CN112237993A - Method for recycling wastewater in collophanite double-reverse flotation process according to quality - Google Patents
Method for recycling wastewater in collophanite double-reverse flotation process according to quality Download PDFInfo
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- CN112237993A CN112237993A CN202010982600.8A CN202010982600A CN112237993A CN 112237993 A CN112237993 A CN 112237993A CN 202010982600 A CN202010982600 A CN 202010982600A CN 112237993 A CN112237993 A CN 112237993A
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- 238000005188 flotation Methods 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000002351 wastewater Substances 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title claims abstract description 29
- 239000012141 concentrate Substances 0.000 claims abstract description 65
- 239000002562 thickening agent Substances 0.000 claims abstract description 58
- 230000008719 thickening Effects 0.000 claims abstract description 42
- 239000012065 filter cake Substances 0.000 claims abstract description 41
- 229910052604 silicate mineral Inorganic materials 0.000 claims abstract description 41
- -1 fatty acid anion Chemical class 0.000 claims abstract description 40
- 229910001748 carbonate mineral Inorganic materials 0.000 claims abstract description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 34
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 229930195729 fatty acid Natural products 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 272
- 239000002518 antifoaming agent Substances 0.000 claims description 46
- 239000000706 filtrate Substances 0.000 claims description 42
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 17
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 15
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 13
- 235000021314 Palmitic acid Nutrition 0.000 claims description 13
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 13
- 235000020778 linoleic acid Nutrition 0.000 claims description 13
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 13
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000344 soap Substances 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 230000001502 supplementing effect Effects 0.000 claims description 12
- 125000005313 fatty acid group Chemical group 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- 238000005187 foaming Methods 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000003814 drug Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 238000005262 decarbonization Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000006324 decarbonylation Effects 0.000 description 2
- 238000006606 decarbonylation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Physical Water Treatments (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a collophanite double reverse flotation process wastewater quality-divided recycling method, collophanite overflow after grinding and grading is subjected to reverse flotation for removing silicate minerals to obtain tailings and rough concentrate, the tailings enter a tailing thickener for thickening and then are filtered to obtain tailings; the coarse ore concentrate enters an intermediate thickener for thickening and then is filtered, and the filter cake obtained after filtering is subjected to size mixing and then reverse flotation for removing carbonate minerals to obtain tailings and ore concentrate slurry; concentrating the tailings by a tailing thickener, and filtering to obtain tailings; the concentrated ore pulp is concentrated by a concentrate thickener and then filtered to obtain concentrate. Reverse flotation for removing silicate minerals is carried out under the alkaline condition that the pH value is 8.5-9.5, and an amine cationic collector is added; the reverse flotation for removing carbonate minerals is carried out under the acidic condition that the pH value is 4.0-5.0, and a fatty acid anion collecting agent is added. The method creates a scientific and economic industrial implementation scheme for recycling the waste water according to the quality for collophanite double reverse flotation.
Description
Technical Field
The invention belongs to the field of collophanite dressing, and relates to a method for recycling waste water in a collophanite double-reverse flotation process by different qualities, which is simultaneously suitable for a double-reverse flotation process for removing silicate minerals and then removing carbonate minerals and a double-reverse flotation process for removing carbonate minerals and then removing silicate minerals.
Background
The collophanite double reverse flotation process is not generally applied at present, and mainly has the defects of difficult control of cation foam and poor selectivity in practice. Meanwhile, in the conventional double reverse flotation of collophanite, the silicate-removing reverse flotation is neutral and alkaline and contains a cation collecting agent, and the carbonate-removing reverse flotation is acidic and contains an anion collecting agent. The mixed recycling of different waste water increases the consumption of the ore pulp in the acid and alkali adjusting process, and meanwhile, the mixed enrichment of the negative and positive ion collecting agents influences the separation performance, thereby further increasing the difficulty of the double reverse flotation industrialization.
