CN104860334B - A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium - Google Patents
A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium Download PDFInfo
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Abstract
The present invention relates to mid low grade phosphate rock preconditioning technique field, especially a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, first choice is by calcining digestion process, calcium carbonate and magnesium carbonate is set fully to decompose, deviate from, then the compound leaching mode of ammonium nitrate solution and salpeter solution, and the further leaching of ammonium sulfate is taken to handle so that magnesium elements are sufficiently leached, ionic state is showed in the solution and then is separated, and improves phosphorus ore quality；And during the waste liquid, the waste gas recovery that produce, solvent after processing is recycled, subsequent treatment is carried out to filtrate while high-quality phosphorus ore is obtained, obtain calcium carbonate and magnesia, effective recycling has not only been carried out to calcium magnesium element, waste liquid, the discharge of waste gas and the accumulation of mine tailing are also avoid, is conducive to the improvement of ecological environment.
Description
Technical field
The present invention relates to phosphate ore processing processing technology field, more particularly to a kind of raising mid low grade phosphate rock quality and recovery
The processing method of calcium and magnesium.
Background technology
China's phosphorus ore reserves occupy second place of the world, but reserves 80% or so is mid low grade phosphate rock, wherein how difficult choosing
Mid-low grade collophanite ore, mineral grain is thin, embedding cloth is close, and the impurity such as association magnesium is higher, and it can reduce the grade of rock phosphate in powder, increases
The quality of sulfuric acid consumption during big phosphorus ore wet-treating, influence phosphoric acid and phosphate deep processing and product.It is low in tradition
After the phosphorus ore of grade is pre-processed, then the production of next step product is carried out, containing for the impurity such as magnesium in phosphorus ore is reduced with this
Amount, and then the purpose of purifying phosphorus ore is reached, improve the quality of phosphorus ore, reduction is follow-up to utilize phosphorus ore to phosphorus ore or phosphoric acid by wet process
Difficulty and energy consumption；The ore dressing especially carbonate mine of current China phosphorus ore is mainly using methods such as flotation, reverse flotations, it is difficult to will
MgO content drops to less than 1%, and P2O5Loss more than 5%.Wherein tail is discharged through a reverse flotation and simple clean
Ore deposit contains P2O5≤ 15%, MgO >=10%；Through secondary reverse flotation discharge mine tailing P2O5≤ 10%, MgO >=15%.Therefore, it is conventional
Not only phosphorus loss is big for beneficiation method, and the most heaps of its mine tailing are stored in Tailings Dam, there is larger environmental risk.
In the prior art, the research of electroplating effluent recycling phosphorus ore is more with sulfuric acid process, although a certain degree of can solve
Partial impurities in phosphorus ore so that the quality of phosphorus ore is improved, but it is because sulfuric acid is using the life of the raw materials such as sulphur
Production, and the market price of sulphur is costly, and after sulfur acid pretreatment phosphorus ore, it will the substantial amounts of ardealite of generation, and phosphorus
Gypsum, which is emitted in natural environment, will cause the severe contamination of environment, and the quality of the phosphorus ore after sulfur acid pretreatment is improved still
It is limited；And in processing procedure, after calcium sulfate formation micro-soluble material, sulfuric acid is difficult to return and recycle, and then
Cause the cost in phosphorus ore preprocessing process is carried out larger.CN85107209 discloses a kind of low grade calcareous phosphorous ore chemistry point
From method, after phosphorus ore is calcined using ammonium chloride and ammonium nitrate mixing leaching by the way of separating magnesium, for improve low-grade phosphate ore product
Matter and by-product recovery, which are utilized, provides a kind of processing mode, but in engineer applied, due to the chlorion in ammonium chloride
And nitrate anion can corrode to stainless steel equipment, it is difficult to the processing of a large amount of and continuation is carried out, so to the material of equipment
Have high requirements, and can not be applied to extensively with economic in the production of actual industrial metaplasia.
