser containing magnesium of subsequent production can be made abundanter.
3), by the acid hydrolysis solution of above-mentioned acquisition mix, join in beaker, start agitator and make rotating speed be 600r/min, adopt ammonia neutralization to be 6.2 to pH, secondary calcium phosphate and magnesium ammonium phosphate are separated out, regulates electric thermal power, temperature of reaction is made to remain on 80 DEG C, filter after continuing reaction 30min and wash, after being dried by filter cake, obtaining magnesium ammonium phosphate, after concentrated for filtrate solidification, obtain ammonium nitrate magnesium, detect the composition of magnesium ammonium phosphate and ammonium nitrate magnesium, result is as table 3:
Table 3
| Vanadium Pentoxide in FLAKES (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Magnesium ammonium phosphate | 38.95 | 0.94 | 14.92 | 2.28 |
| Ammonium nitrate magnesium | 0.00 | 0.19 | 4.65 | 25.28 |
From experimental result, in magnesium ammonium phosphate, phosphorus content improves greatly, and the content of nitrogen and phosphorus is more than 40%, and the content of moderate-element magnesium and calcium is about 15%, and nutritive element content enriches, and reasonable ratio, there is good fertilizer efficiency.In the ammonium nitrate magnesium obtained, nitrogen content is more than 25%, and nitric nitrogen is more than 14%, the content about 5% of moderate-element calcium, magnesium, is that a kind of nitro is preferably containing fertiliser containing magnesium.
Embodiment
Conveniently those skilled in the art will recognize that the present invention will be further described below in conjunction with embodiment.Embodiment is only illustrating this invention, is not limitation of the invention, and the step not doing in embodiment to illustrate is all prior arts, is not described in detail at this.
The main chemical reactions equation that the present invention relates to is as follows:
Reaction formula one:
CaCO
3·MgCO
3+4HNO
3→Ca(NO
3)
2+M(NO
3)
2+2H
2O+2CO
2
Reaction formula two:
10HNO
3+Ca
5F(PO
4)
3+SiO
2→5Ca(NO
3)
2+3H
3PO
4+H
2SiF
6
Reaction formula three:
Ca(NO
3)
2+(NH
4)
2SO
4+2H
2O→CaSO
4·2H
2O+2NH
4NO
3
Reaction formula four:
Mg(NO
3)
2+H
3PO
4+3NH
3+H
2O→2NH
4NO
3+MgNH
4PO
4·H
2O
Embodiment one
Utilize phosphorus mine tailing to prepare a method for magnesium ammonium phosphate and ammonium nitrate magnesium, comprise the following steps:
(1) acidolysis: first nitric acid is joined in reactive tank, temperature is regulated to be keep constant temperature after 50 DEG C, and after rotating speed is adjusted to 200r/min, add phosphorus mine tailing, then with the speed of 10r/min, rotating speed be increased to 450r/min, adopt ammoniacal liquor be used for absorption reaction generate carbon dioxide, obtain sal volatile, the mass ratio of nitric acid and phosphorus mine tailing is 2:1, after reaction 1h, obtains reaction feed liquid;
(2) filter, wash: reaction feed liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtain residue and washing lotion, washing lotion is returned in hydrolysis procedure;
(3) decalcification: first acid hydrolysis solution being preheated to temperature is 50 DEG C, the rotating speed of agitator is adjusted to 550r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 15g/L, in the process adding ammoniumsulphate soln, with the speed of 10r/min, rotating speed is increased to 700r/min, and temperature is increased to 70 DEG C, after reaction 100min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is carried out four washings, first three time adopts cold water washing, the washings that first time washs turns back in decalcification operation, second time and third time adopt countercurrent washing, secondary washings is used for third time washing, after adopting for 4th time the hot water of 60 DEG C to carry out countercurrent washing, filter residue and drying is obtained gypsum,
(4) neutralize: ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.2, and regulate temperature of reaction to be 70 DEG C, after the rotating speed stirring reaction 30min of 500r/min, stop heating and stir, reaction feed liquid being filtered, obtains neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate;
(5) granulation: adopted by neutralizer the temperature evaporation concentration of 100 DEG C to be after the fused solution of 94% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
In described phosphorus mine tailing, calcium oxide content is 33.4%, and content of magnesia is 17.6%, and the content of Vanadium Pentoxide in FLAKES is 5.5%; The concentration of salpeter solution is 50%; The concentration of ammoniacal liquor is 25%; The concentration of ammonium sulfate is 30%.
