CN104860287B - A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing - Google Patents
A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing Download PDFInfo
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Abstract
The invention discloses a kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, acidolysis is first carried out to phosphorus mine tailing using nitric acid, after reaction material liquid is filtered and washed, obtain acid hydrolysis solution and acidolysis slag, acid hydrolysis solution is first preheated, then ammonium sulfate is added, stirring reaction is filtered afterwards for a period of time at a certain temperature, gypsum and decalcifying Fluid are obtained, ammoniacal liquor is added to after decalcifying Fluid is neutralized and filtered, obtains neutralizer and filter residue, filter residue is granulated, ammonium magnesium phosphate is obtained, is granulated after neutralizer is concentrated, produces ammonium nitrate magnesium.The present invention can largely handle phosphorus mine tailing, effectively solve the problems, such as phosphorus mine tailing bulk deposition, and the product ammonium magnesium phosphate and ammonium nitrate magnesium that obtain contain active magnesium elements, have preferable fertilizer efficiency.
Description
Technical field
The present invention relates to the utilization technology field of phosphorus mine tailing, it particularly relates to which one kind prepares phosphorus using phosphorus mine tailing
The method of sour ammonium magnesium and ammonium nitrate magnesium.
Background technology
The solid waste for failing to be used that phosphorus mine tailing is discharged when being phosphate rock floating concentrate.The product of China's rock phosphate in powder raw ore
Position is not high, and substantial amounts of phosphorus mine tailing will outwards be discharged in phosphate rock floating concentrate by causing sulphur dioxide of phosphor chemical industry, often produces 3 tons of phosphorus
Ore deposit, 1 ton of phosphorus mine tailing is discharged, the bulk deposition of phosphorus mine tailing, does not only take up substantial amounts of soil, but also environmental pollution can be brought.
With the continuous development of China's phosphorus chemical industry and being continuously increased for social demand, the demand of phosphorus product also increases as, phosphorus tail
The accumulation problem of ore deposit is increasingly severe.Phosphorus mine tailing is when being corroded, and some transportable elements generation chemistry move in mine tailing
During shifting, it will serious pollution is caused to air and water and soil, serious meeting causes land deterioration, and vegetation is destroyed, and is threatened
The safety of people and animals.China is up to million mu by the land area of phosphorus tailings pollution at present.
Because the phosphorus ore constituent of various regions is different, the component difference of various regions phosphorus mine tailing is larger, Guizhou province phosphorus mine tailing
Main component is dolomite (account for phosphorus mine tailing 80% or so), and secondly also containing a small amount of apatite, (account for phosphorus mine tailing 15% is left
It is right).At present, utilization of the China to phosphorus mine tailing is mainly reflected in the following aspects：First, phosphorus mine tailing is used as to prepare Building wood
The raw material of material, construction material such as cement, air entrained concrete and devitrified glass etc., although above-mentioned several approach can consume a part
Phosphorus mine tailing, the situation of phosphorus mine tailing bulk deposition is alleviated to a certain extent, but phosphorus mine tailing is not utilized sufficiently, make
Into the waste of part useful element in phosphorus mine tailing；Second, phosphorus mine tailing is subjected to secondary flotation, this method is to the phosphorus in phosphorus mine tailing
Further utilized, can effectively reduce the phosphorus content in phosphorus mine tailing, but it is still relatively low to the utilization rate of phosphorus in phosphorus mine tailing, and not
Can fundamentally solve the present situation of phosphorus mine tailing bulk deposition；3rd, phosphorus mine tailing is decomposed using Mixed phosphoric acid and sulfuric acid and prepares phosphorus fertiliser containing magnesium, should
Although kind of a method can solve the Utilizing question of part phosphorite tailings, it will consume substantial amounts of sulfuric acid and phosphoric acid and go to prepare phosphorus magnesium
Fertilizer, the economic benefit of acquirement are bad.