Therefore, this researcher carries out analysis and discussion by the form existed to magnesium elements in phosphorus ore, and to traditional
The technique of phosphorus ore pretreatment is compared, and is combined processing using ammonium nitrate and salpeter solution, then phosphorus ore is entered with ammonium sulfate
The processing of one step de-magging, so as to improve the quality of phosphorus ore, improves the quality of phosphorus ore.At present for using the compound leaching of ammonium nitrate and nitric acid
Raising mid low grade phosphate rock quality, and the processing method of effectively recovery calcium and magnesium is taken to yet there are no document report, this is middle-low grade
The de-magging pretreatment of phosphorus ore and recovery calcium and magnesium, increase added value of product provide a kind of new approaches.
The content of the invention
The present invention provides a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, its step of preparation process
Simply, the treatment fluid of consumption can be recycled, no waste gas, waste liquid, the discharge of waste residue, and can aoxidize two by the five of phosphorus ore
The content of phosphorus brings up to more than 38%, content of magnesium in phosphorus ore fine powder is reduced into≤0.5%, so as to improve mid low grade phosphate rock
Quality, reduces follow-up phosphorus ore and carries out additional processing cost and the difficulty such as phosphoric acid by wet process, while obtaining magnesia and calcium carbonate product, carry
The added value that high mid low grade phosphate rock is utilized.
Concrete technical scheme is as follows：
A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, comprises the following steps：By middle-low grade
Phosphorus ore high-temperature calcination, hot water digestion；Postdigestive slurry adds ammonium nitrate solution and salpeter solution, and stirring leaching is separated, obtained
Ammonium nitrate leached mud and ammonium nitrate leachate；Ammonium nitrate leached mud is stirred with ammonium sulfate and leached, the mixed liquor after leaching
Separation, obtains filter residue and ammonium sulfate leaching liquid, and filter residue drying produces low magnesium phosphorus concentrate；The carbon dioxide produced and leaching will be calcined
The ammonia produced during taking is handled using water absorption, is obtained sal volatile, is then mixed with ammonium sulfate leaching liquid, and stirring is anti-
Should after separate, filter cake drying after calcine, produce magnesia；Ammonium nitrate leachate is mixed with sal volatile, is divided after stirring reaction
From filter cake drying produces calcium carbonate.
Further, a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, comprises the following steps：
(1) calcining digestion：Mid low grade phosphate rock is placed in calcining furnace, high-temperature calcination, hot water digestion；
(2) ammonium nitrate leaches：Phosphorus ore after calcining is placed in leaching groove, the ammonium nitrate that concentration is 10%-50% is added
The salpeter solution of solution and 5%-90%, stirring leaching；
(3) separate：Slurry after step (2) leaching is handled is filtered, washed, and obtains leached mud and leachate；
(4) ammonium sulfate leaches：Leached mud is stirred with 10-40% ammonium sulfate and leached；Mixed liquor mistake after leaching
Filter, washing, obtain filter residue and ammonium sulfate leaching liquid；Filter residue is dried, and obtains low magnesium phosphorus concentrate；
(5) absorb：Step (1) is calcined into the carbon dioxide produced and the ammonia produced in step (2), (4) leaching process
It is passed into absorption tower, is handled using water absorption, obtains sal volatile；
(6) sal volatile for obtaining step (5) is mixed with the ammonium sulfate leaching liquid that step (4) is obtained, stirring reaction,
Return in ammonium sulfate leaching step and recycle after reacting liquid filtering, washing, filtrate and cleaning solution mixing；Forged after filter cake drying
Burn, produce magnesia；
(7) leachate for obtaining step (3) adds the sal volatile that concentration is 10-35%, stirring reaction；After reaction
Mixed liquor filtering, washing, filtrate and cleaning solution mixing after return ammonium nitrate leaching step in recycle；Filter cake after leaching
Drying, produces calcium carbonate.
A kind of foregoing raising mid low grade phosphate rock quality and the processing method of recovery calcium and magnesium, wherein：
In the step (2) consumption of ammonium nitrate be according to every 100g phosphorus ores add 80-120g (folding 100% ammonium nitrate, under
Together), the addition of salpeter solution is to add 2-15g (100% nitric acid of folding, similarly hereinafter) according to every 100g phosphorus ores, in 60-85 DEG C of temperature
The lower stirring leaching 50-80min of degree.
