CN110484970A - A kind of recycling processing method of High-Mg phosphate tailings - Google Patents

A kind of recycling processing method of High-Mg phosphate tailings Download PDF

Info

Publication number
CN110484970A
CN110484970A CN201910860847.XA CN201910860847A CN110484970A CN 110484970 A CN110484970 A CN 110484970A CN 201910860847 A CN201910860847 A CN 201910860847A CN 110484970 A CN110484970 A CN 110484970A
Authority
CN
China
Prior art keywords
phosphate tailings
processing method
recycling processing
reaction
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910860847.XA
Other languages
Chinese (zh)
Other versions
CN110484970B (en
Inventor
张华丽
潘益
吴汉军
潘志权
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Institute of Technology
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CN201910860847.XA priority Critical patent/CN110484970B/en
Publication of CN110484970A publication Critical patent/CN110484970A/en
Application granted granted Critical
Publication of CN110484970B publication Critical patent/CN110484970B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/12Halides
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/46Sulfur-, selenium- or tellurium-containing compounds
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62Whiskers or needles
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B7/00Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The present invention provides a kind of recycling processing method of High-Mg phosphate tailings, the recycling processing 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, the calcium in High-Mg phosphate tailings is isolated by sulfuric acid acidification, magnesium, finally, calcium sulfate crystal whiskers and magnesium chloride whisker are obtained by substep concentration, products obtained therefrom added value is high, and entirely High-Mg phosphate tailings resource utilization process is simple, 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

