CN104860278A - Method for extracting phosphate concentrate from phosphate tailings and cooperatively producing calcium carbonate and magnesium oxide - Google Patents
Method for extracting phosphate concentrate from phosphate tailings and cooperatively producing calcium carbonate and magnesium oxide Download PDFInfo
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Abstract
The invention discloses a method for extracting phosphate concentrate from phosphate tailings and cooperatively producing calcium carbonate and magnesium oxide. First, phosphate tailings are calcined under high temperature, hot water is added into the calcined material for digestion treatment, an ammonium nitrate solution is added to the calcined material, the mixture is stirred, calcium is extracted under a certain temperature, calcium-containing leaching liquid and leaching residues are obtained, phosphate concentrate and magnesium-containing leaching liquid are obtained after magnesium is extracted from the leaching residues with an ammonium sulfate solution, calcium carbonate is obtained after the calcium-containing leaching liquid is precipitated by an ammonium carbonate solution, magnesium carbonate is obtained after the magnesium-containing leaching liquid is precipitated by an ammonium carbonate solution, and magnesium oxide is obtained after the magnesium carbonate is calcined. According to the method, phosphate concentrate, calcium carbonate and magnesium oxide are prepared with phosphate tailings as the main raw materials, large-scale treatment can be carried out on the phosphate tailings, the problem that because phosphate tailings pile up in quantity, the phosphate tailings occupy a lot of land and pollute the environment is solved, and the products of phosphate concentrate, calcium carbonate and magnesium oxide are obtained.
Description
Technical field
The present invention relates to the recovery and utilization technology field of phosphorus mine tailing, specifically, relate to a kind of phosphorus mine tailing and extract phosphorus concentrate co-production calcium carbonate and method of magnesium oxide.
Background technology
Phosphorus ore is a kind of non-renewable resource, although China's phosphate rock resource is abundanter, but the grade of phosphorus ore is lower, could for the production of phosphoric acid and high concentration phosphate fertilizer etc. after major part phosphorus ore has to pass through beneficiation enrichment, because the impurity in phosphorus ore is more, cause the practical efficiency of China's phosphorus ore lower, and China is large especially to the demand of phosphorus, utilize through exploitation for many years, the phosphate rock resource of China is day by day exhausted.
The solid waste of failing to be used of discharging when phosphorus mine tailing is phosphate rock floating concentrate.The grade of China's Rock Phosphate (72Min BPL) raw ore is all not high, causes sulphur dioxide of phosphor chemical industry and all outwards will discharge a large amount of phosphorus mine tailings when phosphate rock floating concentrate, often produces 300 tons of phosphorus concentrate, discharge 100 tons of phosphorus mine tailings, the bulk deposition of phosphorus mine tailing, not only takies a large amount of soils, but also can bring environmental pollution.Along with the development of China's phosphorus ore work industry and the continuous increase of social demand, the demand of phosphorus product is also along with increase, and the accumulation problem of phosphorus mine tailing is more and more serious.Phosphorus mine tailing is when suffering erosion, and in mine tailing during some transportable element generation chemical transport, will cause serious pollution to air and water and soil, serious meeting causes land deterioration, and vegetation is destroyed, and threatens the safety of people and animals.China at present by the land area of phosphorus tailings pollution up to 1,000,000 mu.
Because the phosphorus ore moiety of various places is different, the component difference of phosphorus mine tailing is larger, the main component of Guizhou province phosphorus mine tailing is rhombspar (accounting for about 80% of phosphorus mine tailing), secondly also containing a small amount of phosphatic rock (accounting for about 15% of phosphorus mine tailing).At present, the utilization of China to phosphorus mine tailing is mainly reflected in the following aspects: first, by phosphorus mine tailing as the raw material preparing material of construction, material of construction is as cement, gas concrete and devitrified glass etc., although above-mentioned several approach can consume a part of phosphorus mine tailing, alleviate the situation of phosphorus mine tailing bulk deposition to a certain extent, but phosphorus mine tailing is not utilized fully, cause the waste of part useful element in phosphorus mine tailing; The second, phosphorus mine tailing is carried out secondary flotation, and the method utilizes further to the phosphorus in phosphorus mine tailing, effectively can reduce the phosphorus content in phosphorus mine tailing, but still on the low side to the utilization ratio of phosphorus in phosphorus mine tailing, and fundamentally can not solve the present situation of phosphorus mine tailing bulk deposition; 3rd, adopt Mixed phosphoric acid and sulfuric acid to divide phosphorus decomposing mine tailing to prepare phosphorus fertiliser containing magnesium, although this kind of method can solve the Utilizing question of part phosphorite tailings, it will consume a large amount of sulfuric acid and phosphoric acid goes to prepare phosphorus fertiliser containing magnesium, and the economic benefit obtained is bad.