Application No. 201410595486.8, a kind of entitled method for preparing high purity magnesium hydrate, with industry
Nitric acid and phosphate fertilizer plant's acid-bearing wastewater extract phosphor tail slag after mixing by a certain percentage, filter out the progress of the extract after acid non-soluble substance
One section of neutralization, filtrate, which dried after two sections of neutralizations are separated by filtration, after filtering is made magnesium hydroxide products.The technology utilization phosphate fertilizer
The waste water of factory, acid consumption is reduced, reduces production cost, and obtained magnesium hydroxide purity is higher.But this kind of method only reclaims profit
With the magnesium in phosphorus mine tailing, other useful elements in phosphorus mine tailing are not made full use of, cause useful member in phosphorus mine tailing
The waste of element such as phosphorus and calcium.
In summary, a kind of technology that fully can be recycled the useful element in phosphorus mine tailing is developed, is had
There are important economic implications and environment protection significance.
The content of the invention
In view of this, it is an object of the invention to provide a kind of side that ammonium magnesium phosphate and ammonium nitrate magnesium are prepared using phosphorus mine tailing
Method, to solve phosphorus mine tailing bulk deposition, cause a large amount of soils occupied, bring environmental pollution, cause land deterioration, vegetation by
Destroy, threaten people and animals safety and existing technical problem.
In order to solve the above technical problems, the present inventor is directed to the characteristic of phosphorus mine tailing, the comprehensive utilization to phosphorus mine tailing
Approach carries out deep developmental research, by long-term research and constantly experiment, draws following technical scheme：
A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, comprises the following steps：
(1) acidolysis：First nitric acid is added in reactive tank, regulation temperature keeps constant temperature after being 50~60 DEG C, and by rotating speed
After being adjusted to 200~300r/min, phosphorus mine tailing is added, rotating speed is then increased to by 450~550r/ with 10~20r/min speed
The mass ratio of min, nitric acid and phosphorus mine tailing is (2~3)：1, after reacting 1~3h, obtain reaction material liquid；
(2) filter, wash：Reaction material liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtained
Residue and washing lotion；
(3) decalcification：Acid hydrolysis solution is first preheated to temperature as 50~60 DEG C, the rotating speed of agitator is adjusted to 550~650r/
Min, ammonium sulfate is added into acid hydrolysis solution, the concentration for adjusting sulfate radical in solution is 15~25g/L, is adding ammonium sulfate
During, rotating speed is increased to by 700~900r/min with 10~20r/min speed, and temperature is increased to 70~80 DEG C,
After reacting 100~150min, reaction material liquid is filtered, filter residue and decalcifying Fluid is obtained, filter residue is washed, then carried out
Drying, obtains gypsum, and cleaning solution is returned in decalcification process；
(4) neutralize：Ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.2~6.5, and adjusts reaction temperature
Spend for 70~90 DEG C, after 500~700r/min 30~80min of rotating speed stirring reaction, stop heating and stirring, by reaction material
Liquid is filtered, and obtains neutralizer and filter residue, and filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate；
(5) it is granulated：By neutralizer use 100~150 DEG C of temperature be concentrated by evaporation to concentration for 94~97% fused solution
Afterwards, it is re-fed into rotary drum vulcanization bed and is granulated, produces ammonium nitrate magnesium.
Calcium oxide content is 30~45% in the phosphorus mine tailing, and content of magnesia is 11~20%, and phosphorus pentoxide contains
Measure as 5~12%.
Preferably, in the phosphorus mine tailing phosphorus pentoxide content be 5.5~6.6%, calcium oxide content be 33.4~
35.9%th, content of magnesia is 17.6~18.9%.
The concentration of the salpeter solution is 50~60%.
The concentration of the ammoniacal liquor is 25~28%.
The concentration of the ammonium sulfate is 30~40%.
In the step (1), it is used for the carbon dioxide of absorbing reaction generation using ammoniacal liquor, obtains sal volatile.
In the step (2), washing lotion is returned in hydrolysis procedure.
In the step (3), acid hydrolysis solution is first preheated to temperature as 55 DEG C, the rotating speed of agitator is adjusted to 600r/min,
Ammonium sulfate is added into acid hydrolysis solution, the concentration for adjusting sulfate radical in solution is 20g/L, is adding the process of ammonium sulfate
In, rotating speed is increased to by 800r/min with 15r/min speed, and temperature is increased to 75 DEG C, after reacting 120min, it will react
Feed liquid is filtered, and obtains filter residue and decalcifying Fluid, filter residue is washed, then dried, obtains gypsum, and cleaning solution is returned
Return in decalcification process.