A kind of recycling processing method of High-Mg phosphate tailings
Technical field
The present invention relates to waste resource utilization technology field, in particular to a kind of recycling treatment of High-Mg phosphate tailings Method.
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 recycling processing method of High-Mg phosphate tailings, to solve existing phosphorus tail Ore resources utilization rate is low, 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 kind of recycling processing method of High-Mg phosphate tailings, 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 and calcium sulfate precipitation;
4) by after calcium sulfate precipitation washing, cleaning solution is stood, calcium sulfate crystal whiskers are obtained;
5) the acidifying solution C is concentrated, filters, obtains calcium sulfate crystal whiskers and concentrate D;
6) the concentrate D is concentrated, filters, obtains magnesium chloride whisker.
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 70-95 DEG C, reaction time 10- 40min。
Optionally, the digestion time of ageing described in the step 3) is 8-16h.
Optionally, the time of repose of standing described in the step 4) is 6-12h.
Optionally, the thickening temperature of concentration described in the step 5) is 80-100 DEG C, the concentrate D and the acidification The volume ratio of liquid C is 0.4-0.6.
Optionally, the thickening temperature of concentration described in the step 6) is 80-118 DEG C.
Compared with the existing technology, the recycling processing method of High-Mg phosphate tailings of the present invention has 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 calcium sulfate crystal whiskers and magnesium chloride whisker by substep concentration, products obtained therefrom added value is high, and entire high magnesium phosphorus Making Use of Tailings is simple using process, is conducive to the resource utilization rate for greatly improving High-Mg phosphate tailings, to advantageously account for Phosphorus tailing accumulates problem, and then advantageously accounts for environmental pollution caused by phosphorus tailing, improves the ecological environment, have 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, to be conducive to that it is promoted and industrialization is answered With.
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 of the recycling treatment of High-Mg phosphate tailings of the present invention.
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 recycling processing method of the High-Mg phosphate tailings of the present embodiment, 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 133mL 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 a water lotion and acidifying solution C are mixed It closes;
4) after calcium sulfate precipitation being distilled water washing with 200mL, cleaning solution 10h is stood, the calcium sulfate of high length-diameter ratio is obtained Whisker;
5) 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, when rear liquid volume to be concentrated is 0.5 times of original volume, i.e., the body of subsequent obtained concentrate D and acidifying solution C When product is than being 0.5, stop concentration, filters, obtain the calcium sulfate crystal whiskers and concentrate D of high length-diameter ratio;
6) concentrate D is placed in dry beaker, is heated to 118 DEG C, is stirred continuously in heating process, make concentrate D 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, wherein Magnesium chloride whisker three times, and is dried with ethanol washing.
Embodiment 2
As shown in connection with fig. 1, the recycling processing method of the High-Mg phosphate tailings of the present embodiment, 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 133mL 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 a water lotion and acidifying solution C are mixed It closes;
4) after calcium sulfate precipitation being distilled water washing with 200mL, cleaning solution 8h is stood, the calcium sulfate for obtaining high length-diameter ratio is brilliant Palpus;
5) 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, when rear liquid volume to be concentrated is 0.45 times of original volume, i.e., subsequent obtained concentrate D and acidifying solution C's When volume ratio is 0.45, stop concentration, filters, obtain the calcium sulfate crystal whiskers and concentrate D of high length-diameter ratio;
6) concentrate D is placed in dry beaker, is heated to 102 DEG C, is stirred continuously in heating process, make concentrate D 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, wherein Magnesium chloride whisker three times, and is dried with ethanol washing.
Embodiment 3
As shown in connection with fig. 1, the recycling processing method of the High-Mg phosphate tailings of the present embodiment, 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, carry out acidolysis reaction, to acidolysis reaction after heat preservation pumping at 60 DEG C 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 -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 a water lotion and acidifying solution C are mixed It closes;
4) after calcium sulfate precipitation being distilled water washing with 200mL, cleaning solution 7h is stood, the calcium sulfate for obtaining high length-diameter ratio is brilliant Palpus;
5) 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, when rear liquid volume to be concentrated is 0.6 times of original volume, i.e., the body of subsequent obtained concentrate D and acidifying solution C When product is than being 0.6, stop concentration, filters, obtain the calcium sulfate crystal whiskers and concentrate D of high length-diameter ratio;
6) concentrate D is placed in dry beaker, is heated to 90 DEG C, is stirred continuously in heating process, make concentrate D 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, wherein chlorine Change magnesium whisker with ethanol washing three times, and dries.
Embodiment 4
As shown in connection with fig. 1, the recycling processing method of the High-Mg phosphate tailings of the present embodiment, 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 a water lotion and acidifying solution C are mixed It closes;
4) after calcium sulfate precipitation being distilled water washing with 200mL, cleaning solution 7.5h is stood, the calcium sulfate of high length-diameter ratio is obtained Whisker;
5) acidifying solution C is placed in dry beaker, is heated to 100 DEG C, is stirred continuously in heating process, make acidifying solution C Constantly it is concentrated by evaporation, when rear liquid volume to be concentrated is 0.5 times of original volume, i.e., subsequent obtained concentrate D and acidifying solution C's When volume ratio is 0.5, stop concentration, filters, obtain the calcium sulfate crystal whiskers and concentrate D of high length-diameter ratio;
6) concentrate D is placed in dry beaker, is heated to 80 DEG C, is stirred continuously in heating process, make concentrate D 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, wherein chlorine Change magnesium whisker with ethanol washing three times, and dries.
Embodiment 5
As shown in connection with fig. 1, the recycling processing method of the High-Mg phosphate tailings of the present embodiment, 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 a water lotion and acidifying solution C are mixed It closes;
4) after calcium sulfate precipitation being distilled water washing with 200mL, cleaning solution 12h is stood, the calcium sulfate of high length-diameter ratio is obtained Whisker;
5) acidifying solution C is placed in dry beaker, is heated to 95 DEG C, is stirred continuously in heating process, make acidifying solution C not It is disconnected to be concentrated by evaporation, when rear liquid volume to be concentrated is 0.53 times of original volume, i.e., subsequent obtained concentrate D and acidifying solution C's When volume ratio is 0.53, stop concentration, filters, obtain the calcium sulfate crystal whiskers and concentrate D of high length-diameter ratio;
6) concentrate D is placed in dry beaker, is heated to 112 DEG C, is stirred continuously in heating process, make concentrate D 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, wherein Magnesium chloride whisker three times, and is dried with ethanol washing.
Embodiment 6
As shown in connection with fig. 1, the recycling processing method of the High-Mg phosphate tailings of the present embodiment, 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 80 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 a water lotion and acidifying solution C are mixed It closes;
4) after calcium sulfate precipitation being distilled water washing with 200mL, cleaning solution 9h is stood, the calcium sulfate for obtaining high length-diameter ratio is brilliant Palpus;
5) acidifying solution C is placed in dry beaker, is heated to 85 DEG C, is stirred continuously in heating process, make acidifying solution C not It is disconnected to be concentrated by evaporation, when rear liquid volume to be concentrated is 0.55 times of original volume, i.e., subsequent obtained concentrate D and acidifying solution C's When volume ratio is 0.55, stop concentration, filters, obtain the calcium sulfate crystal whiskers and concentrate D of high length-diameter ratio;
6) concentrate D is placed in dry beaker, is heated to 107 DEG C, is stirred continuously in heating process, make concentrate D 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, wherein Magnesium chloride whisker three times, and is dried with ethanol washing.
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 (10)