Application number is 201210155826.6, denomination of invention is a kind of method utilizing High-Mg phosphate tailings to produce light magnesium oxide, it is calcined at 850 ~ 1200 DEG C by High-Mg phosphate tailings, burn till calcining material, calcining material is mixed by weight 1:4 ~ 40 with water, stir 10 ~ 100 minutes at temperature 20 ~ 90 DEG C, obtain digesting slurries; In digestion slurries, make up water makes digestion slurry solid content be massfraction 2% ~ 15%, at 10 ~ 35 DEG C, carry out carburizing reagent to the gas passed into containing carbonic acid gas in digestion slurries again and obtain carbodiimide solution, the stopped reaction when the pH value of carbodiimide solution is down to 6.5 ~ 8.0, filtered by carbodiimide solution, filtrate is that heavy magnesium water filter cake is mainly calcium carbonate; By heavy magnesium water pyrolysis 0.2 ~ 3h at 80 ~ 105 DEG C, obtain basic carbonate magnesium precipitate, obtain magnesium basic carbonate filter cake after filtration, filtrate water is back to digestion, carbonization; Magnesium basic carbonate filter cake dries 0.5 ~ 5h and obtains white magnesium basic carbonate at 90 ~ 220 DEG C, and this magnesium basic carbonate calcines 0.5 ~ 5h at 450 ~ 900 DEG C, obtains light magnesium oxide.The method can process in a large number to phosphorus mine tailing, and the magnesium oxide product obtained can bring certain economic benefit.But this kind of method has only recycled the magnesium in phosphorus mine tailing, and make full use of other useful elements in phosphorus mine tailing, cause the waste of raw material, the economic benefit obtained is not high.
In sum, develop a kind of technology of the phosphorus in phosphorus mine tailing being carried out recycle and carry out other useful elements in phosphorus mine tailing effectively to utilize, for solving the problem of phosphorus mine tailing bulk deposition and alleviating the day by day exhausted present situation of phosphate rock resource, there is important economic implications and environment protection significance.
Summary of the invention
In view of this, the object of this invention is to provide a kind of phosphorus mine tailing and extract phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, to solve phosphorus mine tailing bulk deposition, cause a large amount of soil occupied, bring environmental pollution, cause land deterioration, vegetation is destroyed, and threatens the problem of the safety of people and animals.
For solving the problems of the technologies described above, the present inventor, for the characteristic of phosphorus mine tailing, carries out deep development research to the comprehensive Utilization Ways of phosphorus mine tailing, through long-term research and constantly test, draws following technical scheme:
A kind of phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, with phosphorus mine tailing for raw material, it is at high temperature calcined, in calcining material, add hot water carry out digestion process, then add ammonium nitrate solution to stir, leaching calcium at 5 ~ 40 DEG C, obtain calcic leach liquor and leached mud, after being adopted by leached mud ammoniumsulphate soln to leach magnesium, obtain phosphorus concentrate and contain magnesium leach liquor, obtain calcium carbonate after calcic leach liquor being adopted volatile salt liquid precipitate, obtain magnesiumcarbonate after volatile salt precipitation being adopted containing magnesium leach liquor, after being calcined by magnesiumcarbonate, namely obtain magnesium oxide.
Described phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, comprises the following steps:
(1) calcine: by the temperature lower calcination 50 ~ 70min of phosphorus mine tailing at 900 ~ 1000 DEG C, obtain calcining material and carbon dioxide, adopt ammoniacal liquor to carry out absorbing carbon dioxide, obtain volatile salt;
(2) digest: the hot water being 60 ~ 100 DEG C by calcining material and temperature mixes, calcining material is (5 ~ 7) with the weight ratio of hot water: 10, and the digestion process time is 30 ~ 50min, obtains digestion slurries;
(3) leaching calcium: slurries and ammonium nitrate solution will be digested with (15 ~ 17): after the weight ratio mixing of (10 ~ 12), 50 ~ 70min is stirred at 5 ~ 40 DEG C, water is adopted to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) leach magnesium: by leached mud and ammoniumsulphate soln with 5:(8 ~ 12) weight ratio mixing after, 50 ~ 70min is stirred at the temperature of 70 ~ 100 DEG C, water is adopted to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, residue is dried and obtains phosphorus concentrate;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 50 ~ 70min at the temperature of 50 ~ 80 DEG C, after then carrying out filtering, wash and dry, obtains calcium carbonate product;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 50 ~ 70min at the temperature of 50 ~ 80 DEG C, then after carrying out filtering, wash and dry, at the temperature lower calcination 40 ~ 60min of 850 ~ 950 DEG C, obtain magnesium oxide product.