Detect the composition of the magnesium ammonium phosphate obtained in this technique and ammonium nitrate magnesium, result is as following table:
Table 4
| Vanadium Pentoxide in FLAKES (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Magnesium ammonium phosphate | 39.01 | 1.03 | 14.32 | 1.73 |
| Ammonium nitrate magnesium | 0.00 | 0.32 | 4.63 | 25.16 |
Embodiment two
Utilize phosphorus mine tailing to prepare a method for magnesium ammonium phosphate and ammonium nitrate magnesium, comprise the following steps:
(1) acidolysis: first nitric acid is joined in reactive tank, temperature is regulated to be keep constant temperature after 60 DEG C, and after rotating speed is adjusted to 300r/min, add phosphorus mine tailing, then with the speed of 20r/min, rotating speed be increased to 550r/min, adopt ammoniacal liquor be used for absorption reaction generate carbon dioxide, obtain sal volatile, the mass ratio of nitric acid and phosphorus mine tailing is 3:1, after reaction 3h, obtains reaction feed liquid;
(2) filter, wash: reaction feed liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtain residue and washing lotion, washing lotion is returned in hydrolysis procedure;
(3) decalcification: first acid hydrolysis solution being preheated to temperature is 60 DEG C, the rotating speed of agitator is adjusted to 650r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 25g/L, in the process adding ammoniumsulphate soln, with the speed of 20r/min, rotating speed is increased to 900r/min, and temperature is increased to 80 DEG C, after reaction 150min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is carried out four washings, first three time adopts cold water washing, the washings that first time washs turns back in decalcification operation, second time and third time adopt countercurrent washing, secondary washings is used for third time washing, after adopting for 4th time the hot water of 60 DEG C to carry out countercurrent washing, filter residue and drying is obtained gypsum,
(4) neutralize: ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.5, and regulate temperature of reaction to be 90 DEG C, after the rotating speed stirring reaction 80min of 700r/min, stop heating and stir, reaction feed liquid being filtered, obtains neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate;
(5) granulation: adopted by neutralizer the temperature evaporation concentration of 150 DEG C to be after the fused solution of 97% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
In described phosphorus mine tailing, phosphorus pentoxide content is 5.64%, calcium oxide content is 33.87%, content of magnesia is 18.88%; The concentration of salpeter solution is 60%; The concentration of ammoniacal liquor is 28%; The concentration of ammonium sulfate is 40%.
Detect the composition of the magnesium ammonium phosphate obtained in this technique and ammonium nitrate magnesium, result is as following table:
Table 5
| Vanadium Pentoxide in FLAKES (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Magnesium ammonium phosphate | 38.36 | 0.79 | 14.90 | 2.84 |
| Ammonium nitrate magnesium | 0.00 | 0.15 | 4.17 | 25.88 |
Embodiment three
Utilize phosphorus mine tailing to prepare a method for magnesium ammonium phosphate and ammonium nitrate magnesium, comprise the following steps:
(1) acidolysis: first nitric acid is joined in reactive tank, temperature is regulated to be keep constant temperature after 55 DEG C, and after rotating speed is adjusted to 250r/min, add phosphorus mine tailing, then with the speed of 15r/min, rotating speed be increased to 500r/min, adopt ammoniacal liquor be used for absorption reaction generate carbon dioxide, obtain sal volatile, the mass ratio of nitric acid and phosphorus mine tailing is 2.5:1, after reaction 2h, obtains reaction feed liquid;
(2) filter, wash: reaction feed liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtain residue and washing lotion, washing lotion is returned in hydrolysis procedure;
(3) decalcification: first acid hydrolysis solution being preheated to temperature is 55 DEG C, the rotating speed of agitator is adjusted to 600r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 20g/L, in the process adding ammoniumsulphate soln, with the speed of 15r/min, rotating speed is increased to 800r/min, and temperature is increased to 75 DEG C, after reaction 120min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is carried out four washings, first three time adopts cold water washing, the washings that first time washs turns back in decalcification operation, second time and third time adopt countercurrent washing, secondary washings is used for third time washing, after adopting for 4th time the hot water of 60 DEG C to carry out countercurrent washing, filter residue and drying is obtained gypsum,
(4) neutralize: ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.3, and regulate temperature of reaction to be 75 DEG C, after the rotating speed stirring reaction 50min of 600r/min, stop heating and stir, reaction feed liquid being filtered, obtains neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate;
(5) granulation: adopted by neutralizer the temperature evaporation concentration of 120 DEG C to be after the fused solution of 96% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
In described phosphorus mine tailing, phosphorus pentoxide content is 5.64%, calcium oxide content is 33.87%, content of magnesia is 18.88%; The concentration of salpeter solution is 55%; The concentration of ammoniacal liquor is 26%; The concentration of ammonium sulfate is 34%.