In the step (3), washing is carried out in four times, preceding to be washed three times using cold water, and the cleaning solution of washing returns for the first time
Return in decalcification process, for the second time and third time uses countercurrent washing, and secondary cleaning solution is used to wash for the third time, the 4th time
Countercurrent washing is carried out using 60 DEG C of hot water.
In the step (4), ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.3, and adjusts reaction temperature
Spend for 80 DEG C, after 600r/min rotating speed stirring reaction 60min, stop heating and stirring, reaction material liquid is filtered, obtained
Neutralizer and filter residue, filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate.
In the step (5), by neutralizer use 120 DEG C of temperature be concentrated by evaporation to concentration for 96% fused solution after,
It is re-fed into rotary drum vulcanization bed and is granulated, produces ammonium nitrate magnesium.
The beneficial effects of the present invention are：
1st, the present invention prepares ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as primary raw material, effectively in phosphorus mine tailing
Phosphorus, calcium and magnesium are recycled, and have good economic benefit.Meanwhile this method can carry out mass disposal to phosphorus mine tailing,
The a large amount of soils for efficiently solving phosphorus mine tailing bulk deposition and bringing are occupied and the problems such as environmental pollution.
2nd, the present invention is advantageous to the abundant dissolving in phosphorus mine tailing, and pass through using phosphorus mine tailing is slowly added into nitric acid
The control of nitric acid and phosphorus mine tailing dosage and mixing speed, the control of reaction temperature, make phosphorus all be dissolved into acid hydrolysis solution, and adopt
The calcium in acid hydrolysis solution is removed with ammonium sulfate, it is ensured that the ammonium magnesium phosphate of subsequent production and the quality of ammonium nitrate magnesium, by acid hydrolysis solution
It is 62~6.5 to be neutralized to pH value, is advantageous to ammonium magnesium phosphate being first separated by filtration away so that phosphorus content in the ammonium magnesium phosphate of preparation
Greatly improve, the content of nitrogen and phosphorus is more than 40%, and the content of moderate-element magnesium and calcium is 15% or so, ammonium magnesium phosphate nutrition member
Cellulose content enriches, and reasonable mixture ratio, has preferable fertilizer efficiency.Nitrogen content is more than 25% in the ammonium nitrate magnesium of acquisition, nitrate nitrogen
For more than 14%, the content of moderate-element magnesium is 4% or so, is a kind of preferably production of compound fertilizer raw material.
3rd, the present invention in process of production, is recycled to waste residue and waste liquid, production greatly reduces
Cost, reduce outside sewage effluent and solid waste, there is significant environment protection significance.
4th, the filter residue after decalcification is carried out four washings by the present invention, and cold water washs three times before use, the 4th hot water wash
Wash, first time following current washing, after countercurrent washing three times mode, thoroughly the phosphorus in filter residue and the washing of magnesium useful element can be arrived
In washing lotion, and washing lotion is recycled, effectively prevent the loss of useful element, improve the comprehensive utilization to phosphorus mine tailing
Rate, further reduce manufacturing cost.
Below the effect of the present invention is verified to test：
Experimental raw：
Phosphorus mine tailing, salpeter solution, ammoniacal liquor.Wherein, in phosphorus mine tailing phosphorus pentoxide content be 5.64%, calcium oxide content be
33.87%th, content of magnesia 18.88%, iron oxide content 0.26%, alumina content 0.37%, Oil repellent are
0.52%；The concentration of salpeter solution is 55%；The purity of ammoniacal liquor is 25~28%, and the concentration of ammonium sulfate is 34%.
Experimental facilities：
Muffle furnace, electronic thermostatic agitator, stirring slurry, glass beaker, temperature adjustable electrically heated device, thermometer, bottle,suction, funnel with
And water ejector.