Described phosphorus mine tailing is by being abandoned mine tailing after phosphate reverse flotation.
Preferably, in described phosphorus mine tailing, calcium oxide content is 30 ~ 45%, and content of magnesia is 11 ~ 20%, and the content of Vanadium Pentoxide in FLAKES is 5 ~ 12%.
More preferably, in described phosphorus mine tailing, phosphorus pentoxide content is 6.5 ~ 8.4%, calcium oxide content is 34.0 ~ 36.0%, content of magnesia is 17.0 ~ 19.0%.
Preferably, the concentration of described ammonium nitrate solution is 10 ~ 50%.
Preferably, the concentration of described sal volatile is 10 ~ 35%.
Preferably, the concentration of described ammoniumsulphate soln is 20 ~ 40%.
Preferably, in described step (3), after digestion slurries and ammonium nitrate solution are mixed with the weight ratio of 10:11,60min is stirred at 20 ~ 30 DEG C, water is adopted to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain calcic leach liquor and leached mud.
Preferably, in described step (4), after leached mud and ammoniumsulphate soln are mixed with the weight ratio of 5:10,60min is stirred at the temperature of 85 DEG C, adopt water to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, residue is dried and obtains phosphorus concentrate.
In described step (5), gained filtrate recycles the operation in leaching calcium.
In described step (6), gained filtrate recycles the operation in leaching magnesium.
Described phosphorus concentrate is as the raw material preparing phosphoric acid or phosphate fertilizer.
Beneficial effect of the present invention is:
1, the present invention with phosphorus mine tailing for main raw material prepares phosphorus concentrate, calcium carbonate and magnesium oxide, can not only phosphoric in effective recycling phosphorus mine tailing, alleviate the present situation of phosphor resource exhaustion, effectively the useful element calcium in phosphorus mine tailing and magnesium are recycled, the calcium carbonate produced and magnesium oxide have larger economic worth, there is obvious economic benefit, and mass disposal can be carried out to phosphorus mine tailing, efficiently solve phosphorus mine tailing bulk deposition and a large amount of soils brought are occupied and the technical problem such as environmental pollution.
2, the present invention is by first calcining phosphorus mine tailing at a certain temperature, effectively the materials such as the rhombspar in phosphorus mine tailing are decomposed, then with after hot water digestion, leaching calcium is carried out again with ammonium nitrate, and by the control to the time leached and temperature, can guarantee that the leaching yield of calcium is higher, and the leaching yield of magnesium is lower, then leached mud ammonium sulfate is leached, by the control to the time leached and temperature, the leaching yield of magnesium can be made to reach more than 92%, thus guarantee that in the phosphorus concentrate obtained, magnesian content is lower than 1.5%, this phosphorus concentrate is made to can be used in phosphoric acid by wet process and production of phosphate fertilizer.
3, the present invention in process of production, all recycles leached mud and leach liquor, do not have outside sewage effluent and solid waste, to environment, can not have significant environment protection significance.
Beneficial effect of the present invention is verified below with experiment:
Experimental raw:
Phosphorus mine tailing, ammonium nitrate, volatile salt and ammonium sulfate.Wherein, in phosphorus mine tailing, phosphorus pentoxide content is 7.23%, calcium oxide content is 34.94%, content of magnesia is 17.65%, iron oxide content is 0.22%, alumina content is 0.24%, Oil repellent is 0.62%; The purity of ammonium nitrate is 99%, and concentration is 25%; Volatile salt be adopt nitrogen content be more than or equal to 17.4% bicarbonate of ammonia and concentration be 25% ammoniacal liquor formulated, the concentration of volatile salt is 30%; Ammonium sulfate is agricultural ammonium sulfate, and its nitrogen content is greater than 21%.
Experimental installation:
Retort furnace, electronic thermostatic agitator, glass beaker, temperature adjustable electrically heated device, thermometer, filter flask, funnel and water-jet exhauster.
Experimental procedure:
1), get 100g phosphorus mine tailing and calcine in retort furnace, controlling calcining temperature is 900 ~ 1000 DEG C, and calcination time is 1h, obtains 62.6g calcining material.Analyze the composition of calcining material, various composition is as table 1:
Table 1
2), the hot water that calcining material 100g temperature is 95 DEG C is carried out digestion process, acquisition digestion slurries.A. verify that different ammonium nitrate consumption is for the impact of calcium, magnesium leaching yield (in one's power the leaching yield of calcium, magnesium can leach after referring to calcine calcium magnesium), in digestion slurries, add ammonium nitrate, at 5 ~ 40 DEG C, stir leaching 60min, result is as table 2:
Table 2
From experimental result, along with the increase of ammonium nitrate consumption, the leaching yield change of calcium is little, and the leaching yield of magnesium significantly increases, and ammonium nitrate consumption is very few, and filtration and the washing of slip are very difficult.
B. verify that leaching temperature is on the impact of calcium, magnesium leaching yield, the add-on controlling ammonium nitrate is 100g, and leaching time is 1h, and result is as table 3:
Table 3
Temperature | 20~25℃ | 65~75℃ | 85~90℃ |
Calcium leaching yield (%) | 72.43 | 72.78 | 72.38 |
Magnesium leaching yield (%) | 7.99 | 24.40 | 33.08 |
Along with the raising of temperature, the leaching yield change of calcium is little, and the leaching yield of magnesium has raising by a relatively large margin, therefore, lower temperature should be adopted to leach.
Be 100g by ammonium nitrate consumption, leaching time is 1h, temperature is obtain leach liquor under the condition of 20 ~ 25 DEG C and leached mud is analyzed, result is as table 4:
Table 4
In leach liquor, add sal volatile, temperature of reaction is 60 DEG C, and the reaction times is 1h, and the calcium carbonate product purity of acquisition is more than 93%.
3), by above-mentioned leached mud 50g ammonium sulfate leach magnesium, at the temperature of 85 DEG C, leach 60min, obtain containing magnesium leach liquor and filter residue, detected result is as table 5:
Table 5
Ammonium sulfate consumption (g) | 60 | 80 | 100 |
Calcium leaching yield (%) | 1.16 | 2.93 | 2.17 |
Magnesium leaching yield (%) | 89.5 | 91.2 | 99.0 |
Along with the increase of ammonium sulfate consumption, the leaching yield of calcium slightly increases, and the leaching yield of magnesium significantly increases.
The filter residue obtained after leaching magnesium by adopting 100g ammonium sulfate obtains phosphorus concentrate after drying, and after testing, in this phosphorus concentrate, the content of Vanadium Pentoxide in FLAKES is 35.63%, and magnesian content is 1.12%.
To adopt sal volatile precipitation containing magnesium leach liquor, temperature of reaction is 60 DEG C, and the reaction times is 1h, and after crossing the oven dry of leaching filter residue, under the high temperature of 900 DEG C, calcine 1h, obtain magnesium oxide product, detected by magnesium oxide product, its purity is more than 95%.
Embodiment
Conveniently those skilled in the art will recognize that the present invention will be further described below in conjunction with embodiment.Embodiment is only illustrating this invention, is not limitation of the invention, and the step not doing in embodiment to illustrate is all prior arts, is not described in detail at this.
The main chemical reactions equation that the present invention relates to is as follows:
Reaction formula one:
CaCO
3·MgCO
3→CaO+MgO+2CO
2
Reaction formula two:
CaO+MgO+2H
2O→Ca(OH)
2+Mg(OH)
2
Reaction formula three:
Ca(OH)
2+2NH
4NO
3→Ca(NO
3)
2+2NH
3+2H
2O
Reaction formula four:
Mg(OH)
2+(NH
4)
2SO
4→MgSO
4+2NH
3+2H
2O
Reaction formula five:
Ca(NO
3)
2+(NH
4)
2CO
3→CaCO
3+2NH
4NO
3
Reaction formula six:
MgSO
4+(NH
4)
2CO
3→MgCO
3+(NH
4)
2SO
4
Embodiment one
A kind of phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, comprises the following steps:
(1) calcine: phosphorus mine tailing is sent into the temperature lower calcination 50min at 900 DEG C in calcining furnace, obtain calcining material and carbon dioxide, carbon dioxide is passed in absorption tower, adopt ammoniacal liquor to absorb, obtain sal volatile;
(2) digest: the hot water being 60 DEG C by calcining material and temperature is sent in digestive shelf and mixed, and calcining material is 5:10 with the weight ratio of hot water, and the digestion process time is 30min, obtains digestion slurries;
(3) leaching calcium: by digestion slurries and ammonium nitrate solution with the weight ratio of 15:10 send into leaching groove in mixing after, 50min is stirred at 5 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid carried out successively filtering and washing, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) magnesium is leached: to send in leaching groove after mixing by leached mud and ammoniumsulphate soln with the weight ratio of 5:8,50min is stirred at the temperature of 70 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, dried by residue and obtain phosphorus concentrate, described phosphorus concentrate is as the raw material preparing phosphoric acid or phosphate fertilizer;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 50min at the temperature of 50 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, obtain calcium carbonate finished product, filtrate recycles the operation in leaching calcium;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 50min at the temperature of 50 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, at the temperature lower calcination 40min of 850 DEG C, obtain magnesium oxide finished product, gained filtrate recycles the operation in leaching magnesium.
In described phosphorus mine tailing, calcium oxide content is 34%, and content of magnesia is 19%, and phosphorus pentoxide content is 6.5%; The concentration of ammonium nitrate solution is 10%; The concentration of sal volatile is 10%; The concentration of ammoniumsulphate soln is 20%.
Adopt this art breading phosphorus mine tailing, the leaching yield of calcium is 72.5%, and the leaching yield of magnesium is 91.3%, and the purity of calcium carbonate is 93.9%, and magnesian purity is 96.7%, and in phosphorus concentrate, the content of Vanadium Pentoxide in FLAKES is 34.46%, and magnesian content is 1.13%.
Embodiment two
A kind of phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, comprises the following steps:
(1) calcine: phosphorus mine tailing is sent into the temperature lower calcination 70min at 1000 DEG C in calcining furnace, obtain calcining material and carbon dioxide, carbon dioxide is passed in absorption tower, adopt ammoniacal liquor to absorb, obtain sal volatile;
(2) digest: the hot water being 100 DEG C by calcining material and temperature is sent in digestive shelf and mixed, and calcining material is 7:10 with the weight ratio of hot water, and the digestion process time is 50min, obtains digestion slurries;
(3) leaching calcium: by digestion slurries and ammonium nitrate solution with the weight ratio of 17:12 send into leaching groove in mixing after, 70min is stirred at 40 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid carried out successively filtering and washing, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) magnesium is leached: to send in leaching groove after mixing by leached mud and ammoniumsulphate soln with the weight ratio of 5:12,70min is stirred at the temperature of 100 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, dried by residue and obtain phosphorus concentrate, described phosphorus concentrate is as the raw material preparing phosphoric acid or phosphate fertilizer;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 70min at the temperature of 80 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, obtain calcium carbonate finished product, filtrate recycles the operation in leaching calcium;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 70min at the temperature of 80 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, at the temperature lower calcination 60min of 950 DEG C, obtain magnesium oxide finished product, gained filtrate recycles the operation in leaching magnesium.
In described phosphorus mine tailing, calcium oxide content is 36%, and content of magnesia is 17%, and phosphorus pentoxide content is 8.4%; The concentration of ammonium nitrate solution is 50%; The concentration of sal volatile is 35%; The concentration of ammoniumsulphate soln is 40%.
Adopt this art breading phosphorus mine tailing, the leaching yield of calcium is 72.4%, and the leaching yield of magnesium is 99.1%, and the purity of calcium carbonate is 93.6%, and magnesian purity is 95.3%, and in phosphorus concentrate, the content of Vanadium Pentoxide in FLAKES is 35.86%, and magnesian content is 1.04%.