In the step (4) ammonium sulfate consumption be according to every 100g phosphorus ores add 80-100g (folding 100% ammonium sulfate, under
Together), the stirring leaching 50-70min at a temperature of 80-90 DEG C.
In the step (6) consumption of ammonium carbonate be according to every 100g phosphorus ores add 100-125g (folding 100% ammonium carbonate,
Similarly hereinafter), the stirring reaction 50-70min at a temperature of 50-80 DEG C.
First adjustment concentration is 10-35% to sal volatile in the step (6) before the reaction.
In the step (7) consumption of ammonium carbonate be according to every 100g phosphorus ores add 100-150g (folding 100% ammonium carbonate,
Similarly hereinafter), the stirring reaction 50-70min at a temperature of 50-80 DEG C.
Step (1) the high temperature calcination processing temperature is 900-1100 DEG C, and the time is 0.5-1.5h；In water digestion process
Hot water temperature is 60-80 DEG C, and the consumption of water is to use 40-60ml water per 100g phosphorus ores.
Stirring in the step (2), (4), (6), (7) is treated substance is fully suspended in treatment fluid.
Washing in the step (3), (4), (6), (7) is to precipitate using the washing per 100g phosphorus ores 20-40ml
Wash.
It in temperature is 100-120 DEG C of drying >=1h that drying in the step (4), (6), (7), which is,.
In the scheme of the compound leaching mid low grade phosphate rock of above-mentioned utilization ammonium nitrate solution and salpeter solution, it can take nitre
Acid ammonium solution is charged first in phosphorus ore, and salpeter solution is added thereto by Rangu again；Or enter salpeter solution and ammonium nitrate solution
After row mixing, then add it in phosphorus ore and leached；, can be by the way of stirring while adding in adition process
Add, it would however also be possible to employ add and be stirred again after completing.
Compared with prior art, the present invention has the advantages that：
(1) present invention is preferred accelerates the decomposable process of calcium carbonate and magnesium carbonate by calcining digestion process, molten in conjunction with ammonium nitrate
The combined-circulation leaching mode of liquid and salpeter solution, and the further leaching of ammonium sulfate are handled, and magnesium elements is largely isolated
In phosphorus ore, and then phosphorus concentrate is obtained, make P2O5Content up to more than 38%, content of magnesium is reduced to≤0.5%, so as to carry high, normal, basic
The quality of grade phosphorus mine；
(2) present invention is absorbed to the ammonia of output in the waste gas and leaching process that are produced in calcination process,
Filtrate and cleaning solution after ammonium carbonate is handled in addition are recycled, it is to avoid waste liquid, the discharge of waste gas, are greatly protected
Environment, adapts to the development need of ecological environment from now on；
(3) it will leach and obtain the follow-up processing of the filtrate progress after high-quality phosphorus ore, and obtain calcium carbonate and magnesia, not only
Effective recycling is carried out to calcium magnesium element, moreover it is possible to greatly reduce the accumulation of phosphorite tailings, not only improve resource regeneration, carry
The added value of high product, is conducive to environmental protection again；
(4) the process step of the invention is simple, and raw material especially leaching agent, which can be partially recovered, to be recycled, and is reduced
The cost of pretreatment；And there is no the discharge of waste gas, waste liquid, waste residue in processing procedure, improve the technical merit of whole technique；
(5) present invention substitutes traditional sulfuric acid treating processes using the compound leaching of ammonium nitrate and nitric acid, reduces ardealite
Discharge capacity, it is to avoid a large amount of of ardealite store up the pollution brought to environment, with the significant value of environmental protection and economic benefit.
Technical scheme is further elaborated using experiment below, to prove the effect of the present invention.