Under the condition that the waste water is recycled according to the quality, the alkaline waste water of desiliconization and the acidity of decarbonation are directly mixed, and the following problems are mainly existed:
1. the consumption of phosphoric acid (or sulfuric acid) and sodium carbonate (or lime and sodium hydroxide) is large, and the beneficiation cost is greatly increased;
2. due to the interference of the cationic collector, the using amount of the anionic collector is obviously increased during the acid salt removal, and the mineral dressing index is influenced;
3. the positive ions enter the whole water return system, so that the whole double-reverse-flow-path foam is difficult to control, and the stability of the flow and the production operation intensity are seriously influenced.
The key of the quality-divided recycling of the wastewater in the double reverse flotation process is to eliminate the influence of the cation wastewater on the anion wastewater, which needs scientific quality-divided blending and effective medicament control.
Disclosure of Invention
The invention aims to provide a method for recycling collophanite double reverse flotation process wastewater according to quality so as to achieve the aims of stable collophanite double reverse flotation production, excellent mineral dressing index and cost reduction. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
carrying out reverse flotation for removing silicate minerals on overflow after grinding and grading collophanite to obtain tailings 1# and rough concentrate, enabling the tailings 1# to enter a tailing thickener 1# for thickening and then enter a filter 1#, enabling the overflow and filtrate to enter a water return tank 1# and enabling tailings 1# filter cakes to be subjected to subsequent treatment; feeding the rough concentrate into an intermediate thickener for thickening, feeding the rough concentrate into a filter No. 2, feeding overflow and filtrate into a water return tank No. 1, and performing reverse flotation for removing carbonate minerals after size mixing of filter cakes to obtain tailings No. 2 and concentrate; enabling the tailings 2# to enter a tailing thickener 2# for thickening and then enter a filter 3#, enabling overflow and filtrate to enter a water return pool 2#, and performing subsequent treatment on tailings 2# filter cakes; and (4) enabling the concentrate pulp to enter a concentrate thickener for thickening and then enter a filter 4#, enabling overflow and filtrate to enter a water return tank 2#, and enabling filter cakes to be used for downstream wet-process phosphoric acid processing. The water return tank 1# is used for ball milling water supply and desilication reverse flotation washing water; the water return tank 2# is used for decarbonated mineral size mixing and replenishing water and flushing water, the water return tank 1# and the water return tank 2# can be provided with communicating pipes for balancing a water system when necessary, defoaming agents are added to the communicating pipes when the water return tank 1# supplements water to the water return tank 2# and clear water is replenished from the clear water tank to the water return tank 1# and the water return tank 2# in real time according to the overall water balance condition.
The method for recycling the wastewater in the double reverse flotation process according to the quality is suitable for the double reverse flotation process of firstly removing carbonate minerals and then removing silicate minerals.
And the filter 1# and the filter 3# adopt a horizontal full-automatic filter press.
The filter No. 2 and the filter No. 4 are selected from ceramic filters or horizontal full-automatic filter presses.
And dredging facilities are arranged in the water return tank 1# and the water return tank 2 #.
Medicine adding points need to be arranged on communicating pipes of the water return tank 1# and the water return tank 2# and a defoaming agent for eliminating amine foaming is added when the water return tank 1# supplements water to the water return tank 2 #; the defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2-3:0.5-2: 2-4.
Preferably, the defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1:2, and the dosage of the defoaming agent is 0.05-0.2kg/m3Preferably 0.1kg/m3。
The water replenishing amount from the water return tank 1# to the water return tank 2# is controlled within 15 percent of the total water amount; the dosage of the defoaming agent is 0.05-0.2kg/m3Preferably 0.1kg/m3。
When a double reverse flotation process of firstly removing carbonate minerals and then removing silicate minerals is adopted, the tailing thickener 1#, the intermediate thickener, the filter 1#, the filter 2# and the water return tank 1# are used for recycling the carbonate removal reverse flotation; and the tailing thickener 2#, the concentrate thickener, the filter 3#, the filter 4# and the water return tank 2# are used for recovering desiliconized acid salt and performing reverse flotation. Adding a defoaming agent for eliminating amine foaming when the water is supplemented to the water return pool 1# from the water return pool 2# (the water return pool 1# and the water return pool 2# are provided with communicating pipes, and defoaming agent adding points are arranged on the communicating pipes); the defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the ratio of 2-3:0.5-2: 2-4.