Embodiment three
A kind of phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, comprises the following steps:
(1) calcine: phosphorus mine tailing is sent into the temperature lower calcination 55min at 930 DEG C in calcining furnace, obtain calcining material and carbon dioxide, carbon dioxide is passed in absorption tower, adopt ammoniacal liquor to absorb, obtain sal volatile;
(2) digest: the hot water being 70 DEG C by calcining material and temperature is sent in digestive shelf and mixed, and calcining material is 6:10 with the weight ratio of hot water, and the digestion process time is 45min, obtains digestion slurries;
(3) leaching calcium: by digestion slurries and ammonium nitrate solution with the weight ratio of 16:10 send into leaching groove in mixing after, 55min is stirred at 20 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid carried out successively filtering and washing, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) magnesium is leached: to send in leaching groove after mixing by leached mud and ammoniumsulphate soln with the weight ratio of 5:9,55min is stirred at the temperature of 75 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, dried by residue and obtain phosphorus concentrate, described phosphorus concentrate is as the raw material preparing phosphoric acid or phosphate fertilizer;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 55min at the temperature of 60 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, obtain calcium carbonate finished product, filtrate recycles the operation in leaching calcium;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 60min at the temperature of 60 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, at the temperature lower calcination 45min of 880 DEG C, obtain magnesium oxide finished product, gained filtrate recycles the operation in leaching magnesium.
In described phosphorus mine tailing, calcium oxide content is 35%, and content of magnesia is 18%, and phosphorus pentoxide content is 6.9%; The concentration of described ammonium nitrate solution is 25%; The concentration of sal volatile is 30%; The concentration of ammoniumsulphate soln is 25%.
Adopt this art breading phosphorus mine tailing, the leaching yield of calcium is 72.3%, and the leaching yield of magnesium is 92.7%, and the purity of calcium carbonate is 93.6%, and magnesian purity is 96.5%, and in phosphorus concentrate, the content of Vanadium Pentoxide in FLAKES is 35.37%, and magnesian content is 1.19%.
Embodiment four
A kind of phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, comprises the following steps:
(1) calcine: phosphorus mine tailing is sent into the temperature lower calcination 65min at 970 DEG C in calcining furnace, obtain calcining material and carbon dioxide, carbon dioxide is passed in absorption tower, adopt ammoniacal liquor to absorb, obtain volatile salt;
(2) digest: the hot water being 90 DEG C by calcining material and temperature is sent in digestive shelf and mixed, and calcining material is 6:10 with the weight ratio of hot water, and the digestion process time is 45min, obtains digestion slurries;
(3) leaching calcium: by digestion slurries and ammonium nitrate solution with the weight ratio of 16:12 send into leaching groove in mixing after, 65min is stirred at 30 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid carried out successively filtering and washing, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) magnesium is leached: to send in leaching groove after mixing by leached mud and ammoniumsulphate soln with the weight ratio of 5:11,65min is stirred at the temperature of 90 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, dried by residue and obtain phosphorus concentrate, described phosphorus concentrate is as the raw material preparing phosphoric acid or phosphate fertilizer;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 65min at the temperature of 70 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, obtain calcium carbonate finished product, filtrate recycles the operation in leaching calcium;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 65min at the temperature of 65 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, at the temperature lower calcination 55min of 920 DEG C, obtain magnesium oxide finished product, gained filtrate recycles the operation in leaching magnesium.
In described phosphorus mine tailing, calcium oxide content is 35%, and content of magnesia is 18%, and phosphorus pentoxide content is 7.2%; The concentration of ammonium nitrate solution is 25%; The concentration of sal volatile is 30%; The concentration of ammoniumsulphate soln is 25%.
Adopt this art breading phosphorus mine tailing, the leaching yield of calcium is 72.6%, and the leaching yield of magnesium is 99.0%, and the purity of calcium carbonate is 93.6%, and magnesian purity is 95.4%, and in phosphorus concentrate, the content of Vanadium Pentoxide in FLAKES is 35.73%, and magnesian content is 1.04%.
Embodiment five
A kind of phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, comprises the following steps:
(1) calcine: phosphorus mine tailing is sent into the temperature lower calcination 60min at 950 DEG C in calcining furnace, obtain calcining material and carbon dioxide, carbon dioxide is passed in absorption tower, adopt ammoniacal liquor to absorb, obtain volatile salt;
(2) digest: the hot water being 95 DEG C by calcining material and temperature is sent in digestive shelf and mixed, and calcining material is 6:10 with the weight ratio of hot water, and the digestion process time is 40min, obtains digestion slurries;
(3) leaching calcium: by digestion slurries and ammonium nitrate solution with the weight ratio of 16:11 send into leaching groove in mixing after, 60min is stirred at 25 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid carried out successively filtering and washing, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) magnesium is leached: to send in leaching groove after mixing by leached mud and ammoniumsulphate soln with the weight ratio of 5:10,60min is stirred at the temperature of 85 DEG C, the ammonia that reaction produces is passed in absorption tower, water is adopted to absorb, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, dried by residue and obtain phosphorus concentrate, described phosphorus concentrate is as the raw material preparing phosphoric acid or phosphate fertilizer;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 60min at the temperature of 60 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, obtain calcium carbonate finished product, filtrate recycles the operation in leaching calcium;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 60min at the temperature of 60 DEG C, then filter, obtain filtrate and filter residue, by residue washing and after drying, at the temperature lower calcination 50min of 900 DEG C, obtain magnesium oxide finished product, gained filtrate recycles the operation in leaching magnesium.
In described phosphorus mine tailing, calcium oxide content is 35%, and content of magnesia is 18%, and phosphorus pentoxide content is 7.4%; The concentration of described ammonium nitrate solution is 25%; The concentration of sal volatile is 30%; The concentration of ammoniumsulphate soln is 25%.
Adopt this art breading phosphorus mine tailing, the leaching yield of calcium is 72.4%, and the leaching yield of magnesium is 99.0%, and the purity of calcium carbonate is 93.4%, and magnesian purity is 95.5%, and in phosphorus concentrate, the content of Vanadium Pentoxide in FLAKES is 35.62%, and magnesian content is 1.03%.
The above, it is only better example of the present invention, not any pro forma restriction is done to the present invention, anyly do not depart from technical solution of the present invention content, the any simple modification done above example according to technical spirit of the present invention, coversion material equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a phosphorus mine tailing extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, it is characterized in that, with phosphorus mine tailing for raw material, it is at high temperature calcined, in calcining material, add hot water carry out digestion process, then add ammonium nitrate solution to stir, leaching calcium at a certain temperature, obtain calcic leach liquor and leached mud, after being adopted by leached mud ammoniumsulphate soln to leach magnesium, obtain phosphorus concentrate and contain magnesium leach liquor, calcium carbonate is obtained after calcic leach liquor being adopted sal volatile precipitation, magnesiumcarbonate will be obtained after adopting sal volatile precipitation containing magnesium leach liquor, namely magnesium oxide is obtained after being calcined by magnesiumcarbonate.
2. phosphorus mine tailing as claimed in claim 1 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, it is characterized in that, comprises the following steps:
(1) calcine: by the temperature lower calcination 50 ~ 70min of phosphorus mine tailing at 900 ~ 1000 DEG C, obtain calcining material and carbon dioxide, adopt ammoniacal liquor to carry out absorbing carbon dioxide, obtain volatile salt;
(2) digest: the hot water being 60 ~ 100 DEG C by calcining material and temperature mixes, calcining material is (5 ~ 7) with the weight ratio of hot water: 10, and the digestion process time is 30 ~ 50min, obtains digestion slurries;
(3) leaching calcium: slurries and ammonium nitrate solution will be digested with (15 ~ 17): after the weight ratio mixing of (10 ~ 12), 50 ~ 70min is stirred at 5 ~ 40 DEG C, water is adopted to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain calcic leach liquor, washing lotion and leached mud, washing lotion reclaims and is used for digestion;
(4) leach magnesium: by leached mud and ammoniumsulphate soln with 5:(8 ~ 12) weight ratio mixing after, 50 ~ 70min is stirred at the temperature of 70 ~ 100 DEG C, water is adopted to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, residue is dried and obtains phosphorus concentrate;
(5) heavy calcium: calcic leach liquor is mixed with sal volatile, after regulating calcium ion concn in mixing solutions equal with carbon acid ion concentration, stirring reaction 50 ~ 70min at the temperature of 50 ~ 80 DEG C, then filter, obtain filtrate and filter residue, filter residue, through washing and after drying, obtains calcium carbonate product;
(6) heavy magnesium: will mix with sal volatile containing magnesium leach liquor, after regulating magnesium ion concentration in mixing solutions equal with carbon acid ion concentration, stirring reaction 50 ~ 70min at the temperature of 50 ~ 80 DEG C, then filter, obtain filtrate and filter residue, filter residue, through washing and after drying, at the temperature lower calcination 40 ~ 60min of 850 ~ 950 DEG C, obtains magnesium oxide product.
3. phosphorus mine tailing as claimed in claim 1 or 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, and it is characterized in that, described phosphorus mine tailing is by being abandoned mine tailing after phosphate reverse flotation.
