CN105399068B - A kind of method phosphorus tailing processing and produce the calcium carbonate containing magnesium - Google Patents
A kind of method phosphorus tailing processing and produce the calcium carbonate containing magnesium Download PDFInfo
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Abstract
The present invention relates to phosphorus tailing working process technical fields, especially a kind of phosphorite tailings processing technology and the method for producing the calcium carbonate containing magnesium, first by calcining digestion process, accelerate the decomposable process of calcium carbonate and magnesium carbonate, the compound leaching of compound leaching or ammonium chloride solution and hydrochloric acid solution in conjunction with ammonium nitrate solution and salpeter solution, so that magnesium elements are adequately leached, largely isolate in phosphorus tailing, improves recycling phosphorus ore quality；And by the waste liquid generated in the process, waste gas recovery, treated, and solvent recycles, calcium carbonate containing magnesium is produced while obtaining high-quality phosphorus ore, effective recycling not only has been carried out to calcium magnesium element, waste liquid, the discharge of exhaust gas and the accumulation of tailing are also avoided, the improvement of ecological environment is conducive to.
Description
Technical field
The present invention relates to phosphorus tailings glass technical field, the side of especially a kind of phosphorus tailing processing and production calcium carbonate containing magnesium
Method.
Background technology
China's phosphorus ore reserves occupy second place of the world, but 80% or so of reserves is mid low grade phosphate rock, wherein being mostly difficult choosing
Mid-low grade collophanite ore, mineral grain is thin, embedding cloth is close, and the impurity such as association magnesium are higher, it can reduce the grade of rock phosphate in powder, increase
Sulfuric acid consumption when big phosphorus ore wet-treating, influences phosphoric acid and the quality of phosphate deep processing and product.Therefore it needs to phosphorus ore
It is pre-processed, the ore dressing of China's phosphorus ore at present mainly uses the methods of flotation, reverse flotation, wherein through a reverse flotation and simply
It cleans discharge tailing and contains P2O5≤ 15%, MgO >=10%；Through secondary reverse flotation discharge tailing P2O5≤ 10%, MgO >=15%.Cause
This, the tailing after ore dressing is more, and wherein also contains more rich available resources, and most heaps are stored in Tailings Dam, deposit
In larger environmental risk.
Since the composition of various regions phosphorus ore is different, the composition difference of phosphorite tailings is also larger, therefore for the comprehensive of phosphorite tailings
It is also not the same to close utilization ways, such as with making cement, the raw material of air entrained concrete, devitrified glass product, to siliceous high phosphorus
Dispensing of the mine tailing for calcium magnesium phosphate or kiln-process phosphoric acid.But the composition of Guizhou province phosphorus ore is mainly dolomite and a small amount of phosphorus ash
Stone produces calcium superphosphate (magnesium) fertilizer, although can be certain using the method that Mixed phosphoric acid and sulfuric acid decomposes tailing in the prior art
The Utilizing question of phosphorite tailings is solved in degree, but a large amount of sulfuric acid of consumption, phosphoric acid go processing to be equivalent to the tailing of dolomite and obtain
To phosphorus fertiliser containing magnesium, convention is not conformed to, and normal superphosphate physical property is poor currently on the market, quality need to wait further increasing.In addition
A large amount of ardealite will be will produce after sulfuric acid treatment, and ardealite discharge will cause the serious dirt of environment in the natural environment
Dye, and the elements such as magnesium are not efficiently separated in tailing, and then the quality for resulting in the tailing after sulfur acid pretreatment does not have
Improve, be not achieved screening concentrate, comprehensive utilization purpose；And in processing procedure, since magnesium sulfate and sulfuric acid form micro-soluble material
Later, sulfuric acid is made to be difficult to return to recycle, the cost in turn resulted in carrying out tailing preprocessing process is larger.
CN85107209 discloses a kind of method of chemical sepn, and ammonium chloride and nitric acid will be used after phosphorus ore radiation roasting
The mode separating magnesium of ammonium mixing leaching, quality and by-product recovery to improve low-grade phosphate ore, which utilize, provides a kind of processing
Mode, but in engineer application, due in ammonium chloride chlorion and nitrate anion stainless steel equipment can be corroded, very
Hardly possible carries out a large amount of and duration processing, so the material to equipment has high requirements, and cannot be applied to extensively with economic
In practical big production.