Experimental procedure：
1), take tetra- volumes of A, B, C and D be 1000mL beaker, sequentially added into four beakers 975g salpeter solutions,
1035g salpeter solutions, 1100g salpeter solutions and 1250g salpeter solutions, the rotating speed for adjusting agitator are 300r/min, then
500g phosphorus mine tailings are separately added into four beakers, feed time 75min, to ensure that foam does not spill over burning in the process
Cup, and rotating speed is gradually increased into 500r/min, after material warms naturally to 50 DEG C, regulation electric thermal power is kept the temperature at
50 DEG C, filtered and washed after material reaction 60min, obtain acid hydrolysis solution and acidolysis slag, determine its chemical composition, such as table 1：
Table 1
From experimental result as can be seen that with the increase of nitric acid dosage, the phosphorus remained in acidolysis slag reduces, when nitric acid is used
When amount reaches 1250g, phosphorus almost all is entered in acid hydrolysis solution.In addition, sour dosage is lower, the slurry of gained is more difficult to filter.By
More in bubble caused by phosphorus mine tailing, the nitrogen oxide taken out of is more, thus to extend feed time.
2), the acid hydrolysis solution of above-mentioned acquisition is mixed, then acid hydrolysis solution is preheated to temperature as 55 DEG C, the rotating speed of agitator is adjusted
For 600r/min, ammonium sulfate is added into acid hydrolysis solution, the concentration for adjusting sulfate radical in solution is 15g/L, is adding ammonium sulfate
During solution, rotating speed is increased into 800r/min, and temperature is increased to keep constant temperature after 70 DEG C, after reacting 120min,
Reaction material liquid is filtered and washed, gypsum and decalcifying Fluid is obtained, the composition of decalcifying Fluid and gypsum is detected, as a result such as
Under：
Table 2
From experimental result as can be seen that also containing a small amount of calcium in decalcifying Fluid, but calcium is as needed for growing process
Moderate-element, a small amount of calcium is present, and the nutrient of the ammonium phosphate fertiliser containing magnesium of subsequent production can be made more abundant.
3), the acid hydrolysis solution of above-mentioned acquisition is mixed, is added in beaker, starting agitator makes rotating speed be 600r/min, adopts
It is 6.2 to be neutralized to pH with ammoniacal liquor, separates out calcium monohydrogen phosphate and ammonium magnesium phosphate, adjusts electric thermal power, reaction temperature is maintained at 80
DEG C, continue to filter and wash after reacting 30min, after filter cake is dried, obtain ammonium magnesium phosphate, after filtrate concentration solidification, obtain nitric acid
Ammonium magnesium, the composition of ammonium magnesium phosphate and ammonium nitrate magnesium is detected, as a result such as table 3：
Table 3
| Phosphorus pentoxide (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Ammonium magnesium phosphate | 38.95 | 0.94 | 14.92 | 2.28 |
| Ammonium nitrate magnesium | 0.00 | 0.19 | 4.65 | 25.28 |
From the point of view of experimental result, phosphorus content greatly improves in ammonium magnesium phosphate, and the content of nitrogen and phosphorus is more than 40%, moderate-element
The content of magnesium and calcium is 15% or so, and nutritive element content enriches, and reasonable mixture ratio, has preferable fertilizer efficiency.The nitric acid of acquisition
Nitrogen content is more than 25% in ammonium magnesium, and nitrate nitrogen is more than 14%, moderate-element calcium, the content about 5% of magnesium, is a kind of preferable
Nitro contains fertiliser containing magnesium.
Embodiment
In order to facilitate the understanding of those skilled in the art, below in conjunction with embodiment, the present invention will be further described.
Embodiment is only for example, not being limitation of the invention, the step of not illustrated in embodiment to the invention
It is prior art, is not described in detail herein.