Preferably, the defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1:2, and the dosage of the defoaming agent is 0.05-0.2kg/m3Preferably 0.1kg/m3。
The water replenishing amount from the water return tank 1# to the water return tank 2# is controlled within 5 percent of the total water amount. The dosage of the defoaming agent is 0.05-0.2kg/m3Preferably 0.1kg/m3。
Reverse flotation for removing silicate minerals in the step (1) is carried out under the alkaline condition that the pH value is 8.5-9.5, and meanwhile, an amine cation collector is added; the reverse flotation for removing the carbonate minerals is carried out in an acidic condition with the pH value of 4.0-5.0, and a fatty acid anion collecting agent is added at the same time.
The method for recycling the waste water in the collophanite double reverse flotation process according to the quality is characterized in that the main component of the amine cationic collector is dodecylamine, and the addition amount of the dodecylamine cationic collector is 0.2-0.4kg/t of raw ore.
The method for recycling the waste water in the collophanite double-reverse flotation process according to the quality is characterized in that the fatty acid anion collecting agent mainly becomes fatty acid soap mixed by palmitic acid and linoleic acid in any proportion, and the addition amount is 1.0-1.5kg/t of raw ore.
Drawings
FIG. 1 is a flow chart of a double reverse flotation process for removing silicate minerals and then removing carbonate minerals.
FIG. 2 is a flow chart of a double reverse flotation process for removing carbonate minerals first and then silicate minerals.
Detailed Description
The present invention is further illustrated by the following examples.
The process for removing silicate minerals and then removing carbonate comprises the following steps:
blank example: in the double reverse flotation process of removing silicate minerals and carbonate minerals, the wastewater quality-grading scheme of the invention is not adopted, the dosage of a desilicated reverse flotation pH regulator (sodium hydroxide) is 6.3kg/t of raw ore, the dosage of an amine cation collector (dodecylamine) is 0.3kg/t of raw ore, the dosage of a decarbonated reverse flotation pH regulator (phosphoric acid) is 5.5kg/t of raw ore, and the dosage of a fatty acid anion collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 1.5kg/t of raw ore. The waste water containing the amine cation collecting agent has great influence on reverse flotation froth of decarbonate, so that the process is unstable.
Example 1: referring to fig. 1, a method for recycling collophanite double reverse flotation process wastewater according to quality mainly comprises the following steps: carrying out reverse flotation for removing silicate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1# to enter a tailing thickener 1# for thickening and then enter a filter 1#, enabling the overflow and filtrate to enter a return water tank 1#, and carrying out subsequent treatment on tailings 1# filter cake (containing 12-15% of water); feeding the rough concentrate into an intermediate thickener for thickening, then feeding the rough concentrate into a filter No. 2, feeding overflow and filtrate into a water return tank No. 1, and performing reverse flotation for removing carbonate minerals after size mixing of a filter cake (containing 10-12 water) to obtain tailings No. 2 and concentrate; enabling the tailings 2# to enter a tailing thickener 2# for thickening and then enter a filter 3#, enabling overflow and filtrate to enter a water return pool 2#, and performing subsequent treatment on tailings 2# filter cakes (containing 12-15% of water); the concentrate slurry enters a concentrate thickener for thickening and then enters a filter No. 4, the overflow and the filtrate enter a return water tank No. 2, and the filter cake (containing 10-12% of water) is supplied for the downstream wet-process phosphoric acid processing. The water return tank 1# is used for ball milling water supply and desilication reverse flotation washing water; and the water return tank 2# is used for decarbonated mineral size mixing, supplementing water and washing water.