4. phosphorus mine tailing as claimed in claim 1 or 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, and it is characterized in that, the concentration of described ammonium nitrate solution is 10 ~ 50%.
5. phosphorus mine tailing as claimed in claim 1 or 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, and it is characterized in that, the concentration of described sal volatile is 10 ~ 35%.
6. phosphorus mine tailing as claimed in claim 1 or 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, and it is characterized in that, the concentration of described ammoniumsulphate soln is 20 ~ 40%.
7. phosphorus mine tailing as claimed in claim 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, it is characterized in that, in described step (3), after digestion slurries and ammonium nitrate solution are mixed with the weight ratio of 16:11, at 20-30 DEG C, stir 60min, adopt water to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain calcic leach liquor and leached mud.
8. phosphorus mine tailing as claimed in claim 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, it is characterized in that, in described step (4), after leached mud and ammoniumsulphate soln are mixed with the weight ratio of 5:10,60min is stirred at the temperature of 85 DEG C, water is adopted to absorb ammonia, the ammoniacal liquor of acquisition is used in absorption step (1), react the carbon dioxide generated, reaction feed liquid is carried out successively filter and wash, obtain containing magnesium leach liquor and residue, residue is dried and obtains phosphorus concentrate.
9. phosphorus mine tailing as claimed in claim 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, and it is characterized in that, in described step (5), gained filtrate recycles the operation in leaching calcium.
10. phosphorus mine tailing as claimed in claim 2 extracts phosphorus concentrate co-production calcium carbonate and method of magnesium oxide, it is characterized in that, in described step (6), gained filtrate recycles the operation in leaching 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 |
CN108314584A (en) * | 2018-03-14 | 2018-07-24 | 贵州芭田生态工程有限公司 | A method of the tailing generated using nitrophosphate fertilizer filter residue, calcium ammonium nitrate filter residue, phosphate rock floating prepares soil conditioner |
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 |
CN110872106A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Phosphorite preparation system with balanced processing speed in each link |
CN110872103A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Control liquid balance's phosphate concentrate preparation system |
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 |
CN111302372A (en) * | 2019-12-31 | 2020-06-19 | 黔南民族师范学院 | Method for separating and extracting magnesium and calcium from phosphate tailings treated by secondary ammonium salt |
CN112694115A (en) * | 2021-01-11 | 2021-04-23 | 湖北三宁化工股份有限公司 | Method for preparing high-quality calcium carbonate and magnesium hydroxide by using phosphate tailings |
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 |
CN114348980A (en) * | 2022-01-20 | 2022-04-15 | 贵州芭田生态工程有限公司 | Method for enriching phosphate concentrate and simultaneously recovering calcium nitrate and magnesium nitrate from phosphate ore |
CN115321573A (en) * | 2022-08-31 | 2022-11-11 | 广西川金诺化工有限公司 | Method for preparing light calcium carbonate, magnesium oxide and phosphate concentrate by recycling and treating phosphate tailings |
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CN108314584A (en) * | 2018-03-14 | 2018-07-24 | 贵州芭田生态工程有限公司 | A method of the tailing generated using nitrophosphate fertilizer filter residue, calcium ammonium nitrate filter residue, phosphate rock floating prepares soil conditioner |
CN110872106A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Phosphorite preparation system with balanced processing speed in each link |
CN110872103A (en) * | 2018-08-31 | 2020-03-10 | 贵州芭田生态工程有限公司 | Control liquid balance's phosphate concentrate preparation system |
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 |
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 |
CN111302372A (en) * | 2019-12-31 | 2020-06-19 | 黔南民族师范学院 | Method for separating and extracting magnesium and calcium from phosphate tailings treated by secondary ammonium salt |
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 |
CN112694115A (en) * | 2021-01-11 | 2021-04-23 | 湖北三宁化工股份有限公司 | Method for preparing high-quality calcium carbonate and magnesium hydroxide by using phosphate tailings |
CN114348980A (en) * | 2022-01-20 | 2022-04-15 | 贵州芭田生态工程有限公司 | Method for enriching phosphate concentrate and simultaneously recovering calcium nitrate and magnesium nitrate from phosphate ore |
CN115321573A (en) * | 2022-08-31 | 2022-11-11 | 广西川金诺化工有限公司 | Method for preparing light calcium carbonate, magnesium oxide and phosphate concentrate by recycling and treating phosphate tailings |
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