The present invention relates to main chemical reactions equation it is as follows：
Reaction equation one：
CaCO3·MgCO3+4HNO3→Ca(NO3)2+M(NO3)2+2H2O+2CO2
Reaction equation two：
10HNO3+Ca5F(PO4)3+SiO2→5Ca(NO3)2+3H3PO4+H2SiF6
Reaction equation three：
Ca(NO3)2+(NH4)2SO4+2H2O→CaSO4·2H2O+2NH4NO3
Reaction equation four：
Mg(NO3)2+H3PO4+3NH3+H2O→2NH4NO3+MgNH4PO4·H2O
Embodiment one
A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, comprises the following steps：
(1) acidolysis：First nitric acid is added in reactive tank, regulation temperature keeps constant temperature after being 50 DEG C, and rotating speed is adjusted to
After 200r/min, phosphorus mine tailing is added, rotating speed is then increased to by 450r/min with 10r/min speed, be used for inhaling using ammoniacal liquor
The mass ratio of the carbon dioxide of receipts reaction generation, acquisition sal volatile, nitric acid and phosphorus mine tailing is 2：1, after reacting 1h, obtain
Reaction material liquid；
(2) filter, wash：Reaction material liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtained
Residue and washing lotion, washing lotion is returned in hydrolysis procedure；
(3) decalcification：Acid hydrolysis solution is first preheated to temperature as 50 DEG C, the rotating speed of agitator is adjusted to 550r/min, to acidolysis
Ammonium sulfate is added in liquid, the concentration for adjusting sulfate radical in solution is 15g/L, during ammonium sulfate is added, with
Rotating speed is increased to 700r/min by 10r/min speed, and temperature is increased into 70 DEG C, after reacting 100min, by reaction material liquid
Filtered, obtain filter residue and decalcifying Fluid, filter residue is subjected to four washings, it is preceding to be washed three times using cold water, washing for the first time
Cleaning solution is returned in decalcification process, and for the second time and third time uses countercurrent washing, and secondary cleaning solution is used to wash for the third time
Wash, after the hot water progress countercurrent washing of the 4th 60 DEG C of use, filter residue and drying is obtained into gypsum；
(4) neutralize：Ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.2, and adjusts reaction temperature as 70
DEG C, after 500r/min rotating speed stirring reaction 30min, stop heating and stirring, reaction material liquid is filtered, obtains neutralizer
And filter residue, filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate；
(5) it is granulated：By neutralizer use 100 DEG C of temperature be concentrated by evaporation to concentration for 94% fused solution after, be re-fed into
It is granulated in rotary drum vulcanization bed, produces ammonium nitrate magnesium.
Calcium oxide content is 33.4% in the phosphorus mine tailing, content of magnesia 17.6%, and the content of phosphorus pentoxide is
5.5%；The concentration of salpeter solution is 50%；The concentration of ammoniacal liquor is 25%；The concentration of ammonium sulfate is 30%.
The ammonium magnesium phosphate and the composition of ammonium nitrate magnesium obtained in the technique is detected, as a result such as following table：
Table 4
| Phosphorus pentoxide (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Ammonium magnesium phosphate | 39.01 | 1.03 | 14.32 | 1.73 |
| Ammonium nitrate magnesium | 0.00 | 0.32 | 4.63 | 25.16 |
Embodiment two
A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, comprises the following steps：
(1) acidolysis：First nitric acid is added in reactive tank, regulation temperature keeps constant temperature after being 60 DEG C, and rotating speed is adjusted to
After 300r/min, phosphorus mine tailing is added, rotating speed is then increased to by 550r/min with 20r/min speed, be used for inhaling using ammoniacal liquor
The mass ratio of the carbon dioxide of receipts reaction generation, acquisition sal volatile, nitric acid and phosphorus mine tailing is 3：1, after reacting 3h, obtain
Reaction material liquid；
(2) filter, wash：Reaction material liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtained
Residue and washing lotion, washing lotion is returned in hydrolysis procedure；
(3) decalcification：Acid hydrolysis solution is first preheated to temperature as 60 DEG C, the rotating speed of agitator is adjusted to 650r/min, to acidolysis
Ammonium sulfate is added in liquid, the concentration for adjusting sulfate radical in solution is 25g/L, during ammonium sulfate is added, with
Rotating speed is increased to 900r/min by 20r/min speed, and temperature is increased into 80 DEG C, after reacting 150min, by reaction material liquid
Filtered, obtain filter residue and decalcifying Fluid, filter residue is subjected to four washings, it is preceding to be washed three times using cold water, washing for the first time
Cleaning solution is returned in decalcification process, and for the second time and third time uses countercurrent washing, and secondary cleaning solution is used to wash for the third time
Wash, after the hot water progress countercurrent washing of the 4th 60 DEG C of use, filter residue and drying is obtained into gypsum；
(4) neutralize：Ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.5, and adjusts reaction temperature as 90
DEG C, after 700r/min rotating speed stirring reaction 80min, stop heating and stirring, reaction material liquid is filtered, obtains neutralizer
And filter residue, filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate；
(5) it is granulated：By neutralizer use 150 DEG C of temperature be concentrated by evaporation to concentration for 97% fused solution after, be re-fed into
It is granulated in rotary drum vulcanization bed, produces ammonium nitrate magnesium.