For this purpose, this researcher is requiring Patent No. 201510226521.3《A kind of processing of phosphorus tailing and production contain
The method of magnesium calcium carbonate》Priority on the basis of, by form existing for phosphorus pentoxide in phosphorus tailing, calcium, magnesium elements
And content etc. carries out analysis and discussion, and is adjusted to traditional tailing processing technology, using hydrochloric acid and ammonium chloride solution or
After nitric acid and ammonium nitrate solution are combined into combined processing liquid, then phosphorus tailing is pre-processed, improves P in tailing2O5Contain
Amount, so as to improve the quality of tailing；Finally the ammonium salt leaching liquid after separation is handled, obtains calcium, magnesium products.At present for
Phosphorite tailings quality is improved using nitric acid and the compound leaching of ammonium nitrate, and the method for production calcium carbonate containing magnesium yet there are no document report
Road, this provides a kind of new approaches for the processing of tailing, increase added value of product.
Invention content
In order to solve the above technical problems existing in the prior art, a kind of phosphorus tailing processing of present invention offer and production contain
The method of magnesium calcium carbonate, step of preparation process is simple, and technological process is short, and the treatment fluid of consumption can recycle, no exhaust gas,
The discharge of waste liquid, waste residue, and the content of the phosphorus pentoxide of phosphorus ore can be improved to 35% or more, it will be in low magnesium phosphorus concentrate
Content of magnesium is reduced to≤1.0%, to improve the quality and quality of phosphorus tailing, achievees the purpose that resource of tailings utilizes, and can obtain
Magnesium calcium carbonate must be contained, improve the comprehensive utilization value of tailing.
It is achieved particular by following technical scheme：
A kind of method phosphorus tailing processing and produce the calcium carbonate containing magnesium digests the high-temperature calcination of phosphorus tailing, hot water；And to disappearing
Change and ammonium nitrate solution and nitric acid composite solution or ammonium chloride solution and hydrochloric acid composite solution are added in treated slurry, stirring is multiple
Leaching is closed, separation obtains leaching slag and leaching liquid；Leaching slag is dried, and low magnesium phosphorus concentrate is obtained；It will be generated during calcination processing
Carbon dioxide gas and leaching process in the ammonia that generates absorbed using water, then add it in leaching liquid and mix, stir
It is detached after reaction, filter residue dries to obtain calcium carbonate containing magnesium.
The method of the above-mentioned processing of phosphorus tailing and the production calcium carbonate containing magnesium, specifically includes following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, high-temperature calcination, hot water digestion；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, addition mass concentration is 10-50%
Ammonium nitrate solution and mass concentration be 5-90% salpeter solution, stirring leaching；
(3) it detaches：By the slurry filtration of leaching completion, washing in step (2), leaching slag and leaching liquid, leaching slag are obtained
Drying, obtains low magnesium phosphorus concentrate；
(4) it absorbs：The ammonia that the carbon dioxide that step (1) calcining generates is generated with step (2) is passed into absorption tower,
It is handled using water absorption, obtains sal volatile；
(5) sal volatile that step (4) obtains is uniformly mixed with the leaching liquid that step (3) obtains, is stirred to react；Instead
Mixed liquor after answering is filtered, washed, and is returned after filtrate and cleaning solution mixing and is recycled in leaching step；Filter residue is dried, and is obtained
Calcium carbonate containing magnesium.
The compound leaching is that the phosphorus tailing that digestion process is completed is placed in leaching slot, and mass concentration, which is added, is
The ammonium chloride solution and mass concentration of 15-25% is the hydrochloric acid solution of 5-31%.
The dosage of the ammonium nitrate solution is that 250-350g is added according to every 100g tailings, and the salpeter solution adds
It is that 2-25g is added according to every 100g tailings to enter amount, stir process 50-70min at a temperature of 80-85 DEG C.
The ammonium carbonate dosage is that 100-110g is added according to every 100g phosphorus tailing, uses preceding a concentration of 10- of adjustment
35%, it is stirred to react 50-70min at a temperature of 50-80 DEG C.
The filter residue drying, temperature are 100-120 DEG C, and the drying and processing time is >=1h.
The high-temperature calcination treatment temperature is 900-1100 DEG C, time 45-75min；The hot water, temperature are
60-100 DEG C, the dosage of water is to use 90-110ml water per 100g phosphorus tailings.
The stirring is that treated substance is made fully to be suspended in treatment fluid.