The mid low grade phosphate rock in selection Guizhou Wengan area is examined as experimental raw, and to every composition in phosphorus ore
Survey, draw raw material phosphorus ore as shown in table 1：
Table 1
| Composition | P2O5 | CaO | MgO | Fe2O3 | Al2O3 | F | AI | Burn and lose |
| % | 26.87 | 46.53 | 6.23 | 0.26 | 0.32 | 2.61 | 5.3 | 15.5 |
The technical study of test example 1
1.1 calcining digestion
By the calcining of mid low grade phosphate rock powder, digestion, occur following react：
CaCO3·MgCO3→CaO+MgO+2CO2
CaO+MgO+4H2O→Ca(OH)2+Mg(OH)2
The calcination processing 0.5-1.5h at a temperature of 900-1100 DEG C, it is ensured that the abundant decomposition of calcium carbonate and magnesium carbonate.
The compound leaching of 1.2 ammonium nitrate, nitric acid
Take 100g phosphorus ores respectively, carry out after calcining digestion process, investigate respectively different ammonium nitrate consumption (80g, 100g,
120g, 140g), concentration (10%, 25%, 40%, 50%, 60%), leaching temperature (20-30 DEG C, 60-85 DEG C, 85-90 DEG C),
Leaching time (30min, 60min, 90min, 120min), concentration of nitric acid (5%, 25%, 50%, 75%, 90%), consumption (2g,
8g, 12g, 14g, 15g) etc. factor to P2O5The influence of content, investigates result and shows, the consumption of selection ammonium nitrate is according to every
100g phosphorus ores add 80-120g, concentration 10%-50%, the addition of salpeter solution be according to every 100g phosphorus ores add 2-15g,
Concentration 5%-90%, leaches 0.5-1.5h, 60-85 DEG C of leaching temperature, P2O5Content improves about 10 percentage points.It is preferred that nitric acid
The consumption of ammonium is to add 100g, concentration 25% according to every 100g phosphorus ores, and the addition of salpeter solution is to add according to every 100g phosphorus ores
Enter 5g, concentration 65%, leach 1.0h, 75 DEG C of leaching temperature.
The leaching of 1.3 ammonium sulfate obtains phosphorus concentrate
The leached mud 50g after the compound leaching of ammonium nitrate, nitric acid is taken, then magnesium is leached with ammonium sulfate, ammonium sulfate consumption is respectively
60th, 80,100,120g is tested, and is as a result shown, the influence of calcium leaching rate is little, but the leaching rate of magnesium is dramatically increased, preferably sulphur
Sour ammonium consumption is 80-100g, and the total leaching rate of magnesium is 100g up to 98.5-99.3%, more preferably consumption.
The process certification of test example 2
Phosphorus ore 1kg is taken respectively, is handled according to 1-3 of embodiment of the present invention method, then to five oxidations in phosphorus concentrate
The content of two phosphorus and the content of magnesia are detected, are drawn：The content of phosphorus pentoxide is 38.2-39.4%, magnesia
Content is 0.26-0.31%；It can be seen that, the technical scheme in the invention enables to the phosphorus pentoxide in the phosphorus ore of middle-low grade
Content improve about 10-12 percentage points, content of magnesium in phosphorus ore can be reduced to≤0.5%, and then reach low product in improvement
The quality of position phosphorus ore, the follow-up difficulty and cost that advanced treating is carried out to phosphorus ore of reduction；Reduce the waste residue of phosphorus ore advanced treating
Discharge rate, is effectively protected environment.
Also, calcium carbonate content is 92.5% in the residue after subsequently heavy calcium, magnesium sinking processing, and content of magnesia is
95.3%, following process processing can be carried out to it, improve value-added content of product after phosphorus ore pretreatment.
In addition, being tested by carrying out the technique under laboratory condition to other regional phosphorus ores such as Fuquan area, Kaiyang Region
Card, as a result shows that technical scheme is equally applicable to the pretreatment of above-mentioned regional phosphorus ore.
Brief description of the drawings
Fig. 1 improves mid low grade phosphate rock quality for the present invention and reclaims the process chart of the processing method of calcium and magnesium.