The filter No. 1 and the filter No. 3 adopt horizontal full-automatic filter presses, and the filter No. 2 and the filter No. 4 adopt ceramic filter presses; dredging facilities are arranged in the water return tank 1# and the water return tank 2 #; the communicating pipes of the water return tank 1# and the water return tank 2# need to be provided with dosing points, when the water replenishing amount from the water return tank 1# to the water return tank 2# is 10 percent of the total water consumption, 0.1kg/m of defoaming agent for eliminating amine foaming is added3The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
According to the method, double reverse flotation is carried out to remove silicate minerals firstly and then remove carbonate minerals, the ore dressing site and the indexes are stable, the dosage of a desilicated reverse flotation pH regulator ((sodium hydroxide) is 2.8kg/t of raw ore, the dosage of an amine cation collector (dodecylamine) is 0.16kg/t of raw ore), the dosage of a decarbonated reverse flotation pH regulator (phosphoric acid) is 2.2kg/t of raw ore, and the dosage of a fatty acid anion collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 0.9kg/t of raw ore, so that the medicament consumption is greatly reduced.
Example 2: referring to fig. 1, a method for recycling collophanite double reverse flotation process wastewater according to quality mainly comprises the following steps: carrying out reverse flotation for removing silicate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the coarse concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing carbonate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and desilication reverse flotation washing water; the water return tank 2 is used for adding water and washing water for the decarbonated mineral size mixing.
The filter 1 and the filter 3 adopt a horizontal full-automatic filter press, and the filter 2 and the filter 4 adopt a ceramic filter; the water return tank 1 and the water return tank 2 are provided with dredging facilities; the communicating pipe of the water return tank 1 and the water return tank 2 needs to be provided with a dosing point, when the water supplementing amount from the water return tank 1 to the water return tank 2 is 15 percent of the total water consumption, 0.1kg/m of defoaming agent for eliminating amine foaming is added3 ，The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
According to the method, double reverse flotation is carried out to remove silicate minerals firstly and then remove carbonate minerals, the ore dressing site and the indexes are stable, the dosage of a desilicated reverse flotation pH regulator (sodium hydroxide) is 2.8kg/t of raw ore, the dosage of an amine cation collector (dodecylamine) is 0.16kg/t of raw ore, the dosage of a decarbonated reverse flotation pH regulator (phosphoric acid) is 2.3kg/t of raw ore, the dosage of a fatty acid anion collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 0.9kg/t of raw ore, and the medicament consumption is greatly reduced.
Example 3: referring to fig. 1, a method for recycling collophanite double reverse flotation process wastewater according to quality mainly comprises the following steps: carrying out reverse flotation for removing silicate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the coarse concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing carbonate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and desilication reverse flotation washing water; the water return tank 2 is used for adding water and washing water for the decarbonated mineral size mixing.
The filter 1 and the filter 3 adopt a horizontal full-automatic filter press, and the filter 2 and the filter 4 adopt a ceramic filter; the water return tank 1 and the water return tank 2 are provided with dredging facilities; the communicating pipe of the water return tank 1 and the water return tank 2 needs to be provided with a dosing point, when the water supplementing amount from the water return tank 1 to the water return tank 2 is 20 percent of the total water consumption, 0.1kg/m of defoaming agent for eliminating amine foaming is added3The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
According to the method, double reverse flotation is carried out to remove silicate minerals firstly and then remove carbonate minerals, the ore dressing site and the indexes are stable, the dosage of a pH regulator (sodium hydroxide) for desiliconization reverse flotation is 2.8kg/t of raw ore, the dosage of an amine cation collector (dodecylamine) is 0.16kg/t of raw ore, the dosage of a pH regulator (phosphoric acid) for decarbonylation reverse flotation is 3.8kg/t of raw ore, and the dosage of a fatty acid anion collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 1.3kg/t of raw ore, and when the water supplement amount is increased, the dosage of the fatty acid anion collector cannot be reduced remarkably.