1. a kind of recycling processing method of High-Mg phosphate tailings, which comprises 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 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 and calcium sulfate precipitation;
4) by after calcium sulfate precipitation washing, cleaning solution is stood, calcium sulfate crystal whiskers are obtained;
5) the acidifying solution C is concentrated, filters, obtains calcium sulfate crystal whiskers and concentrate D;
6) the concentrate D is concentrated, filters, obtains magnesium chloride whisker.
2. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 1) The concentration for stating hydrochloric acid is 8.80-12.07mol/L, and the mass ratio of the hydrochloric acid and the High-Mg phosphate tailings is (2.0-2.8): 1。
3. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 1) 20-60 DEG C of reaction temperature for stating acidolysis reaction, reaction time 20-60min.
4. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 2) The ice bath temperature for stating ice bath is -10 DEG C -0 DEG C, and the time of repose of the standing is 10-24h.
5. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 3) Concentration≤10% of sulfuric acid is stated, and the additional amount of the sulfuric acid is 1-1.5 times of the amount of substance of calcium in the acid hydrolysis solution B.
6. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 3) The reaction temperature for stating heating reaction is 70-95 DEG C, reaction time 10-40min.
7. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 3) The digestion time for stating ageing is 8-16h.
8. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 4) The time of repose for stating standing is 6-12h.
9. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that institute in the step 5) The thickening temperature for stating concentration is 80-100 DEG C, and the volume ratio of the concentrate D and the acidifying solution C are 0.4-0.6.
10. the recycling processing method of High-Mg phosphate tailings according to claim 1, which is characterized in that in the step 6) The thickening temperature of the concentration is 80-118 DEG C.
CN201910860847.XA 2019-09-11 2019-09-11 Resourceful treatment method for high-magnesium phosphate tailings Active CN110484970B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910860847.XA CN110484970B (en) 2019-09-11 2019-09-11 Resourceful treatment method for high-magnesium phosphate tailings

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910860847.XA CN110484970B (en) 2019-09-11 2019-09-11 Resourceful treatment method for high-magnesium phosphate tailings

Publications (2)

Publication Number Publication Date
CN110484970A true CN110484970A (en) 2019-11-22
CN110484970B CN110484970B (en) 2021-11-12

Family

ID=68557620

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910860847.XA Active CN110484970B (en) 2019-09-11 2019-09-11 Resourceful treatment method for high-magnesium phosphate tailings

Country Status (1)

Country Link
CN (1) CN110484970B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111364094A (en) * 2020-02-27 2020-07-03 武汉工程大学 Method for preparing gypsum whiskers by using phosphate tailings