The washing, by precipitation using the water washing per 100g phosphorus tailings 20-40ml.
The dosage of the ammonium chloride solution is that 700-1000ml is added per 200g phosphorus tailings；The use of the hydrochloric acid solution
Amount is per 200g phosphorus tailing additions 15-30g.
Compared with prior art, technique effect of the invention is embodied in：
(1) present invention accelerates the decomposable process of calcium carbonate and magnesium carbonate, was descended in conjunction with high temperature first by calcining digestion process
Measure the combined-circulation leaching mode of ammonium nitrate solution and salpeter solution or using ammonium chloride solution and hydrochloric acid solution combined-circulation
The method of leaching so that magnesium elements are adequately leached, and are largely isolated in phosphorus ore, and then obtain low magnesium phosphorus concentrate, make P2O5
Content improve to 35% or more, content of magnesium is reduced to≤1.0%, improves tailing quality, resource is made to be fully used；
(2) ammonia of output in the exhaust gas and leaching process that are generated in calcination process is absorbed and utilized in the present invention,
In addition ammonium carbonate treated filtrate and cleaning solution are recycled, greatly protect environment, adapt to ecological ring from now on
The development need in border；
(3) by ammonium nitrate and the leaching of nitric acid combined-circulation or ammonium chloride solution and the compound leaching of hydrochloric acid, high-quality is obtained
Filter residue or filtrate after phosphorus ore carry out subsequent processing, obtain calcium carbonate containing magnesium, not only to calcium magnesium element effectively return
It receives and utilizes, moreover it is possible to which the accumulation for greatly reducing phosphorite tailings not only improves resource regeneration, improves value-added content of product, and be conducive to
Environmental protection；
(4) the process step of the invention is simple, and process cycle is short, and low energy consumption in processing procedure, and raw material especially leaches
Agent can be partially recovered and recycle, and reduce pretreated cost；And there is no the row of waste liquid, waste residue in processing procedure
It puts, improves the added value of product of entire technique；
(5) present invention substitutes traditional sulfuric acid treating processes using ammonium nitrate and the compound leaching of nitric acid, reduces ardealite
Discharge capacity, avoid ardealite largely stores up the pollution brought to environment, have the significant value of environmental protection and economic benefit.
Technical scheme of the present invention is further elaborated using experiment below, to prove the effect of the present invention.
One, it selects the phosphorite tailings in Guizhou Wengan area as experimental raw, and every ingredient in phosphorus ore is examined
It surveys, obtains raw material phosphor tailing as shown in Table 1：
Table 1
| Ingredient | P2O5 | CaO | MgO | Fe2O3 | Al2O3 | F | AI | It burns and loses |
| % | 7.23 | 34.94 | 17.65 | 0.22 | 0.24 | 0.62 | 3.15 | 37.2 |
1 technical study of test example
1.1 calcining digestion
By the calcining of phosphorus tailing, digestion, following reaction occurs：
CaCO3·MgCO3→CaO+MgO+2CO2
CaO+MgO+2H2O→Ca(OH)2+Mg(OH)2
Calcination processing 45-75min at a temperature of 900-1100 DEG C ensures the abundant decomposition of calcium carbonate and magnesium carbonate.
The compound leaching of 1.2 ammonium nitrate, nitric acid
Take 100g phosphorus tailings respectively, after carrying out calcining digestion process, investigate respectively different ammonium nitrate dosages (200g,
250g, 300g, 350g, 400g), concentration (10%, 20%, 30%, 40%, 50%), leaching temperature (20-25 DEG C, 65-75 DEG C,
80-85 DEG C), leaching time (40min, 50min, 60min, 70min, 80min, 90min), concentration of nitric acid (5%, 15%,
25%, 35%, 45%, 60%, 75%, 90%), the factors such as dosage (2g, 5g, 10g, 18g, 20g, 22g, 25g) are to P2O5Content
Influence, investigate the result shows that, select the dosage of ammonium nitrate be according to every 100g phosphorus tailing addition 250-350g, concentration 10%-
50%, the addition of salpeter solution is that 2-25g, concentration 5%-90% is added according to every 100g phosphorus tailing, leaches 50-70min, leaching
Take 80-85 DEG C of temperature, P2O5Content is improved to 36.14%.It is preferred that the dosage of ammonium nitrate is to be added according to every 100g phosphorus tailing
300g, concentration 30%, the addition of salpeter solution are that 20g, concentration 60% is added according to every 100g phosphorus tailing, leach 60min, leaching
Take 80 DEG C of temperature.