Example 4: referring to fig. 1, a method for recycling collophanite double reverse flotation process wastewater according to quality mainly comprises the following steps: carrying out reverse flotation for removing silicate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the coarse concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing carbonate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and desilication reverse flotation washing water; the water return tank 2 is used for adding water and washing water for the decarbonated mineral size mixing.
The filter 1 and the filter 3 adopt a horizontal full-automatic filter press, and the filter 2 and the filter 4 adopt a ceramic filter; the water return tank 1 and the water return tank 2 are provided with dredging facilities; the communicating pipe of the water return tank 1 and the water return tank 2 needs to be provided with a dosing point, when the water supplementing amount from the water return tank 1 to the water return tank 2 is 15 percent of the total water consumption, 0.05kg/m of defoaming agent for eliminating amine foaming is added3The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
According to the method, double reverse flotation is carried out to remove silicate minerals firstly and then remove carbonate minerals, the ore dressing site and the indexes are stable, the dosage of a pH regulator (phosphoric acid) for desiliconization reverse flotation is 2.8kg/t of raw ore, the dosage of an amine cation collector (dodecylamine) is 0.16kg/t of raw ore, the dosage of a pH regulator (phosphoric acid) for decarbonylation reverse flotation is 2.3kg/t of raw ore, and the dosage of a fatty acid anion collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 0.9kg/t of raw ore, so that the medicament consumption is greatly reduced, but reverse flotation foams for removing carbonate minerals are seriously influenced, the foams are sticky and are not defoamed, and the stability of the process is influenced.
The process for removing silicate minerals and then removing carbonate comprises the following steps:
blank example: in the double reverse flotation process of removing carbonate minerals and then removing silicate minerals, the wastewater quality-classification scheme of the invention is not adopted, the consumption of a pH regulator (phosphoric acid) for the reverse flotation of the carbonate is 4.5kg/t of raw ore, the consumption of a fatty acid anion collecting agent (mixed fatty acid soap with the mass ratio of palmitic acid to linoleic acid being 1: 2) is 1.3kg/t of raw ore, the consumption of a pH regulator (sodium hydroxide) for the reverse flotation of the silicate is 7.5kg/t of raw ore, and the consumption of an amine cation collecting agent (dodecylamine) is 0.4kg/t of raw ore.
Example 5: referring to fig. 2, the method for recycling the wastewater in the collophanite double reverse flotation process by different qualities mainly comprises the following steps: carrying out reverse flotation for removing carbonate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the rough concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing silicate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and decarbonization reverse flotation washing water; the water return tank 2 is used for desiliconizing mineral size mixing and replenishing water and flushing water, the water return tank 1 and the water return tank 2 can be provided with communicating pipes for balancing a water system when necessary, but the water return tank 2 is controlled not to replenish water to the water return tank 1.
The filter 1 and the filter 3 adopt horizontal full-automatic filter presses, and the filter 2 and the filter 4 adopt horizontal full-automatic filter presses; the water return pool 1 and the water return pool 2 are provided with dredging facilities.
According to the method, double reverse flotation is carried out to remove carbonate minerals firstly and then remove silicate minerals, the ore dressing site and the indexes are stable, the dosage of a pH regulator (phosphoric acid) for the carbonate removal reverse flotation is 2.7kg/t of raw ore, the dosage of a fatty acid anion collecting agent (mixed fatty acid soap with the mass ratio of palmitic acid to linoleic acid being 2: 1) is 0.8kg/t of raw ore, the dosage of a pH regulator (sodium hydroxide) for the desiliconization reverse flotation is 3.1kg/t of raw ore, the dosage of an amine cation collecting agent (dodecylamine) is 0.2kg/t of raw ore, and the medicament consumption is obviously reduced.