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311337A (en) * 2008-04-25 2008-11-26 东北大学 Process for preparing calcium sulphate whiskers by using flue gas desulfurization gypsum
CN101353815A (en) * 2008-08-19 2009-01-28 浙江大学 Method for preparing basic magnesium chloride whisker from dolomite and bittern
CN104328481A (en) * 2014-10-14 2015-02-04 瓮福(集团)有限责任公司 Method for preparing gypsum whisker by using phosphate tailings and raffinate phosphoric acid
CN104556158A (en) * 2014-12-25 2015-04-29 昆明钢铁集团有限责任公司 Method for preparing calcium sulfate whiskers and magnesium sulfate
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
CN106495191A (en) * 2016-10-09 2017-03-15 宜昌富升化工有限公司 A kind of method that hydrochloric acid decomposes phosphorus mine tailing preparing magnesium hydroxide and calcium sulfate
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311337A (en) * 2008-04-25 2008-11-26 东北大学 Process for preparing calcium sulphate whiskers by using flue gas desulfurization gypsum
CN101353815A (en) * 2008-08-19 2009-01-28 浙江大学 Method for preparing basic magnesium chloride whisker from dolomite and bittern
CN104328481A (en) * 2014-10-14 2015-02-04 瓮福(集团)有限责任公司 Method for preparing gypsum whisker by using phosphate tailings and raffinate phosphoric acid
CN104556158A (en) * 2014-12-25 2015-04-29 昆明钢铁集团有限责任公司 Method for preparing calcium sulfate whiskers and magnesium sulfate
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
CN106495191A (en) * 2016-10-09 2017-03-15 宜昌富升化工有限公司 A kind of method that hydrochloric acid decomposes phosphorus mine tailing preparing magnesium hydroxide and calcium sulfate
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈佳伟 等: "磷矿浮选尾矿循环酸浸制备硫酸钙晶须", 《化工矿物与加工》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111364094A (en) * 2020-02-27 2020-07-03 武汉工程大学 Method for preparing gypsum whiskers by using phosphate tailings

Also Published As

Publication number Publication date
CN110484970B (en) 2021-11-12

Similar Documents

Publication Publication Date Title
CN105274622B (en) The method for preparing magnesium hydroxide crystal whisker and calcium sulfate as raw material using phosphorus tailing
CN110451473A (en) A kind of method of comprehensive utilization recycling acidleach High-Mg phosphate tailings
CN110424055A (en) A kind of resource utilization method of High-Mg phosphate tailings
CN105442048B (en) The technique for preparing magnesium hydroxide crystal whisker and calcium sulfate as raw material using phosphorus tailing
CN102383179B (en) A kind of method that industrial waste acid and phosphogypsum fully utilize
CN103510151B (en) Method for preparing calcium sulfate whiskers from dolomite
CN108273826B (en) A kind of complete mutually high-valued recoverying and utilizing method of lithium slag
CN110467172A (en) The method that circulation acidleach High-Mg phosphate tailings prepare calcium chlorophosphate and magnesium hydroxide
CN104694761A (en) Method for extracting vanadium from vanadium solution through vanadium slag sodium salt roasting vanadium extraction process
CN102030354A (en) Treatment method of waste sulfuric acid
WO2018233687A1 (en) Method for producing sodium aluminate from medium and low-grade bauxite by one-step alkali thermal treatment through andradite
WO2018233688A1 (en) Method for preparing aluminum hydroxide by treating medium- and low-grade bauxite by using one-step alkali heat process of andradite
CN104294061A (en) Technology for extraction of vanadium pentoxide from stone coal mine
CN110467171A (en) A kind of recycling processing method recycling acidleach High-Mg phosphate tailings
CN102424426B (en) Method for preparing iron oxide red and sodium phosphate by using yellow phosphorus by-product phosphor-iron slag
CN110422869A (en) A kind of method and super strong gypsum of coproducing alpha-super strong gypsum and sodium chloride
CN109734105A (en) A kind of method that titanium gypsum conversion and cycle metal self enrichment and whole amount utilize
CN109250736A (en) The method for preparing activated magnesia using reverse flotation phosphorus tailing
CN1006635B (en) Method for preparing titanium white power using iron-smelting blast-furnace slag containing titanium
WO2018233686A1 (en) Method for preparing metallurgical-level aluminum oxide by treating medium- and low-grade bauxite by using one-step alkali heat process of andradite
CN110510652A (en) A kind of method of comprehensive utilization of High-Mg phosphate tailings
CN102912145B (en) Comprehensive utilization method for converter slag
CN110484970A (en) A kind of recycling processing method of High-Mg phosphate tailings
CN110482517A (en) A kind of resource utilization method recycling acidleach High-Mg phosphate tailings
CN110451474A (en) A method of calcium chlorophosphate and magnesium hydroxide are prepared using High-Mg phosphate tailings

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant