CN110436435A - The method that circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium chloride whisker - Google Patents
The method that circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium chloride whisker Download PDFInfo
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- CN110436435A CN110436435A CN201910860183.7A CN201910860183A CN110436435A CN 110436435 A CN110436435 A CN 110436435A CN 201910860183 A CN201910860183 A CN 201910860183A CN 110436435 A CN110436435 A CN 110436435A
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- phosphate tailings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
Abstract
The present invention provides a kind of method that circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium chloride whisker, this method first passes through hydrochloric acidolysis, isolate the silicon slag in High-Mg phosphate tailings, pass through stand at low temperature again, the phosphorus in High-Mg phosphate tailings is precipitated in the form of calcium chlorophosphate, then, it is acidified by sulfuric acid, isolate the calcium in High-Mg phosphate tailings, magnesium, finally, magnesium chloride whisker is obtained by concentration, and hydrochloric acid is added in final concentrate, circulation acidleach is carried out to High-Mg phosphate tailings, on the one hand, products obtained therefrom added value can be improved, on the other hand, be conducive to greatly improve the resource utilization rate of High-Mg phosphate tailings, to advantageously account for phosphorus tailing accumulation problem, and then advantageously account for environmental pollution caused by phosphorus tailing, it improves the ecological environment, with tremendous economic, society, environmental benefit.
Description
Technical field
The present invention relates to waste resource utilization technology field, in particular to a kind of circulation acidleach High-Mg phosphate tailings preparation
The method of calcium chlorophosphate and magnesium chloride whisker.
Background technique
Phosphorus tailing mostlys come from ore dressing and extracts remaining tailings after concentrate, and the mining industry belonged in industrial solid castoff is solid
Body waste.Its mineral mainly has dolomite, fluorine phosphorus ash and quartz, and CaO content is about 30.0~34.0%, P2O5Content is about
For 4-8.5%, content of MgO is about 12-18%.
With the increase that phosphorus ore is exploited, the quantity of phosphorus tailing is also being risen rapidly.It can be generated after every 1,000,000 t phosphorus ore is selected
30~400,000 t phosphorus tailings.Currently, phosphorus comprehensive utilization of tailing rate is only 18%, be emitted into after Tailings Dam or dehydration mostly store up to
Tailings stack.Its comprehensive Utilization Ways mainly have new medicament again flotation, recrystallization again flotation, prepare cement, prepare building brick,
Prepare devitrified glass, prepare phosphorus fertiliser containing magnesium etc..But the exploitation of high-efficient collecting agent used in floatation and inhibitor is there are difficulty,
And medicament has greater environmental impacts.Although the exploitation of building material product and fertilizer utilizes phosphorite tailings largely, but attached
Value added low, resource is not utilized rationally.
Summary of the invention
In view of this, the present invention is directed to propose a kind of circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium chloride whisker
Method, it is low to solve existing phosphorus Making Use of Tailings utilization rate, and the problem that added value of product is low.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A method of circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium chloride whisker, comprising the following steps:
1) by after High-Mg phosphate tailings and mixed in hydrochloric acid, acidolysis reaction is carried out, after the acidolysis reaction, filters, obtains
To acid hydrolysis solution A and silicon slag；
2) it after standing the acid hydrolysis solution A under condition of ice bath, is separated by solid-liquid separation, obtains calcium chlorophosphate and acid hydrolysis solution B；
3) under room temperature, certain density sulfuric acid is added dropwise in Xiang Suoshu acid hydrolysis solution B and is aged after heating reaction a period of time, takes out
Filter, obtains acidifying solution C；
4) it by after acidifying solution C concentration, is separated by solid-liquid separation, obtains magnesium chloride whisker and concentrate D；
5) hydrochloric acid is added in Xiang Suoshu concentrate D, carries out the circulation acidolysis reaction of High-Mg phosphate tailings.
Optionally, the concentration of hydrochloric acid described in the step 1) is 8.80-12.07mol/L, and the hydrochloric acid and the height
The mass ratio of magnesium phosphorus tailing is (2.0-2.8): 1.
Optionally, 20-60 DEG C of the reaction temperature of acidolysis reaction described in the step 1), reaction time 20-60min.
Optionally, the ice bath temperature of ice bath described in the step 2) is -10 DEG C -0 DEG C, and the time of repose of the standing is
10-24h。
Optionally, concentration≤10% of sulfuric acid described in the step 3), and the additional amount of the sulfuric acid is the acidolysis
1-1.5 times of the amount of substance of calcium in liquid B.