Example 6: referring to fig. 2, aThe process of recovering waste water from double reverse collophanite flotation includes the following steps: carrying out reverse flotation for removing carbonate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the rough concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing silicate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and decarbonization reverse flotation washing water; the water return tank 2 is used for desiliconizing the silicate mineral, mixing the slurry, supplementing water and flushing water, the water return tank 1 and the water return tank 2 can be provided with communicating pipes for balancing a water system when necessary, the water supplementing amount from the water return tank 2 to the water return tank 1 is controlled to be 5% of the total water amount, and 0.1kg/m of defoaming agent for eliminating amine foaming is added3The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
The filter 1 and the filter 3 adopt horizontal full-automatic filter presses, and the filter 2 and the filter 4 adopt horizontal full-automatic filter presses; the water return pool 1 and the water return pool 2 are provided with dredging facilities.
According to the method, double reverse flotation is carried out to remove carbonate minerals firstly and then remove silicate minerals, the ore dressing site and the indexes are stable, the dosage of a pH regulator (phosphoric acid) for the carbonate removal reverse flotation is 2.8kg/t of raw ore, the dosage of a fatty acid anionic collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 0.9kg/t of raw ore, the dosage of a pH regulator (sodium hydroxide) for the silicate removal reverse flotation is 3.0kg/t of raw ore, the dosage of an amine cationic collector (dodecylamine) is 0.2kg/t of raw ore, when a small amount of 5% of water is supplemented to a water return pool 1 from a water return pool 2, the dosage of the pH regulator for the carbonate removal reverse flotation and the dosage of the fatty acid anionic collector are obviously reduced, and flotation foams are not influenced.
Example 7: referring to fig. 2, the method for recycling the wastewater in the collophanite double reverse flotation process by different qualities mainly comprises the following steps: carrying out reverse flotation for removing carbonate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the rough concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing silicate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and decarbonization reverse flotation washing water; the water return tank 2 is used for desiliconizing the silicate mineral, mixing the slurry, supplementing water and flushing water, the water return tank 1 and the water return tank 2 can be provided with communicating pipes for balancing a water system when necessary, the water supplementing amount from the water return tank 2 to the water return tank 1 is controlled to be 7% of the total water amount, and 0.1kg/m of defoaming agent for eliminating amine foaming is added3The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
The filter 1 and the filter 3 adopt horizontal full-automatic filter presses, and the filter 2 and the filter 4 adopt horizontal full-automatic filter presses; the water return pool 1 and the water return pool 2 are provided with dredging facilities.
According to the method, double reverse flotation is carried out to remove carbonate minerals firstly and then remove silicate minerals, the ore dressing site and the indexes are stable, the dosage of a pH regulator (phosphoric acid) for the carbonate removal reverse flotation is 2.9kg/t of raw ore, the dosage of a fatty acid anionic collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 1.0kg/t of raw ore, the dosage of a pH regulator (sodium hydroxide) for the silicate removal reverse flotation is 3.0kg/t of raw ore, the dosage of an amine cationic collector (dodecylamine) is 0.2kg/t of raw ore, and when water is supplemented to a water return pool 1 from a water return pool 2 to the water return pool 1, the dosage of the pH regulator for the carbonate removal reverse flotation and the dosage of the fatty acid anionic collector are slightly increased when water is not supplemented and 5% of water is supplemented.
Example 8: referring to fig. 2, the method for recycling the wastewater in the collophanite double reverse flotation process by different qualities mainly comprises the following steps: carrying out reverse flotation for removing carbonate minerals on overflow after grinding and grading collophanite to obtain tailings 1 and rough concentrate, enabling the tailings 1 to enter a tailing thickener 1 for thickening and enter a filter 1, enabling the overflow and filtrate to enter a water return pool 1, and carrying out subsequent treatment on a filter cake (containing 12-15% of water) of the tailings 1; the rough concentrate enters an intermediate thickener for thickening and then enters a filter 2, overflow and filtrate enter a water return pool 1, and reverse flotation for removing silicate minerals is carried out after filter cake (containing 10-12% of water) is subjected to size mixing to obtain tailings 2 and concentrate; the tailings 2 enter a tailing thickener 2 for thickening and then enter a filter 3, overflow and filtrate enter a water return pool 2, and the filter cake (containing 12-15% of water) of the tailings 2 is subjected to subsequent treatment; the concentrate slurry enters a concentrate thickener for thickening and then enters a filter 4, overflow and filtrate enter a water return pool 2, and filter cakes (containing 10-12 percent of water) are supplied for downstream wet-process phosphoric acid processing. The water return tank 1 is used for ball milling water supply and decarbonization reverse flotation washing water; the water return tank 2 is used for desiliconizing the silicate mineral, mixing the slurry, supplementing water and flushing water, the water return tank 1 and the water return tank 2 can be provided with communicating pipes for balancing a water system when necessary, the water supplementing amount from the water return tank 2 to the water return tank 1 is controlled to be 5% of the total water amount, and 0.05kg/m of defoaming agent for eliminating amine foaming is added3The defoaming agent is a mixture of tributyl phosphate, an organic silicon defoaming agent (linear polysiloxane) and sodium oleate which are compounded according to the mass ratio of 2:1: 2.
The filter 1 and the filter 3 adopt horizontal full-automatic filter presses, and the filter 2 and the filter 4 adopt horizontal full-automatic filter presses; the water return pool 1 and the water return pool 2 are provided with dredging facilities.
According to the method, double reverse flotation is carried out to remove carbonate minerals firstly and then remove silicate minerals, the ore dressing site and the indexes are stable, the dosage of a pH regulator (phosphoric acid) for the carbonate removal reverse flotation is 3.0kg/t of raw ore, the dosage of a fatty acid anionic collector (mixed fatty acid soap with palmitic acid and linoleic acid in a mass ratio of 2: 1) is 1.1kg/t of raw ore, the dosage of a pH regulator (sodium hydroxide) for the silicate removal reverse flotation is 3.0kg/t of raw ore, the dosage of an amine cationic collector (dodecylamine) is 0.2kg/t of raw ore, when a water return pool 2 is supplemented with a small amount of 5% of water to the water return pool 1, the dosage of the pH regulator for the carbonate removal reverse flotation and the dosage of the fatty acid anionic collector are increased compared with the dosage of a defoaming agent, and flotation foams are obviously influenced.
Claims (10)
1. A method for recycling wastewater in a collophanite double reverse flotation process according to quality is characterized in that a double reverse flotation process of firstly removing silicate minerals and then removing carbonate minerals is adopted, and the method comprises the following steps:
(1) grinding collophanite, classifying, performing reverse flotation to remove silicate minerals to obtain tailings and rough concentrate, and filtering the tailings in a filter 1# after the tailings enter a tailing thickener 1# for thickening to obtain tailings 1 #; the coarse ore concentrate enters an intermediate thickener for thickening and then enters a filter No. 2, and the filter cake obtained after filtering through the filter No. 2 is subjected to size mixing and then reverse flotation for removing carbonate minerals to obtain tailings and ore concentrate slurry; concentrating the tailings by a tailing thickener 2# and filtering by a filter 3# to obtain tailings 2 #; after the concentrated ore pulp is concentrated by a concentrate thickener, filtering by a filter 4# to obtain concentrate;
(2) in the step (1), the overflow of the tailing thickener 1# and the filtrate filtered by the filter 1# and the filter 2# enter a water return tank 1 #;
(3) in the step (1), the tailings overflow through a tailing thickener 2# and the filtrate filtered by a filter 3# enters a water return tank 2 #;
(4) and (3) enabling the overflow of the concentrate thickener in the step (1) and the filtered filtrate of the filter 4# to enter a water return pool 2 #.
2. The method for recycling the waste water in the double reverse flotation process of the collophanite according to the claim 1, which is characterized in that a water return tank 1# is used for supplying water for grinding ore and reverse flotation washing water for removing silicate minerals; and the water return tank 2# is used for supplementing water for filter cake size mixing and washing water for reverse flotation for removing carbonate minerals.