In the phosphorus mine tailing phosphorus pentoxide content be 5.64%, calcium oxide content 33.87%, content of magnesia be
18.88%；The concentration of salpeter solution is 60%；The concentration of ammoniacal liquor is 28%；The concentration of ammonium sulfate is 40%.
The ammonium magnesium phosphate and the composition of ammonium nitrate magnesium obtained in the technique is detected, as a result such as following table：
Table 5
| Phosphorus pentoxide (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Ammonium magnesium phosphate | 38.36 | 0.79 | 14.90 | 2.84 |
| Ammonium nitrate magnesium | 0.00 | 0.15 | 4.17 | 25.88 |
Embodiment three
A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, comprises the following steps：
(1) acidolysis：First nitric acid is added in reactive tank, regulation temperature keeps constant temperature after being 55 DEG C, and rotating speed is adjusted to
After 250r/min, phosphorus mine tailing is added, rotating speed is then increased to by 500r/min with 15r/min speed, be used for inhaling using ammoniacal liquor
The mass ratio of the carbon dioxide of receipts reaction generation, acquisition sal volatile, nitric acid and phosphorus mine tailing is 2.5：1, after reacting 2h,
Obtain reaction material liquid；
(2) filter, wash：Reaction material liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtained
Residue and washing lotion, washing lotion is returned in hydrolysis procedure；
(3) decalcification：Acid hydrolysis solution is first preheated to temperature as 55 DEG C, the rotating speed of agitator is adjusted to 600r/min, to acidolysis
Ammonium sulfate is added in liquid, the concentration for adjusting sulfate radical in solution is 20g/L, during ammonium sulfate is added, with
Rotating speed is increased to 800r/min by 15r/min speed, and temperature is increased into 75 DEG C, after reacting 120min, by reaction material liquid
Filtered, obtain filter residue and decalcifying Fluid, filter residue is subjected to four washings, it is preceding to be washed three times using cold water, washing for the first time
Cleaning solution is returned in decalcification process, and for the second time and third time uses countercurrent washing, and secondary cleaning solution is used to wash for the third time
Wash, after the hot water progress countercurrent washing of the 4th 60 DEG C of use, filter residue and drying is obtained into gypsum；
(4) neutralize：Ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.3, and adjusts reaction temperature as 75
DEG C, after 600r/min rotating speed stirring reaction 50min, stop heating and stirring, reaction material liquid is filtered, obtains neutralizer
And filter residue, filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate；
(5) it is granulated：By neutralizer use 120 DEG C of temperature be concentrated by evaporation to concentration for 96% fused solution after, be re-fed into
It is granulated in rotary drum vulcanization bed, produces ammonium nitrate magnesium.
In the phosphorus mine tailing phosphorus pentoxide content be 5.64%, calcium oxide content 33.87%, content of magnesia be
18.88%；The concentration of salpeter solution is 55%；The concentration of ammoniacal liquor is 26%；The concentration of ammonium sulfate is 34%.
The ammonium magnesium phosphate and the composition of ammonium nitrate magnesium obtained in the technique is detected, as a result such as following table：
Table 6
| Phosphorus pentoxide (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Ammonium magnesium phosphate | 38.46 | 0.89 | 14.46 | 2.08 |
| Ammonium nitrate magnesium | 0.00 | 0.24 | 4.34 | 25.31 |
Example IV
A kind of method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, comprises the following steps：
(1) acidolysis：First nitric acid is added in reactive tank, regulation temperature keeps constant temperature after being 58 DEG C, and rotating speed is adjusted to
After 280r/min, phosphorus mine tailing is added, rotating speed is then increased to by 480r/min with 12r/min speed, be used for inhaling using ammoniacal liquor
The mass ratio of the carbon dioxide of receipts reaction generation, acquisition sal volatile, nitric acid and phosphorus mine tailing is 2.6：1, react 2.5h
Afterwards, reaction material liquid is obtained；
(2) filter, wash：Reaction material liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtained
Residue and washing lotion, washing lotion is returned in hydrolysis procedure；
(3) decalcification：Acid hydrolysis solution is first preheated to temperature as 52 DEG C, the rotating speed of agitator is adjusted to 620r/min, to acidolysis
Ammonium sulfate is added in liquid, the concentration for adjusting sulfate radical in solution is 18g/L, during ammonium sulfate is added, with
Rotating speed is increased to 750r/min by 16r/min speed, and temperature is increased into 72 DEG C, after reacting 130min, by reaction material liquid
Filtered, obtain filter residue and decalcifying Fluid, filter residue is subjected to four washings, it is preceding to be washed three times using cold water, washing for the first time
Cleaning solution is returned in decalcification process, and for the second time and third time uses countercurrent washing, and secondary cleaning solution is used to wash for the third time
Wash, after the hot water progress countercurrent washing of the 4th 60 DEG C of use, filter residue and drying is obtained into gypsum；
(4) neutralize：Ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.4, and adjusts reaction temperature as 76
DEG C, after 600r/min rotating speed stirring reaction 60min, stop heating and stirring, reaction material liquid is filtered, obtains neutralizer
And filter residue, filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate；
(5) it is granulated：By neutralizer use 110 DEG C of temperature be concentrated by evaporation to concentration for 95% fused solution after, be re-fed into
It is granulated in rotary drum vulcanization bed, produces ammonium nitrate magnesium.
In the phosphorus mine tailing phosphorus pentoxide content be 6.64%, calcium oxide content 35.87%, content of magnesia be
18.88%；The concentration of salpeter solution is 55%；The concentration of ammoniacal liquor is 26%；The concentration of ammonium sulfate is 34%.
The ammonium magnesium phosphate and the composition of ammonium nitrate magnesium obtained in the technique is detected, as a result such as following table：
Table 7
| Phosphorus pentoxide (%) | Calcium (%) | Magnesium (%) | Nitrogen (%) | |
| Ammonium magnesium phosphate | 38.52 | 0.86 | 14.27 | 2.16 |
| Ammonium nitrate magnesium | 0.00 | 0.23 | 4.26 | 25.42 |
It is described above, only it is the preferable example of the present invention, any formal limitation not is made to the present invention, it is any not take off
From technical solution of the present invention content, any simple modification made according to technical spirit of the invention to above example, conversion material
Equivalent variations and modification are expected, in the range of still falling within technical solution of the present invention.
Claims (8)
- A kind of 1. method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing, it is characterised in that comprise the following steps：(1) acidolysis：First nitric acid is added in reactive tank, regulation temperature keeps constant temperature after being 50~60 DEG C, and rotating speed is adjusted to After 200~300r/min, phosphorus mine tailing is added, rotating speed is then increased to by 450~550r/min with 10~20r/min speed, The mass ratio of nitric acid and phosphorus mine tailing is (2~3)：1, after reacting 1~3h, obtain reaction material liquid；(2) filter, wash：Reaction material liquid is filtered, obtains acid hydrolysis solution and acidolysis slag, acidolysis slag is washed, obtains residue And washing lotion；(3) decalcification：Acid hydrolysis solution is first preheated to temperature as 50~60 DEG C, the rotating speed of agitator is adjusted to 550~650r/min, to Ammonium sulfate is added in acid hydrolysis solution, the concentration for adjusting sulfate radical in solution is 15~25g/L, is adding the process of ammonium sulfate In, rotating speed is increased to by 700~900r/min with 10~20r/min speed, and temperature is increased to 70~80 DEG C, reaction After 100~150min, reaction material liquid is filtered, filter residue and decalcifying Fluid is obtained, filter residue is washed, then dried Gypsum is obtained, and cleaning solution is returned in decalcification process；(4) neutralize：Ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.2~6.5, and adjusts reaction temperature and be 70~90 DEG C, after 500~700r/min 30~80min of rotating speed stirring reaction, stop heating and stirring, reaction material liquid is entered Row filtering, obtains neutralizer and filter residue, and filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate；(5) it is granulated：By neutralizer use 100~150 DEG C of temperature be concentrated by evaporation to concentration for 94~97% fused solution after, then It is sent into rotary drum vulcanization bed and is granulated, produces ammonium nitrate magnesium；The concentration of the salpeter solution is 50~60%；Calcium oxide content is 30~45% in the phosphorus mine tailing, and content of magnesia is 11~20%,The content of phosphorus pentoxide is 5~12%.
- 2. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described The concentration of ammoniacal liquor is 25~28%.
- 3. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described The concentration of ammonium sulfate is 30~40%.
- 4. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described In step (1), it is used for the carbon dioxide of absorbing reaction generation using ammoniacal liquor, obtains sal volatile.
- 5. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described In step (2), washing lotion is returned in hydrolysis procedure.
- 6. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described In step (3), acid hydrolysis solution is first preheated to temperature as 55 DEG C, the rotating speed of agitator is adjusted to 600r/min, is added into acid hydrolysis solution Enter ammonium sulfate, the concentration for adjusting sulfate radical in solution is 20g/L, during ammonium sulfate is added, with 15r/min's Rotating speed is increased to 800r/min by speed, and temperature is increased into 75 DEG C, and after reacting 120min, reaction material liquid is filtered, Filter residue and decalcifying Fluid are obtained, filter residue is washed, then dried, obtains gypsum, and cleaning solution is returned into decalcification process In.
- 7. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described In step (4), ammoniacal liquor is added in decalcifying Fluid, the pH value for adjusting mixed liquor is 6.3, and adjusts reaction temperature as 80 DEG C, with After 600r/min rotating speed stirring reaction 60min, stop heating and stirring, reaction material liquid is filtered, obtains neutralizer and filter Slag, filter residue is sent into rotary drum vulcanization bed and is granulated, obtains ammonium magnesium phosphate.
- 8. the method for preparing ammonium magnesium phosphate and ammonium nitrate magnesium using phosphorus mine tailing as claimed in claim 1, it is characterised in that described In step (5), by neutralizer use 120 DEG C of temperature be concentrated by evaporation to concentration for 96% fused solution after, be re-fed into rotary drum sulphur Change and be granulated in bed, produce ammonium nitrate magnesium.
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| CN107879363A (en) * | 2017-11-06 | 2018-04-06 | 湖北三宁化工股份有限公司 | A kind of method that nitric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate by-product magnesium hydroxide and ammonium nitrate magnesium |
| CN110817911B (en) * | 2019-11-08 | 2020-10-30 | 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 |
| CN110697674B (en) * | 2019-12-03 | 2021-03-30 | 中化重庆涪陵化工有限公司 | Method for producing magnesium ammonium phosphate by using 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 |
| CN111451004B (en) * | 2020-04-20 | 2022-03-15 | 武汉工程大学 | Method for producing phosphate concentrate and by-producing alpha-semi-hydrated 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 |
| 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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| US3761239A (en) * | 1971-11-24 | 1973-09-25 | C Cook | Process for producing land fill compositions |
| DE2813358C2 (en) * | 1978-03-28 | 1984-05-10 | Uhde Gmbh, 4600 Dortmund | Process for processing a magnesium-containing rock phosphate into phosphoric acid and a magnesium carbonate-calcium carbonate mixture |
| CN102417169B (en) * | 2011-08-15 | 2013-11-20 | 武善东 | Acidolysis method of magnesium-containing phosphate rock |
| CN102992284B (en) * | 2012-12-12 | 2014-10-29 | 贵州开磷（集团）有限责任公司 | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate |
| CN103922372B (en) * | 2014-04-11 | 2016-04-13 | 武汉工程大学 | Indirect sulfuric acid process reclaims phosphorus in High-Mg phosphate tailings and prepares the method for magnesium sulfate |
| CN104401956A (en) * | 2014-10-14 | 2015-03-11 | 安徽六国化工股份有限公司 | Method for producing magnesium ammonium phosphate from high-magnesium phosphorite powder extraction waste liquid |
| CN104326771B (en) * | 2014-10-22 | 2016-08-31 | 瓮福（集团）有限责任公司 | A kind of method utilizing phosphorus mine tailing to prepare calcium nitrate fertiliser containing magnesium |
| CN104445299A (en) * | 2014-10-30 | 2015-03-25 | 瓮福（集团）有限责任公司 | Method for preparing high-purity magnesium hydroxide |
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