Optionally, the reaction temperature that reaction is heated described in the step 3) is 70-90 DEG C, reaction time 10-
40min。
Optionally, the digestion time of ageing described in the step 3) is 8-16h.
Optionally, the thickening temperature of concentration described in the step 4) is 80-118 DEG C.
Optionally, hydrochloric acid is added into the concentrate D in the step 5), comprising: salt is added in Xiang Suoshu concentrate D
Acid is to H+Concentration is 8.8-12.8mol/L
Compared with the existing technology, circulation acidleach High-Mg phosphate tailings of the present invention prepare calcium chlorophosphate and magnesium chloride whisker
Method have the advantage that
1, the present invention first passes through hydrochloric acidolysis, isolates the silicon slag in High-Mg phosphate tailings, then by stand at low temperature, make high magnesium
Phosphorus in phosphorus tailing is precipitated in the form of calcium chlorophosphate, then, is acidified by sulfuric acid, and calcium, magnesium in High-Mg phosphate tailings are isolated,
Finally, obtaining magnesium chloride whisker by concentration, and hydrochloric acid is added in final concentrate, High-Mg phosphate tailings are followed
Naphthenic acid leaching, on the one hand, products obtained therefrom added value can be improved, on the other hand, be conducive to the recycling for greatly improving High-Mg phosphate tailings
Utilization rate to advantageously account for phosphorus tailing accumulation problem, and then advantageously accounts for environmental pollution caused by phosphorus tailing, improves life
State environment has tremendous economic, society, environmental benefit.
2, the hydrochloric acid in acidolysis reaction of the present invention can be technical hydrochloric acid, belong to trade waste, to advantageously reduce
The resource utilization cost of High-Mg phosphate tailings, and be conducive to the reducing farmers' burdens and increasing their incomes of enterprise, and the entire High-Mg phosphate tailings resource of the present invention
It is simple to change the process of utilizing, to be conducive to its popularization and industrial applications.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the process flow chart that present invention circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium chloride whisker.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Below in conjunction with drawings and examples, the present invention will be described in detail.
Embodiment 1
As shown in connection with fig. 1, the circulation acidleach High-Mg phosphate tailings of the present embodiment prepare the side of calcium chlorophosphate and magnesium chloride whisker
Method, specifically includes the following steps:
1) technical hydrochloric acid that 520mL mass fraction is 32% (10.34mol/L) is measured to be placed in clean three-necked flask,
261.8g High-Mg phosphate tailings powder is weighed, and gradually High-Mg phosphate tailings are added into three-necked flask, is added to High-Mg phosphate tailings,
Open condensed water, start stirring, flow back 30min at 60 DEG C, progress acidolysis reaction, to acidolysis reaction after, kept the temperature at 60 DEG C
It filters, obtains acid hydrolysis solution A and silicon slag, wherein silicon slag distills water washing silicon slag three times with 100mL, and by a water lotion and acid
Solve liquid A mixing；
2) acid hydrolysis solution A is poured into dry beaker, is placed in -2 DEG C of ice baths, stand 11h, make the calcium chlorophosphate analysis of white
Out completely after, at -2 DEG C keep the temperature filtering, make to be separated by solid-liquid separation, obtain calcium chlorophosphate and acid hydrolysis solution B；
3) it measures 98% sulfuric acid of 132mL and is added dropwise in acid hydrolysis solution B after being diluted to concentration≤10%, wherein dilution
The additional amount of sulfuric acid afterwards is 1 times of the amount of substance of calcium in acid hydrolysis solution B, opens stirring, gradually has white heavy in whipping process
It forms sediment and generates, finished to sulfuric acid addition, be heated to 85 DEG C, after the reaction was continued 30min, be aged 12h, filter, obtain acidifying solution C and sulphur
Sour calcium precipitate, wherein calcium sulfate precipitation 300mL distills water washing precipitating three times, and the calcium sulfate that high length-diameter ratio can be obtained is brilliant
Must, and a water lotion for washing calcium sulfate precipitation can be mixed for the concentration of step 4) with acidifying solution C；
4) acidifying solution C is placed in dry beaker, is heated to 118 DEG C, is stirred continuously in heating process, make acidifying solution C
It is constantly concentrated by evaporation, to there is epitaxial generation in beaker, stops heating, be cooled to room temperature, filter, obtain magnesium chloride whisker and concentration
Liquid D, wherein magnesium chloride whisker with ethanol washing three times after, drying；
5) hydrochloric acid is added into concentrate D, obtains MH +For the mixed solution of 10.8mol/L, can be used as sour in step 1)
The solution of High-Mg phosphate tailings is solved, to realize the circulation acidolysis reaction of High-Mg phosphate tailings.
Embodiment 2
As shown in connection with fig. 1, the circulation acidleach High-Mg phosphate tailings of the present embodiment prepare the side of calcium chlorophosphate and magnesium chloride whisker
Method, specifically includes the following steps:
1) technical hydrochloric acid that 513mL mass fraction is 33% (10.41mol/L) is measured to be placed in clean three-necked flask,
261.8g High-Mg phosphate tailings powder is weighed, and gradually High-Mg phosphate tailings are added into three-necked flask, is added to High-Mg phosphate tailings,
Open condensed water, start stirring, flow back 20min at 45 DEG C, progress acidolysis reaction, to acidolysis reaction after, kept the temperature at 60 DEG C
It filters, obtains acid hydrolysis solution A and silicon slag, wherein silicon slag distills water washing silicon slag three times with 100mL, and by a water lotion and acid
Solve liquid A mixing；
2) acid hydrolysis solution A is poured into dry beaker, is placed in -8 DEG C of ice baths, stand 8h, make the calcium chlorophosphate analysis of white
Out completely after, at -8 DEG C keep the temperature filtering, make to be separated by solid-liquid separation, obtain calcium chlorophosphate and acid hydrolysis solution B；
3) it measures 98% sulfuric acid of 165mL and is added dropwise in acid hydrolysis solution B after being diluted to concentration≤10%, wherein dilution
The additional amount of sulfuric acid afterwards is 1.14 times of the amount of substance of calcium in acid hydrolysis solution B, opens stirring, gradually there is white in whipping process
Precipitating generates, and finishes to sulfuric acid addition, is heated to 87 DEG C, after the reaction was continued 20min, is aged 10h, filters, obtain acidifying solution C and
Calcium sulfate precipitation, wherein calcium sulfate precipitation 300mL distills water washing precipitating three times, and the calcium sulfate of high length-diameter ratio can be obtained
Whisker, and a water lotion for washing calcium sulfate precipitation can be mixed for the concentration of step 4) with acidifying solution C；
4) acidifying solution C is placed in dry beaker, is heated to 102 DEG C, is stirred continuously in heating process, make acidifying solution C
It is constantly concentrated by evaporation, to there is epitaxial generation in beaker, stops heating, be cooled to room temperature, filter, obtain magnesium chloride whisker and concentration
Liquid D, wherein magnesium chloride whisker with ethanol washing three times after, drying；
5) hydrochloric acid is added into concentrate D, obtains MH +For the mixed solution of 10.8mol/L, can be used as sour in step 1)
The solution of High-Mg phosphate tailings is solved, to realize the circulation acidolysis reaction of High-Mg phosphate tailings.
Embodiment 3
As shown in connection with fig. 1, the circulation acidleach High-Mg phosphate tailings of the present embodiment prepare the side of calcium chlorophosphate and magnesium chloride whisker
Method, specifically includes the following steps:
1) technical hydrochloric acid that 493mL mass fraction is 34% (10.76mol/L) is measured to be placed in clean three-necked flask,
261.8g High-Mg phosphate tailings powder is weighed, and gradually High-Mg phosphate tailings are added into three-necked flask, is added to High-Mg phosphate tailings,
Open condensed water, start stirring, flow back 35min at 35 DEG C, progress acidolysis reaction, to acidolysis reaction after, kept the temperature at 60 DEG C
It filters, obtains acid hydrolysis solution A and silicon slag, wherein silicon slag distills water washing silicon slag three times with 100mL, and by a water lotion and acid
Solve liquid A mixing；
2) acid hydrolysis solution A is poured into dry beaker, is placed in -11 DEG C of ice baths, stand 5.5h, make the calcium chlorophosphate of white
After being precipitated completely, filtering is kept the temperature at -11 DEG C, makes to be separated by solid-liquid separation, obtains calcium chlorophosphate and acid hydrolysis solution B；
3) it measures 98% sulfuric acid of 172mL and is added dropwise in acid hydrolysis solution B after being diluted to concentration≤10%, wherein dilution
The additional amount of sulfuric acid afterwards is 1.20 times of the amount of substance of calcium in acid hydrolysis solution B, opens stirring, gradually there is white in whipping process
Precipitating generates, and finishes to sulfuric acid addition, is heated to 90 DEG C, after the reaction was continued 20min, is aged 9h, filters, obtain acidifying solution C and
Calcium sulfate precipitation, wherein calcium sulfate precipitation 300mL distills water washing precipitating three times, and the calcium sulfate of high length-diameter ratio can be obtained
Whisker, and a water lotion for washing calcium sulfate precipitation can be mixed for the concentration of step 4) with acidifying solution C；
4) acidifying solution C is placed in dry beaker, is heated to 90 DEG C, is stirred continuously in heating process, make acidifying solution C not
It is disconnected to be concentrated by evaporation, to there is epitaxial generation in beaker, stop heating, be cooled to room temperature, filters, obtain magnesium chloride whisker and concentrate
D, wherein magnesium chloride whisker with ethanol washing three times after, drying；
5) hydrochloric acid is added into concentrate D, obtains MH +For the mixed solution of 10.8mol/L, can be used as sour in step 1)
The solution of High-Mg phosphate tailings is solved, to realize the circulation acidolysis reaction of High-Mg phosphate tailings.
Embodiment 4
As shown in connection with fig. 1, the circulation acidleach High-Mg phosphate tailings of the present embodiment prepare the side of calcium chlorophosphate and magnesium chloride whisker
Method, specifically includes the following steps:
1) technical hydrochloric acid that 450mL mass fraction is 37% (11.43mol/L) is measured to be placed in clean three-necked flask,
261.8g High-Mg phosphate tailings powder is weighed, and gradually High-Mg phosphate tailings are added into three-necked flask, is added to High-Mg phosphate tailings,
Open condensed water, start stirring, flow back 55min at 20 DEG C, progress acidolysis reaction, to acidolysis reaction after, kept the temperature at 60 DEG C
It filters, obtains acid hydrolysis solution A and silicon slag, wherein silicon slag distills water washing silicon slag three times with 100mL, and by a water lotion and acid
Solve liquid A mixing；
2) acid hydrolysis solution A is poured into dry beaker, is placed in 0 DEG C of ice bath, stand 15h, make the calcium chlorophosphate analysis of white
Out completely after, at 0 DEG C keep the temperature filtering, make to be separated by solid-liquid separation, obtain calcium chlorophosphate and acid hydrolysis solution B；
3) it measures 98% sulfuric acid of 185mL and is added dropwise in acid hydrolysis solution B after being diluted to concentration≤10%, wherein dilution
The additional amount of sulfuric acid afterwards is 1.21 times of the amount of substance of calcium in acid hydrolysis solution B, opens stirring, gradually there is white in whipping process
Precipitating generates, and finishes to sulfuric acid addition, is heated to 70 DEG C, after the reaction was continued 45min, is aged 12h, filters, obtain acidifying solution C and
Calcium sulfate precipitation, wherein calcium sulfate precipitation 300mL distills water washing precipitating three times, and the calcium sulfate of high length-diameter ratio can be obtained
Whisker, and a water lotion for washing calcium sulfate precipitation can be mixed for the concentration of step 4) with acidifying solution C；
4) acidifying solution C is placed in dry beaker, is heated to 80 DEG C, is stirred continuously in heating process, make acidifying solution C not
It is disconnected to be concentrated by evaporation, to there is epitaxial generation in beaker, stop heating, be cooled to room temperature, filters, obtain magnesium chloride whisker and concentrate
D, wherein magnesium chloride whisker with ethanol washing three times after, drying；
5) hydrochloric acid is added into concentrate D, obtains MH +For the mixed solution of 10.8mol/L, can be used as sour in step 1)
The solution of High-Mg phosphate tailings is solved, to realize the circulation acidolysis reaction of High-Mg phosphate tailings.