Reaction equation is as follows：
Ca(OH)2+NH4NO3+HNO3→Ca(NO3)2+NH3+2H2O
1.3 compliance test result
Phosphorus tailing 1kg is taken respectively, is handled according to the method for 1-3 of the embodiment of the present invention, then in low magnesium phosphorus concentrate
The content of phosphorus pentoxide and the content of magnesia are detected, and are obtained：The content of phosphorus pentoxide is 36.4-37.0%, oxygen
The content for changing magnesium is 0.7-0.9%；As it can be seen that the technical solution in the invention enables to containing for the phosphorus pentoxide in phosphorus tailing
Amount improves 28-30 percentage points, can content of magnesium in phosphorus tailing be reduced to≤1.0%；Achieve the purpose that recycling；It reduces
The waste residue saturation of phosphorus ore advanced treating, reduces environmental pollution.
Also, the calcium carbonate containing magnesium for subsequently producing ammonium salt leaching liquid with ammonium carbonate liquid precipitate forms and converts into calcium carbonate
Content is 53.1%, magnesium carbonate 46.5%.The filler of Plastic Rubber Products is can be used as, conventional calcium carbonates are better than.It is pre- to improve phosphorus tailing
Value-added content of product after processing.
In addition, carrying out the technique under laboratory condition by the phosphorus tailing to other area such as Fuquan areas, Kaiyang Region
As a result verification shows that technical scheme of the present invention is equally applicable to the processing and utilization of above-mentioned regional phosphorus tailing, five oxidations can be obtained
Low magnesium phosphorus concentrate of two phosphorus contents 35% or more, and calcium carbonate product containing magnesium can also be obtained, while also resource is fully returned
It receives, there is no the discharge of exhaust gas, waste liquid, waste residue in processing procedure, improve the added value of product of entire technique.
Two present invention have also selected Guizhou Wengan phosphorus tailing as experimental raw, and are examined to every ingredient in phosphorus ore
It surveys, obtains raw material phosphor tailing as shown in Table 2：
Table 2
| Ingredient | P2O5 | CaO | MgO | Fe2O3 | Al2O3 | F | AI | It burns and loses |
| % | 6.15 | 35.53 | 18.63 | 0.24 | 0.31 | 2.53 | 4.51 | 37.2 |
2.1 calcining digestion
By the calcining of phosphorus tailing, digestion, following reaction occurs：
CaCO3·MgCO3→CaO+MgO+2CO2
CaO+MgO+2H2O→Ca(OH)2+Mg(OH)2
Calcination processing 45-75min at a temperature of 900-1100 DEG C ensures the abundant decomposition of calcium carbonate and magnesium carbonate.
The compound leaching of 2.2 ammonium chlorides, hydrochloric acid
By it according to embodiment 9-12 processing, reaction equation is as follows：
Ca(OH)2+2NH4Cl→Ca Cl2+2NH3+2H2O
Mg(OH)2+2NH4Cl→Mg Cl2+2NH3+2H2O
2.3 compliance test result
It obtains：The content of phosphorus pentoxide is 37.3-38.21%, and the content of magnesia is 0.4-0.9%；As it can be seen that the hair
Technical solution in bright enables to the content of the phosphorus pentoxide in phosphorus tailing to improve 31-32 percentage points, can be by phosphorus tail
Content of magnesium is reduced to≤1.0% in mine；Achieve the purpose that recycling；The waste residue saturation of phosphorus ore advanced treating is reduced, is dropped
Low environmental pollution.In addition to this, this researcher additionally uses above-mentioned technical solution, that is, is exactly molten using hydrochloric acid and ammonium chloride
After liquid is compound, Anning phosphorus tailing is handled, as a result shows that technical scheme of the present invention is equally applicable to above-mentioned area
The processing and utilization of phosphorus tailing.
In addition to this, this researcher also using above-mentioned two kinds to Guizhou Wengan phosphorus tailing as the two methods of feedstock processing
It is compared, it is seen that at the effect ratio ammonium nitrate and nitric acid composite solution of ammonium chloride and hydrochloric acid composite solution processing phosphorus tailing
The effect for managing phosphorus tailing is slightly excellent；And in conjunction with being easy to get for ammonium chloride raw material, management and control is not stringent and obtains the advantages that cost is relatively low,
So that using ammonium chloride come the cost for carrying out processing phosphorus tailing relatively low, and industrialized production easy to implement, expand ammonium chloride and
The range of hydrochloric acid combined processing phosphorus tailing, reduces cost, kicks enough benefits.
In addition to this, this researcher also uses sulfuric acid to carry out combined processing with ammonium sulfate, can also reach certain skill
Art effect enables to the quality of low magnesium phosphorus concentrate in phosphorus tailing to be improved, and reduces what magnesium component handled phosphorus tailing once again
Difficulty reduces cost.Sulfurous acid and sulphite can also be used to carry out combined processing.
Description of the drawings
Fig. 1 is the process flow chart for the method that the calcium carbonate containing magnesium was processed and produced to phosphorite tailings of the present invention.
Specific implementation mode
It is limited technical scheme of the present invention is further, but is required with specific embodiment below in conjunction with the accompanying drawings
The range of protection describes made by being not only limited to.
Embodiment 1
A kind of method phosphorite tailings processing and produce the calcium carbonate containing magnesium, includes the following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, calcination processing 60min at a temperature of 950 DEG C, then carried out
Water digestion process；The water digestion process is carried out using 85 DEG C of hot water, and the dosage of water is to use 100ml per 100g phosphorus tailings
Water；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, a concentration of 30% nitre is then added
Acid ammonium solution and 60% salpeter solution, stir process 60min at a temperature of 85 DEG C；The dosage of ammonium nitrate is according to every 100g phosphorus
300g is added in tailing, and the addition of salpeter solution is that 20g is added according to every 100g phosphorus tailing；
(3) it detaches：By step 2) leaching, treated that slurry is filtered, washs, and obtains leached mud and leachate；Filter residue
1h is dried at 110 DEG C, obtains low magnesium phosphorus concentrate；
(4) it absorbs：The carbon dioxide that step (1) calcining generates is passed through with the ammonia generated in step (2) leaching process
It into absorption tower, is handled using water absorption, obtains sal volatile；
(5) the sal volatile adjustment a concentration of 25% obtained step (4), is mixed with the leachate for obtaining step (3)
It closes uniformly, is stirred to react 60min, reaction temperature is 65 DEG C；Mixed liquor after reaction is filtered, washed, ammonium nitrate filtrate and washing
It returns after liquid mixing and is recycled in leaching step；110 DEG C of drying >=1h of filter cake after leaching are to get calcium carbonate containing magnesium.It is described
Ammonium carbonate dosage is that 105g is added according to every 100g phosphorus tailing.Stirring in the step (2), (5) is to keep treated substance abundant
It is suspended in treatment fluid.Washing in the step (3), (5) is the washing that will be precipitated using per 100g phosphorus tailings 20-40ml
It washs.
Handling result：P in low magnesium phosphorus concentrate2O5Content 36.6%, content of magnesium 0.80%.
Embodiment 2
A kind of method phosphorite tailings processing and produce the calcium carbonate containing magnesium, includes the following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, calcination processing 75min at a temperature of 900 DEG C, then carried out
Water digestion process；The water digestion process is carried out using 60 DEG C of hot water, and the dosage of water is to use 110ml per 100g phosphorus tailings
Water；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, a concentration of 10% nitre is then added
Acid ammonium solution and 50% salpeter solution, stir process 70min at a temperature of 80 DEG C；The dosage of ammonium nitrate is according to every 100g phosphorus
250g is added in tailing, and the addition of salpeter solution is that 18g is added according to every 100g phosphorus tailing；
(3) it detaches：By step 2) leaching, treated that slurry is filtered, washs, and obtains leached mud and leachate；Filter residue
1.5h is dried at 110 DEG C, obtains low magnesium phosphorus concentrate；
(4) it absorbs：The carbon dioxide that step (1) calcining generates is passed through with the ammonia generated in step (2) leaching process
It into absorption tower, is handled using water absorption, obtains sal volatile；
(5) the sal volatile adjustment a concentration of 10% obtained step (4), is mixed with the leachate for obtaining step (3)
It closes uniformly, is stirred to react 70min, reaction temperature is 50 DEG C；Mixed liquor after reaction is filtered, washed, ammonium nitrate filtrate and washing
It returns after liquid mixing and is recycled in leaching step；110 DEG C of drying 1h of filter cake after leaching are to get calcium carbonate containing magnesium.The carbon
Sour ammonium dosage is that 100g is added according to every 100g phosphorus tailing.Stirring in the step (2), (5) is to keep treated substance fully outstanding
Float in treatment fluid.Washing in the step (3), (5) is the washing that will be precipitated using per 100g phosphorus tailings 20-40ml
It washs.
Handling result：P in low magnesium phosphorus concentrate2O5Content 36.4%, content of magnesium 0.87%.
Embodiment 3
A kind of method phosphorite tailings processing and produce the calcium carbonate containing magnesium, includes the following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, calcination processing 45min at a temperature of 1100 DEG C, then carried out
Water digestion process；The water digestion process is carried out using 100 DEG C of hot water, and the dosage of water is to use 90ml per 100g phosphorus tailings
Water；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, a concentration of 50% nitre is then added
Acid ammonium solution and 80% salpeter solution, stir process 50min at a temperature of 85 DEG C；The dosage of ammonium nitrate is according to every 100g phosphorus
350g is added in tailing, and the addition of salpeter solution is that 22g is added according to every 100g phosphorus tailing；
(3) it detaches：By step 2) leaching, treated that slurry is filtered, washs, and obtains leached mud and leachate；Filter residue
In 110 DEG C of drying >=1h, low magnesium phosphorus concentrate is obtained；
(4) it absorbs：The carbon dioxide that step (1) calcining generates is passed through with the ammonia generated in step (2) leaching process
It into absorption tower, is handled using water absorption, obtains sal volatile；
(5) the sal volatile adjustment a concentration of 35% obtained step (4), is mixed with the leachate for obtaining step (3)
It closes uniformly, is stirred to react 50min, reaction temperature is 80 DEG C；Mixed liquor after reaction is filtered, washed, ammonium nitrate filtrate and washing
It returns after liquid mixing and is recycled in leaching step；110 DEG C of drying >=1h of filter cake after leaching are to get calcium carbonate containing magnesium.It is described
Ammonium carbonate dosage is that 110g is added according to every 100g phosphorus tailing.Stirring in the step (2), (5) is to keep treated substance abundant
It is suspended in treatment fluid.Washing in the step (3), (5) is the washing that will be precipitated using per 100g phosphorus tailings 20-40ml
It washs.
Handling result：P in low magnesium phosphorus concentrate2O5Content 37.0%, content of magnesium 0.65%.
Embodiment 4
A kind of method phosphorite tailings processing and produce the calcium carbonate containing magnesium, includes the following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, calcination processing 60min at a temperature of 1000 DEG C, then carried out
Water digestion process；The water digestion process is carried out using 100 DEG C of hot water, and the dosage of water is to use 90ml per 100g phosphorus tailings
Water；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, a concentration of 20% nitre is then added
Acid ammonium solution and 90% salpeter solution, stir process 60min at a temperature of 85 DEG C；The dosage of ammonium nitrate is according to every 100g phosphorus
280g is added in tailing, and the addition of salpeter solution is that 21g is added according to every 100g phosphorus tailing；
(3) it detaches：By step 2) leaching, treated that slurry is filtered, washs, and obtains leached mud and leachate；Filter residue
In 110 DEG C of drying >=1h, low magnesium phosphorus concentrate is obtained；
(4) it absorbs：The carbon dioxide that step (1) calcining generates is passed through with the ammonia generated in step (2) leaching process
It into absorption tower, is handled using water absorption, obtains sal volatile；
(5) the sal volatile adjustment a concentration of 25% obtained step (4), is mixed with the leachate for obtaining step (3)
It closes uniformly, is stirred to react 50min, reaction temperature is 80 DEG C；Mixed liquor after reaction is filtered, washed, ammonium nitrate filtrate and washing
It returns after liquid mixing and is recycled in leaching step；110 DEG C of drying >=1h of filter cake after leaching are to get calcium carbonate containing magnesium.It is described
Ammonium carbonate dosage is that 110g is added according to every 100g phosphorus tailing.Stirring in the step (2), (5) is to keep treated substance abundant
It is suspended in treatment fluid.Washing in the step (3), (5) is the washing that will be precipitated using per 100g phosphorus tailings 20-40ml
It washs.
Handling result：P in low magnesium phosphorus concentrate2O5Content 36.8%, content of magnesium 0.73%.
Embodiment 5
A kind of method phosphorite tailings processing and produce the calcium carbonate containing magnesium, includes the following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, calcination processing 60min at a temperature of 1000 DEG C, then carried out
Water digestion process；The water digestion process is carried out using 100 DEG C of hot water, and the dosage of water is to use 90ml per 100g phosphorus tailings
Water；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, a concentration of 20% nitre is then added
Acid ammonium solution and 90% salpeter solution, stir process 60min at a temperature of 85 DEG C；The dosage of ammonium nitrate is according to every 100g phosphorus
280g is added in tailing, and the addition of salpeter solution is that 21g is added according to every 100g phosphorus tailing；
(3) it detaches：By step 2) leaching, treated that slurry is filtered, washs, and obtains leached mud and leachate；Filter residue
In 110 DEG C of drying >=1h, low magnesium phosphorus concentrate is obtained；
(4) it absorbs：The carbon dioxide that step (1) calcining generates is passed through with the ammonia generated in step (2) leaching process
It into absorption tower, is handled using water absorption, obtains sal volatile；
(5) the sal volatile adjustment a concentration of 25% obtained step (4), is mixed with the leachate for obtaining step (3)
It closes uniformly, is stirred to react 50min, reaction temperature is 80 DEG C；Mixed liquor after reaction is filtered, washed, ammonium nitrate filtrate and washing
It returns after liquid mixing and is recycled in leaching step；110 DEG C of drying >=1h of filter cake after leaching are to get calcium carbonate containing magnesium.
Handling result：P in low magnesium phosphorus concentrate2O5Content 36.7%, content of magnesium 0.74%.
Embodiment 6
On the basis of embodiment 1, other are that phosphorus tailing is placed in calcining furnace, using 900- with embodiment 1
After 950 DEG C of calcination processing 1h, the ammonium chloride solution that mass percent is 15% and the salt that mass percent is 31% is added in digestion
Acid, the amount that ammonium chloride solution is added are that 350ml is added according to every 100g phosphorus ores, and the amount that hydrochloric acid is added is to be added according to 100g phosphorus ores
7.5g, control temperature leach 60min at 60 DEG C.
Handling result：P in low magnesium phosphorus concentrate2O5Content 36.4%, content of magnesium 0.71%.
Embodiment 7
On the basis of embodiment 2, other are by the phosphorus tailing after the calcination processing in calcining furnace with embodiment 2
Digestion is being added the ammonium chloride solution that mass percent is 25% and the hydrochloric acid that mass percent is 31%, it is molten that ammonium chloride is added
The amount of liquid is that 500ml is added according to every 100g phosphorus ores, and the amount that hydrochloric acid is added is that 15g is added according to 100g phosphorus ores, and control temperature exists
85 DEG C of leaching 60min.
Handling result：P in low magnesium phosphorus concentrate2O5Content 37.4%, content of magnesium 0.83%.
Embodiment 8
On the basis of embodiment 3, other are by the phosphorus tailing after the calcination processing in calcining furnace with embodiment 3
Digestion is being added the ammonium chloride solution that mass percent is 20% and the hydrochloric acid that mass percent is 31%, it is molten that ammonium chloride is added
The amount of liquid is that 450ml is added according to every 100g phosphorus ores, and the amount that hydrochloric acid is added is that 12g is added according to 100g phosphorus ores, and control temperature exists
75 DEG C of leaching 60min.
Handling result：P in low magnesium phosphorus concentrate2O5Content 37.9%, content of magnesium 0.41%.
Claims (8)
1. a kind of method of phosphorus tailing processing and production calcium carbonate containing magnesium, which is characterized in that the high-temperature calcination of phosphorus tailing, hot water disappear
Change；And addition ammonium nitrate solution and nitric acid composite solution or ammonium chloride solution and hydrochloric acid are compound molten into the slurry after digestion process
Liquid stirs compound leaching, and separation obtains leaching slag and leaching liquid；Leaching slag is dried, and low magnesium phosphorus concentrate is obtained；By calcination processing
The ammonia generated in the carbon dioxide gas and leaching process that generate in the process is absorbed using water, then is added it in leaching liquid
Mixing, detaches, filter residue dries to obtain calcium carbonate containing magnesium after being stirred to react；
Specifically include following steps：
(1) calcining digestion：Phosphorus tailing is placed in calcining furnace, high-temperature calcination, hot water digestion；
(2) compound leaching：The phosphorus tailing that digestion process is completed is placed in leaching slot, the nitre that mass concentration is 10-50% is added
Acid ammonium solution and the salpeter solution that mass concentration is 5-90%, stirring leaching；Or the phosphorus tailing that digestion process is completed is placed in leaching
It takes in slot, the ammonium chloride solution that mass concentration is 15-25% and the hydrochloric acid solution that mass concentration is 5-31%, stirring leaching is added
It takes；
(3) it detaches：By the slurry filtration of leaching completion, washing in step (2), leaching slag and leaching liquid are obtained, leaching slag is dried,
Obtain low magnesium phosphorus concentrate；
(4) it absorbs：The ammonia that the carbon dioxide that step (1) calcining generates is generated with step (2) is passed into absorption tower, is used
Water absorption is handled, and obtains sal volatile；
(5) sal volatile that step (4) obtains is uniformly mixed with the leaching liquid that step (3) obtains, is stirred to react；After reaction
Mixed liquor be filtered, washed, filtrate and cleaning solution mixing after return leaching step in recycle；Filter residue is dried, and obtains containing magnesium
Calcium carbonate；The high-temperature calcination, temperature are 900-1100 DEG C.
2. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that the nitric acid
The dosage of ammonium salt solution is that 250-350g is added according to every 100g tailings, and the addition of the salpeter solution is according to every 100g tails
2-25g is added in mine, stir process 50-70min at a temperature of 80-85 DEG C.
3. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that the carbonic acid
Ammonium dosage is that 100-110g is added according to every 100g phosphorus tailing, using preceding a concentration of 10-35% of adjustment, in 50-80 DEG C of temperature
Under be stirred to react 50-70min.
4. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that the filter residue
Drying, temperature are 100-120 DEG C, and the drying and processing time is >=1h.
5. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that the high temperature
Calcination processing temperature is 900-1100 DEG C, time 45-75min；The hot water, temperature are 60-100 DEG C, the dosage of water
90-110ml water is used for every 100g phosphorus tailing.
6. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that described stirs
It mixes, is that treated substance is made fully to be suspended in treatment fluid.
7. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that described washes
It washs, by precipitation using the water washing per 100g phosphorus tailings 20-40ml.
8. the method for phosphorus tailing processing as described in claim 1 and production calcium carbonate containing magnesium, which is characterized in that the chlorination
The dosage of ammonium salt solution is that 700-1000ml is added per 200g phosphorus tailings；The dosage of the hydrochloric acid solution is to add per 200g phosphorus tailings
Enter 15-30g.
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| CN105367176B (en) * | 2015-12-02 | 2019-03-08 | 武汉工程大学 | A kind of multielement composite of phosphorus potassium associated minerals utilizes technique |
| CN106365134B (en) * | 2016-08-30 | 2018-04-17 | 晋宁上蒜明亮选矿厂 | Rock phosphate in powder recycling and processing device |
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| CN110872128A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Control phosphorite preparation system of component balance among phosphorite |
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| CN109354000A (en) * | 2018-10-09 | 2019-02-19 | 湖南化工职业技术学院（湖南工业高级技工学校） | A kind of method of High-Mg phosphate tailings enrichment co-production precipitated calcium carbonate and magnesium hydroxide |
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| CN112794737A (en) * | 2021-01-04 | 2021-05-14 | 贵州芭田生态工程有限公司 | Process for preparing potassium calcium magnesium nitrate and potassium magnesium ammonium nitrate from medium-low grade phosphate ore |
| CN113149053B (en) * | 2021-02-23 | 2022-04-05 | 湖北省长江资源循环利用及装备创新中心有限公司 | Chemical demagging method for collophanite |
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Address after: 550400 maolishan formation, Yuhua community, Yinzhan Town, Weng'an county, Qiannan Buyei and Miao Autonomous Prefecture, Guizhou Province (Weng'an Phosphate Mine yellow phosphorus plant) Patentee after: GUIZHOU SHENGYUAN NEW MAT Co.,Ltd. Address before: 550400 maolishan formation, Yuhua community, Yinzhan Town, Weng'an county, Qiandongnan Miao and Dong Autonomous Prefecture, Guizhou Province (Weng'an Phosphate Mine yellow phosphorus plant) Patentee before: GUIZHOU SHENGYUAN NEW MAT Co.,Ltd. |