Detect the composition of the magnesium ammonium phosphate obtained in this technique and ammonium nitrate magnesium, result is as following table:
Table 6
| Vanadium Pentoxide in FLAKES (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Magnesium ammonium phosphate | 38.46 | 0.89 | 14.46 | 2.08 |
| Ammonium nitrate magnesium | 0.00 | 0.24 | 4.34 | 25.31 |
Embodiment four
Utilize phosphorus mine tailing to prepare a method for magnesium ammonium phosphate and ammonium nitrate magnesium, comprise the following steps:
(1) acidolysis: first nitric acid is joined in reactive tank, temperature is regulated to be keep constant temperature after 58 DEG C, and after rotating speed is adjusted to 280r/min, add phosphorus mine tailing, then with the speed of 12r/min, rotating speed be increased to 480r/min, adopt ammoniacal liquor be used for absorption reaction generate carbon dioxide, obtain sal volatile, the mass ratio of nitric acid and phosphorus mine tailing is 2.6:1, after reaction 2.5h, obtains reaction feed liquid;
(2) filter, wash: reaction feed liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtain residue and washing lotion, washing lotion is returned in hydrolysis procedure;
(3) decalcification: first acid hydrolysis solution being preheated to temperature is 52 DEG C, the rotating speed of agitator is adjusted to 620r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 18g/L, in the process adding ammoniumsulphate soln, with the speed of 16r/min, rotating speed is increased to 750r/min, and temperature is increased to 72 DEG C, after reaction 130min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is carried out four washings, first three time adopts cold water washing, the washings that first time washs turns back in decalcification operation, second time and third time adopt countercurrent washing, secondary washings is used for third time washing, after adopting for 4th time the hot water of 60 DEG C to carry out countercurrent washing, filter residue and drying is obtained gypsum,
(4) neutralize: ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.4, and regulate temperature of reaction to be 76 DEG C, after the rotating speed stirring reaction 60min of 600r/min, stop heating and stir, reaction feed liquid being filtered, obtains neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate;
(5) granulation: adopted by neutralizer the temperature evaporation concentration of 110 DEG C to be after the fused solution of 95% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
In described phosphorus mine tailing, phosphorus pentoxide content is 6.64%, calcium oxide content is 35.87%, content of magnesia is 18.88%; The concentration of salpeter solution is 55%; The concentration of ammoniacal liquor is 26%; The concentration of ammonium sulfate is 34%.
Detect the composition of the magnesium ammonium phosphate obtained in this technique and ammonium nitrate magnesium, result is as following table:
Table 7
| Vanadium Pentoxide in FLAKES (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Magnesium ammonium phosphate | 38.52 | 0.86 | 14.27 | 2.16 |
| Ammonium nitrate magnesium | 0.00 | 0.23 | 4.26 | 25.42 |
The above, it is only better example of the present invention, not any pro forma restriction is done to the present invention, anyly do not depart from technical solution of the present invention content, the any simple modification done above example according to technical spirit of the present invention, coversion material equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. utilize phosphorus mine tailing to prepare a method for magnesium ammonium phosphate and ammonium nitrate magnesium, it is characterized in that, comprise the following steps:
(1) acidolysis: first nitric acid is joined in reactive tank, temperature is regulated to be keep constant temperature after 50 ~ 60 DEG C, and after rotating speed is adjusted to 200 ~ 300r/min, add phosphorus mine tailing, then with the speed of 10 ~ 20r/min, rotating speed is increased to 450 ~ 550r/min, the mass ratio of nitric acid and phosphorus mine tailing is (2 ~ 3): 1, after reaction 1 ~ 3h, obtains reaction feed liquid;
(2) filter, wash: reaction feed liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtain residue and washing lotion;
(3) decalcification: first acid hydrolysis solution being preheated to temperature is 50 ~ 60 DEG C, the rotating speed of agitator is adjusted to 550 ~ 650r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 15 ~ 25g/L, in the process adding ammoniumsulphate soln, with the speed of 10 ~ 20r/min, rotating speed is increased to 700 ~ 900r/min, and temperature is increased to 70 ~ 80 DEG C, after reaction 100 ~ 150min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is washed, then carry out drying to obtain gypsum, and washings is turned back in decalcification operation,
(4) neutralize: ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.2 ~ 6.5, and regulate temperature of reaction to be 70 ~ 90 DEG C, after the rotating speed stirring reaction 30 ~ 80min of 500 ~ 700r/min, stop heating and stir, reaction feed liquid being filtered, obtains neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate;
(5) granulation: adopted by neutralizer the temperature evaporation concentration of 100 ~ 150 DEG C to be after the fused solution of 94 ~ 97% to concentration, then send into granulation in rotary drum vulcanization bed, obtain ammonium nitrate magnesium.
2. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, in described phosphorus mine tailing, calcium oxide content is 30 ~ 45%, and content of magnesia is 11 ~ 20%, and the content of Vanadium Pentoxide in FLAKES is 5 ~ 12%.
3. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, the concentration of described salpeter solution is 50 ~ 60%.
4. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, the concentration of described ammoniacal liquor is 25 ~ 28%.
5. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, the concentration of described ammonium sulfate is 30 ~ 40%.
6. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, in described step (1), adopt ammoniacal liquor be used for absorption reaction generate carbon dioxide, obtain sal volatile.
7. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, in described step (2), washing lotion is returned in hydrolysis procedure.
8. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, in described step (3), first acid hydrolysis solution being preheated to temperature is 55 DEG C, the rotating speed of agitator is adjusted to 600r/min, ammoniumsulphate soln is added in acid hydrolysis solution, in adjustment solution, the concentration of sulfate radical is 20g/L, in the process adding ammoniumsulphate soln, with the speed of 15r/min, rotating speed is increased to 800r/min, and temperature is increased to 75 DEG C, after reaction 120min, reaction feed liquid is filtered, obtain filter residue and decalcifying Fluid, filter residue is washed, then dry, obtain gypsum, and washings is turned back in decalcification operation.
9. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, in described step (4), ammoniacal liquor is joined in decalcifying Fluid, the pH value regulating mixed solution is 6.3, and regulate temperature of reaction to be 80 DEG C, after the rotating speed stirring reaction 60min of 600r/min, stop heating and stir, reaction feed liquid is filtered, obtain neutralizer and filter residue, filter residue is sent into granulation in rotary drum vulcanization bed, obtain magnesium ammonium phosphate.
10. utilize phosphorus mine tailing to prepare the method for magnesium ammonium phosphate and ammonium nitrate magnesium as claimed in claim 1, it is characterized in that, in described step (5), the temperature evaporation concentration of 120 DEG C is adopted by neutralizer to be after the fused solution of 96% to concentration, send into granulation in rotary drum vulcanization bed again, obtain ammonium nitrate magnesium.
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| CN110697674A (en) * | 2019-12-03 | 2020-01-17 | 中化重庆涪陵化工有限公司 | Method for producing magnesium ammonium phosphate by using high-magnesium phosphate tailings |
| CN110817911A (en) * | 2019-11-08 | 2020-02-21 | 三峡公共检验检测中心 | Method for preparing gypsum whisker, magnesium chloride, ammonium magnesium phosphate and ammonium chloride from phosphate tailings |
| CN111451004A (en) * | 2020-04-20 | 2020-07-28 | 武汉工程大学 | Method for producing phosphate concentrate and byproducts α -hemihydrate gypsum and magnesium carbonate from calcium collophanite |
| CN111484020A (en) * | 2020-04-20 | 2020-08-04 | 武汉工程大学 | Tail-free utilization method of high-magnesium phosphate tailings |
| CN111498891A (en) * | 2020-04-20 | 2020-08-07 | 武汉工程大学 | Method for efficiently utilizing calcium, magnesium and phosphorus in high-magnesium phosphorus tailings |
| CN111498826A (en) * | 2020-04-20 | 2020-08-07 | 武汉工程大学 | Preparation of magnesium ammonium phosphate and CaCO from phosphate tailings3And recycle by-product (NH)4)2SO4And CO2Method (2) |
| CN111498820A (en) * | 2020-04-26 | 2020-08-07 | 贵州省化工研究院 | Process for simultaneously preparing high-quality calcium sulfate whiskers from phosphorus concentrate enriched by medium-low-grade phosphate ore or phosphorus tailings |
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| CN111498891A (en) * | 2020-04-20 | 2020-08-07 | 武汉工程大学 | Method for efficiently utilizing calcium, magnesium and phosphorus in high-magnesium phosphorus tailings |
| CN111498826A (en) * | 2020-04-20 | 2020-08-07 | 武汉工程大学 | Preparation of magnesium ammonium phosphate and CaCO from phosphate tailings3And recycle by-product (NH)4)2SO4And CO2Method (2) |
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