Embodiment 5
As shown in connection with fig. 1, the circulation acidleach High-Mg phosphate tailings of the present embodiment prepare the side of calcium chlorophosphate and magnesium chloride whisker
Method, specifically includes the following steps:
1) it measures the technical hydrochloric acid that 560mL mass fraction is 27% (9.71mol/L) to be placed in clean three-necked flask, claim
261.8g High-Mg phosphate tailings powder is taken, and gradually High-Mg phosphate tailings are added into three-necked flask, adds, beats to High-Mg phosphate tailings
Open condensed water, start stirring, flow back 60min at 55 DEG C, carry out acidolysis reaction, to acidolysis reaction after, at 60 DEG C keep the temperature take out
Filter, obtains acid hydrolysis solution A and silicon slag, wherein silicon slag distills water washing silicon slag three times with 100mL, and by a water lotion and acidolysis
Liquid A mixing；
2) acid hydrolysis solution A is poured into dry beaker, is placed in -3 DEG C of ice baths, stand 11h, make the calcium chlorophosphate analysis of white
Out completely after, at -3 DEG C keep the temperature filtering, make to be separated by solid-liquid separation, obtain calcium chlorophosphate and acid hydrolysis solution B；
3) it measures 98% sulfuric acid of 200mL and is added dropwise in acid hydrolysis solution B after being diluted to concentration≤10%, wherein dilution
The additional amount of sulfuric acid afterwards is 1.38 times of the amount of substance of calcium in acid hydrolysis solution B, opens stirring, gradually there is white in whipping process
Precipitating generates, and finishes to sulfuric acid addition, is heated to 85 DEG C, after the reaction was continued 25min, is aged 14h, filters, obtain acidifying solution C and
Calcium sulfate precipitation, wherein calcium sulfate precipitation 300mL distills water washing precipitating three times, and the calcium sulfate of high length-diameter ratio can be obtained
Whisker, and a water lotion for washing calcium sulfate precipitation can be mixed for the concentration of step 4) with acidifying solution C；
4) acidifying solution C is placed in dry beaker, is heated to 112 DEG C, is stirred continuously in heating process, make acidifying solution C
It is constantly concentrated by evaporation, to there is epitaxial generation in beaker, stops heating, be cooled to room temperature, filter, obtain magnesium chloride whisker and concentration
Liquid D, wherein magnesium chloride whisker with ethanol washing three times after, drying；
5) hydrochloric acid is added into concentrate D, obtains MH +For the mixed solution of 10.8mol/L, can be used as sour in step 1)
The solution of High-Mg phosphate tailings is solved, to realize the circulation acidolysis reaction of High-Mg phosphate tailings.
Embodiment 6
As shown in connection with fig. 1, the circulation acidleach High-Mg phosphate tailings of the present embodiment prepare the side of calcium chlorophosphate and magnesium chloride whisker
Method, specifically includes the following steps:
1) it measures the technical hydrochloric acid that 537mL mass fraction is 31.6% (10.06mol/L) and is placed in clean three-necked flask
In, weigh 261.8g High-Mg phosphate tailings powder, and gradually High-Mg phosphate tailings are added into three-necked flask, to High-Mg phosphate tailings plus
It is complete, open condensed water, start stirring, flow back 30min at 60 DEG C, progress acidolysis reaction, to acidolysis reaction after, protected at 60 DEG C
Temperature filters, and obtains acid hydrolysis solution A and silicon slag, wherein silicon slag distills water washing silicon slag three times with 100mL, and by water lotion and
Acid hydrolysis solution A mixing；
2) acid hydrolysis solution A is poured into dry beaker, is placed in 0 DEG C of ice bath, stand 12h, make the calcium chlorophosphate analysis of white
Out completely after, at 0 DEG C keep the temperature filtering, make to be separated by solid-liquid separation, obtain calcium chlorophosphate and acid hydrolysis solution B；
3) it measures 98% sulfuric acid of 213mL and is added dropwise in acid hydrolysis solution B after being diluted to concentration≤10%, wherein dilution
The additional amount of sulfuric acid afterwards is 1.38 times of the amount of substance of calcium in acid hydrolysis solution B, opens stirring, gradually there is white in whipping process
Precipitating generates, and finishes to sulfuric acid addition, is heated to 85 DEG C, after the reaction was continued 28min, is aged 16h, filters, obtain acidifying solution C and
Calcium sulfate precipitation, wherein calcium sulfate precipitation 300mL distills water washing precipitating three times, and the calcium sulfate of high length-diameter ratio can be obtained
Whisker, and a water lotion for washing calcium sulfate precipitation can be mixed for the concentration of step 4) with acidifying solution C；
4) acidifying solution C is placed in dry beaker, is heated to 107 DEG C, is stirred continuously in heating process, make acidifying solution C
It is constantly concentrated by evaporation, to there is epitaxial generation in beaker, stops heating, be cooled to room temperature, filter, obtain magnesium chloride whisker and concentration
Liquid D, wherein magnesium chloride whisker with ethanol washing three times after, drying；
5) hydrochloric acid is added into concentrate D, obtains MH +For the mixed solution of 10.8mol/L, can be used as sour in step 1)
The solution of High-Mg phosphate tailings is solved, to realize the circulation acidolysis reaction of High-Mg phosphate tailings.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of circulation acidleach High-Mg phosphate tailings method for preparing calcium chlorophosphate and magnesium chloride whisker, which is characterized in that including with
Lower step:
1) by after High-Mg phosphate tailings and mixed in hydrochloric acid, acidolysis reaction is carried out, after the acidolysis reaction, filters, obtains acid
Solve liquid A and silicon slag；
2) it after standing the acid hydrolysis solution A under condition of ice bath, is separated by solid-liquid separation, obtains calcium chlorophosphate and acid hydrolysis solution B；
3) under room temperature, certain density sulfuric acid is added dropwise in Xiang Suoshu acid hydrolysis solution B and is aged after heating reaction a period of time, filters,
Obtain acidifying solution C；
4) it by after acidifying solution C concentration, is separated by solid-liquid separation, obtains magnesium chloride whisker and concentrate D；
5) hydrochloric acid is added in Xiang Suoshu concentrate D, carries out the circulation acidolysis reaction of High-Mg phosphate tailings.
2. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, the concentration of hydrochloric acid described in the step 1) is 8.80-12.07mol/L, and the hydrochloric acid and the high magnesium phosphorus tail
The mass ratio of mine is (2.0-2.8): 1.
3. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, 20-60 DEG C of the reaction temperature of acidolysis reaction described in the step 1), reaction time 20-60min.
4. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, the ice bath temperature of ice bath described in the step 2) is -10 DEG C -0 DEG C, and the time of repose of the standing is 10-
24h。
5. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, concentration≤10% of sulfuric acid described in the step 3), and the additional amount of the sulfuric acid is calcium in the acid hydrolysis solution B
1-1.5 times of amount of substance.
6. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, the reaction temperature that reaction is heated described in the step 3) is 70-90 DEG C, reaction time 10-40min.
7. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, the digestion time of ageing described in the step 3) is 8-16h.
8. the method that circulation acidleach High-Mg phosphate tailings according to claim 1 prepare calcium chlorophosphate and magnesium chloride whisker,
It is characterized in that, the thickening temperature of concentration described in the step 4) is 80-118 DEG C.
9. the resource utilization method of circulation acidleach High-Mg phosphate tailings according to claim 1, which is characterized in that the step
It is rapid 5) in hydrochloric acid is added into the concentrate D, comprising: hydrochloric acid is added in Xiang Suoshu concentrate D to H+Concentration is 8.8-
12.8mol/L。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111304749A (en) * | 2020-02-27 | 2020-06-19 | 武汉工程大学 | Method for preparing gypsum whisker and composite flame retardant by circulating acid leaching of phosphate tailings |
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| CN103922372A (en) * | 2014-04-11 | 2014-07-16 | 武汉工程大学 | Method for recovering phosphorus in phosphate tailings with high magnesium content and preparing magnesium sulfate by adopting indirect sulfuric acid method |
| CN105274622A (en) * | 2015-11-16 | 2016-01-27 | 武汉工程大学 | Method for preparing magnesium hydrate crystal whiskers and calcium sulfate with phosphate tailings as raw material |
| CN109290060A (en) * | 2018-11-29 | 2019-02-01 | 武汉工程大学 | A kind of process for subsequent treatment and phosphate ore floatation method of phosphate ore flotation tailings |
-
2019
- 2019-09-11 CN CN201910860183.7A patent/CN110436435A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922372A (en) * | 2014-04-11 | 2014-07-16 | 武汉工程大学 | Method for recovering phosphorus in phosphate tailings with high magnesium content and preparing magnesium sulfate by adopting indirect sulfuric acid method |
| CN105274622A (en) * | 2015-11-16 | 2016-01-27 | 武汉工程大学 | Method for preparing magnesium hydrate crystal whiskers and calcium sulfate with phosphate tailings as raw material |
| CN109290060A (en) * | 2018-11-29 | 2019-02-01 | 武汉工程大学 | A kind of process for subsequent treatment and phosphate ore floatation method of phosphate ore flotation tailings |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304749A (en) * | 2020-02-27 | 2020-06-19 | 武汉工程大学 | Method for preparing gypsum whisker and composite flame retardant by circulating acid leaching of phosphate tailings |
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Application publication date: 20191112 |