Embodiment：
Technical scheme is described further with specific embodiment below in conjunction with the accompanying drawings, but required
The scope of protection is not only limited to made description
Embodiment 1
A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, comprises the following steps：
(1) calcining digestion：Mid low grade phosphate rock is placed in calcining furnace, the calcination processing 1.0h at a temperature of 950 DEG C, then
Enter water-filling digestion process；Described water digestion process is carried out using 65 DEG C of hot water, and the consumption of water is to be used per 100g phosphorus ores
50ml water；
(2) ammonium nitrate leaches：The phosphorus ore that digestion process is completed is placed in leaching groove, then adds the nitre that concentration is 25%
Acid ammonium solution and 65% salpeter solution, stir process 60min at a temperature of 75 DEG C；The consumption of ammonium nitrate is according to every 100g phosphorus
Ore deposit adds 100g, and the addition of salpeter solution is to add 12g according to every 100g phosphorus ores；
(3) separate：Slurry after step (2) leaching is handled is filtered, washed, and obtains leached mud and leachate；
(4) ammonium sulfate leaches：Leached mud is leached into 60min with 25% ammonium sulfate stirring, leaching temperature is 85 DEG C；
Mixed liquor filtering, washing after leaching, obtain filter residue and ammonium sulfate leaching liquid；Filter residue is obtained using 110 DEG C of temperature baking 1h
Low magnesium phosphorus concentrate；Ammonium sulfate consumption is to add 100g according to every 100g phosphorus ores；
(5) absorb：Step (1) is calcined into the carbon dioxide produced and the ammonia produced in step (2), (4) leaching process
It is passed into absorption tower, is handled using water absorption, obtains sal volatile；
(6) the sal volatile adjustment concentration obtained step (5) is 30%, is leached with the ammonium sulfate that step (4) is obtained
Liquid is mixed, stirring reaction 60min, and reaction temperature is 60 DEG C, reacting liquid filtering, washing, and sulphur is returned after filtrate and cleaning solution mixing
Recycled in sour ammonium leaching step；Calcined after filter cake drying under the conditions of 900 DEG C, produce magnesia；The consumption of ammonium carbonate is
125g is added according to every 100g phosphorus ores；
(7) leachate for obtaining step (3) adds the sal volatile that concentration is 30%, stirring reaction 60min, reaction
Temperature is 60 DEG C；Return in leaching step and circulate after reacted mixed liquor filtering, washing, ammonium nitrate filtrate and cleaning solution mixing
Use；Filter cake drying after leaching, produces calcium carbonate, and the consumption of ammonium carbonate is to add 150g according to every 100g phosphorus ores.
Stirring in the step (2), (4), (6), (7) is treated substance is fully suspended in treatment fluid.
Washing in the step (3), (4), (6), (7) is to precipitate using the washing per 100g phosphorus ores 20-40ml
Wash.
Filter cake drying temperature in the step (6), (7) is 110 DEG C, drying and processing time >=1h.
Result：P in phosphorus concentrate2O5Content 38.9%, content of magnesium 0.27%.
Embodiment 2
A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, comprises the following steps：
(1) calcining digestion：Mid low grade phosphate rock is placed in calcining furnace, the calcination processing 0.5h at a temperature of 1100 DEG C,
Enter water-filling digestion process again；Described water digestion process is carried out using 70 DEG C of hot water, and the consumption of water is to be used per 100g phosphorus ores
40ml water；
(2) ammonium nitrate leaches：The phosphorus ore that digestion process is completed is placed in leaching groove, then adds the nitre that concentration is 10%
Acid ammonium solution and 5% salpeter solution, stir process 50min at a temperature of 85 DEG C；The consumption of ammonium nitrate is according to every 100g phosphorus
Ore deposit adds 80g, and the addition of salpeter solution is to add 5g according to every 100g phosphorus ores；
(3) separate：Slurry after step (2) leaching is handled is filtered, washed, and obtains leached mud and leachate；
(4) ammonium sulfate leaches：Leached mud is leached into 70min with 10% ammonium sulfate stirring, leaching temperature is 80 DEG C；
Mixed liquor filtering, washing after leaching, obtain filter residue and ammonium sulfate leaching liquid；Filter residue uses 110 DEG C of temperature baking >=1h, obtains
Obtain low magnesium phosphorus concentrate；Ammonium sulfate consumption is to add 80g according to every 100g phosphorus ores；
(5) absorb：Step (1) is calcined into the carbon dioxide produced and the ammonia produced in step (2), (4) leaching process
It is passed into absorption tower, is handled using water absorption, obtains sal volatile；
(6) the sal volatile adjustment concentration obtained step (5) is 10%, is leached with the ammonium sulfate that step (4) is obtained
Liquid is mixed, stirring reaction 70min, and reaction temperature is 50 DEG C, reacting liquid filtering, washing, and sulphur is returned after filtrate and cleaning solution mixing
Recycled in sour ammonium leaching step；Calcined after filter cake drying under the conditions of 850 DEG C, produce magnesia, the consumption of ammonium carbonate is
100g is added according to every 100g phosphorus ores；
(7) leachate for obtaining step (3) adds the sal volatile that concentration is 10%, stirring reaction 70min, reaction
Temperature is 50 DEG C；Return in leaching step and circulate after reacted mixed liquor filtering, washing, ammonium nitrate filtrate and cleaning solution mixing
Use；Filter cake drying after leaching, produces calcium carbonate, and the consumption of ammonium carbonate is to add 100g according to every 100g phosphorus ores.
Stirring in the step (2), (4), (6), (7) is treated substance is fully suspended in treatment fluid.
Washing in the step (3), (4), (6), (7) is to precipitate using the washing per 100g phosphorus ores 20-40ml
Wash.
Filter cake drying temperature in the step (6), (7) is 110 DEG C, drying and processing time >=1h.
Result：P in phosphorus concentrate2O5Content 38.2%, content of magnesium 0.31%.
Embodiment 3
A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, comprises the following steps：
(1) calcining digestion：Mid low grade phosphate rock is placed in calcining furnace, the calcination processing 1.5h at a temperature of 900 DEG C, then
Enter water-filling digestion process, the water digestion process is carried out using 60 DEG C of hot water, and the consumption of water is to use 55ml per 100g phosphorus ores
Water；
(2) ammonium nitrate leaches：The phosphorus ore that digestion process is completed is placed in leaching groove, then adds the nitre that concentration is 50%
Acid ammonium solution and 95% salpeter solution, stir process 80min at a temperature of 60 DEG C；The consumption of ammonium nitrate is according to every 100g phosphorus
Ore deposit adds 120g, and the addition of salpeter solution is to add 12g according to every 100g phosphorus ores；
(3) separate：Slurry after step (2) leaching is handled is filtered, washed, and obtains leached mud and leachate；
(4) ammonium sulfate leaches：Leached mud is leached into 50min with 40% ammonium sulfate stirring, leaching temperature is 90 DEG C；
Mixed liquor filtering, washing after leaching, obtain filter residue and ammonium sulfate leaching liquid；Filter residue is obtained using 110 DEG C of temperature baking 1h
Low magnesium phosphorus concentrate；Ammonium sulfate consumption is to add 90g according to every 100g phosphorus ores；
(5) absorb：Step (1) is calcined into the carbon dioxide produced and the ammonia produced in step (2), (4) leaching process
It is passed into absorption tower, is handled using water absorption, obtains sal volatile；
(6) the sal volatile adjustment concentration obtained step (5) is 35%, is leached with the ammonium sulfate that step (4) is obtained
Liquid is mixed, stirring reaction 50min, and reaction temperature is 80 DEG C, reacting liquid filtering, washing, and sulphur is returned after filtrate and cleaning solution mixing
Recycled in sour ammonium leaching step；Calcined after filter cake drying under the conditions of 950 DEG C, produce magnesia；The consumption of ammonium carbonate is
115g is added according to every 100g phosphorus ores；
(7) leachate for obtaining step (3) adds the sal volatile that concentration is 35%, stirring reaction 50min, reaction
Temperature is 80 DEG C；Return in leaching step and circulate after reacted mixed liquor filtering, washing, ammonium nitrate filtrate and cleaning solution mixing
Use；Filter cake drying after leaching, produces calcium carbonate；The consumption of ammonium carbonate is to add 125g according to every 100g phosphorus ores.
Stirring in the step (2), (4), (6), (7) is treated substance is fully suspended in treatment fluid.
Washing in the step (3), (4), (6), (7) is to precipitate using the water washing per 100g phosphorus ores 30ml.
Filter cake drying temperature in the step (6), (7) is 110 DEG C, drying and processing time >=1h.
Result：P in phosphorus concentrate2O5Content 39.4%, content of magnesium 0.26%.
Embodiment 4
A kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, comprises the following steps：
(1) calcining digestion：Mid low grade phosphate rock is placed in calcining furnace, the calcination processing 1h at a temperature of 100 DEG C, then entered
Water-filling digestion process, the water digestion process is carried out using 80 DEG C of hot water, and the consumption of water is to use 60ml water per 100g phosphorus ores；
(2) ammonium nitrate leaches：The phosphorus ore that digestion process is completed is placed in leaching groove, then adds the nitre that concentration is 30%
Acid ammonium solution and 65% salpeter solution, stir process 80min at a temperature of 60 DEG C；The consumption of ammonium nitrate is according to every 100g phosphorus
Ore deposit adds 110g, and the addition of salpeter solution is to add 10g according to every 100g phosphorus ores；
(3) separate：Slurry after step (2) leaching is handled is filtered, washed, and obtains leached mud and leachate；
(4) ammonium sulfate leaches：Leached mud is leached into 50min with 30% ammonium sulfate stirring, leaching temperature is 90 DEG C；
Mixed liquor filtering, washing after leaching, obtain filter residue and ammonium sulfate leaching liquid；Filter residue is obtained using 110 DEG C of temperature baking 1h
Low magnesium phosphorus concentrate；Ammonium sulfate consumption is to add 90g according to every 100g phosphorus ores；
(5) absorb：Step (1) is calcined into the carbon dioxide produced and the ammonia produced in step (2), (4) leaching process
It is passed into absorption tower, is handled using water absorption, obtains sal volatile；
(6) the sal volatile adjustment concentration obtained step (5) is 25%, is leached with the ammonium sulfate that step (4) is obtained
Liquid is mixed, stirring reaction 50min, and reaction temperature is 80 DEG C, reacting liquid filtering, washing, and sulphur is returned after filtrate and cleaning solution mixing
Recycled in sour ammonium leaching step；Calcined after filter cake drying under the conditions of 950 DEG C, produce magnesia；The consumption of ammonium carbonate is
100g is added according to every 100g phosphorus ores；
(7) leachate for obtaining step (3) adds the sal volatile that concentration is 25%, stirring reaction 50min, reaction
Temperature is 80 DEG C；Return in leaching step and circulate after reacted mixed liquor filtering, washing, ammonium nitrate filtrate and cleaning solution mixing
Use；Filter cake drying after leaching, produces calcium carbonate；The consumption of ammonium carbonate is to add 125g according to every 100g phosphorus ores.
Stirring in the step (2), (4), (6), (7) is treated substance is fully suspended in treatment fluid.
Washing in the step (3), (4), (6), (7) is to precipitate using the water washing per 100g phosphorus ores 30ml.
Filter cake drying temperature in the step (6), (7) is 110 DEG C, drying and processing time >=1h.
Result：P in phosphorus concentrate2O5Content 38.7%, content of magnesium 0.29%.
Claims (9)
1. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium, it is characterised in that comprise the following steps：
(1) calcining digestion：Mid low grade phosphate rock is placed in calcining furnace, high-temperature calcination, hot water digestion；
(2) ammonium nitrate leaches：Postdigestive phosphorus ore will be calcined to be placed in leaching groove, the ammonium nitrate that concentration is 10%-50% is added
The salpeter solution of solution and 5%-95%, stirring leaching；
(3) separate：Slurry after step (2) leaching is handled is filtered, washed, and obtains leached mud and leachate；
(4) ammonium sulfate leaches：Leached mud is stirred with 10-40% ammonium sulfate and leached；Mixed liquor after leaching is filtered, washed
Wash, obtain filter residue and ammonium sulfate leaching liquid；Filter residue is dried, and obtains low magnesium phosphorus concentrate；
(5) absorb：Step (1) is calcined into the carbon dioxide produced to be passed through with the ammonia produced in step (2), (4) leaching process
Into absorption tower, handled using water absorption, obtain sal volatile；
(6) sal volatile for obtaining step (5) is mixed with the ammonium sulfate leaching liquid that step (4) is obtained, stirring reaction, reaction
Return in ammonium sulfate leaching step and recycle after liquid filtering, washing, filtrate and cleaning solution mixing；Calcined after filter cake drying, i.e.,
Obtain magnesia；
(7) leachate for obtaining step (3) adds the sal volatile that concentration is 10-35%, stirring reaction；It is reacted mixed
Close to return in ammonium nitrate leaching step after liquid filtering, washing, filtrate and cleaning solution mixing and recycle；Filter cake after leaching dries
It is dry, produce calcium carbonate.
2. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In, the consumption of ammonium nitrate is to add 80-120g according to every 100g phosphorus ores in the step (2), the addition of salpeter solution be by
2-15g is added according to every 100g phosphorus ores, the stirring leaching 50-80min at a temperature of 60-85 DEG C.
3. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：Ammonium sulfate consumption is to add 80-100g according to every 100g phosphorus ores in the step (4), and leaching is stirred at a temperature of 80-90 DEG C
Take 50-70min.
4. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：The consumption of ammonium carbonate is to add 100-125g according to every 100g phosphorus ores in the step (6), and first adjustment concentration is before the reaction
10-35%, the stirring reaction 50-70min at a temperature of 50-80 DEG C.
5. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：The consumption of ammonium carbonate is to add 100-150g according to every 100g phosphorus ores in the step (7), is stirred at a temperature of 50-80 DEG C
Mix reaction 50-70min.
6. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：Step (1) the high temperature calcination processing temperature is 900-1100 DEG C, and the time is 0.5-1.5h；Hot water in water digestion process
Temperature is 60-80 DEG C, and the consumption of water is to use 40-60ml water per 100g phosphorus ores.
7. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：Stirring in the step (2), (4), (6), (7) is treated substance is fully suspended in treatment fluid.
8. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：Washing in the step (3), (4), (6), (7) is to precipitate using the water washing per 100g phosphorus ores 20-40ml.
9. a kind of processing method for improving mid low grade phosphate rock quality and reclaiming calcium and magnesium as claimed in claim 1, its feature exists
In：Drying in the step (4), (6), (7) be temperature be 100-120 DEG C, drying >=1h.
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| CN106669962B (en) * | 2016-12-30 | 2019-10-29 | 四川玖长科技有限公司 | A kind of application method for the beneficiation method of the siliceous phosphorus ore of calcareous or calcium, ore-sorting system and ore-sorting system |
| CN107793180A (en) * | 2017-09-12 | 2018-03-13 | 徐州市禾协肥业有限公司 | Improve the method for magnesium leaching efficiency and application in phosphorus ore |
| CN107697893A (en) * | 2017-09-29 | 2018-02-16 | 徐州市禾协肥业有限公司 | Improve the method for calcium leaching efficiency and its product and application in phosphorus ore |
| CN108101602A (en) * | 2017-11-27 | 2018-06-01 | 贵州芭田生态工程有限公司 | A kind of calcium nitrate magnesium compositions and preparation method thereof |
| CN110872104A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Method for leaching magnesium ions in phosphorite |
| CN110872105A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Method for efficiently leaching calcium and magnesium ions in phosphorite |
| CN110872199A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Method for leaching calcium ions in phosphorite |
| CN109336072A (en) * | 2018-09-30 | 2019-02-15 | 贵州芭田生态工程有限公司 | Phosphorus ore calcines utilization method and phosphorus concentrate of exhaust gas washing water and preparation method thereof |
| CN112723404A (en) * | 2021-01-04 | 2021-04-30 | 贵州芭田生态工程有限公司 | Method for separating calcium, magnesium and phosphorus in chemical beneficiation by-product |
| CN112794354A (en) * | 2021-01-04 | 2021-05-14 | 贵州芭田生态工程有限公司 | Method for preparing calcium carbonate and potassium magnesium nitrate/potassium calcium magnesium nitrate from calcium magnesium-containing leaching solution |
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