3. The method for recycling the waste water in the double reverse flotation process of the collophanite according to the claim 1, which is characterized in that a communicating pipe is arranged between the water return tank 1# and the water return tank 2#, and when the water return tank 2 replenishes water to the water return tank 1, a defoaming agent is added to the communicating pipe; the defoaming agent is a mixture of tributyl phosphate, polysiloxane and sodium oleate which are compounded according to the ratio of 2-3:0.5-2: 2-4; preferably, the defoaming agent is a mixture of tributyl phosphate, polysiloxane and sodium oleate which are compounded according to a ratio of 2:1: 2.
4. The method for recycling the separated quality of the wastewater generated in the double reverse flotation process of collophanite according to claim 3, wherein the amount of water supplied from the water return tank 1# to the water return tank 2# is controlled within 15% of the total water amount; the dosage of the defoaming agent is 0.05-0.2kg/m3Preferably 0.1kg/m3。
5. The method for recycling the waste water in the double reverse flotation process of the collophanite according to the claim 1, which is characterized in that the reverse flotation for removing the silicate minerals in the step (1) is carried out by using a pH regulator to adjust the pH value of ore pulp to be 8.5-9.5 under an alkaline condition, and simultaneously adding an amine cation collector, namely dodecylamine, with the addition amount of 0.2-0.4kg/t raw ore; the reverse flotation for removing carbonate minerals is carried out under the acidic condition that the pH value of ore pulp is adjusted to 4.0-5.0 by utilizing a pH adjusting agent, and a fatty acid anion collecting agent is added at the same time, wherein the fatty acid anion collecting agent is a fatty acid soap formed by mixing palmitic acid and linoleic acid in any proportion, and the addition amount is 1.0-1.5kg/t of raw ore.
6. The method for recycling collophanite double reverse flotation process wastewater according to any one of claims 1-5, wherein the method is also applicable to a double reverse flotation process for removing carbonate minerals first and then silicate minerals, and the method comprises the following steps:
(1) grinding collophanite, grading, performing overflow, removing carbonate minerals, performing reverse flotation to obtain tailings and rough concentrate, feeding the tailings into a tailing thickener 1# for thickening, and filtering by a filter 1# to obtain tailings 1 #; the rough concentrate enters an intermediate thickener for thickening and then enters a filter No. 2, and the filter cake obtained after filtering through the filter No. 2 is subjected to size mixing and then reverse flotation for removing silicate minerals to obtain tailings and concentrate pulp; concentrating the tailings by a tailing thickener 2, and filtering by a filter 3# to obtain tailings 2 #; the concentrated ore pulp is concentrated by a concentrate thickener and then filtered by a filter 4# to obtain concentrate 4 #;
(2) in the step (1), the overflow of the tailing thickener 1# and the filtrate filtered by the filter 1# and the filter 2# enter a water return pool 1;
(3) in the step (1), the tailings overflow through a tailing thickener 2# and filtrate filtered by a filter 3# enters a water return pool 2;
(4) and (3) enabling the overflow of the concentrate thickener in the step (1) and the filtered filtrate of the filter 4# to enter a water return pool 2 #.
7. The method for recycling the waste water of the collophanite double reverse flotation process according to the claim 6, which is characterized in that a water return tank 1# is used for supplying water for grinding ore and reverse flotation washing water for removing silicate minerals; and the water return tank 2# is used for supplementing water for filter cake size mixing and washing water for reverse flotation for removing carbonate minerals.
8. The method for recycling the waste water of the double reverse flotation process of the collophanite according to the claim 6, which is characterized in that the water return pool 1 and the water return pool 2 are provided with communicating pipes, and when the water return pool 2 replenishes water to the water return pool 1, defoaming agents are added on the communicating pipes;
the defoaming agent is a mixture of tributyl phosphate, polysiloxane and sodium oleate which are compounded according to the ratio of 2-3:0.5-2: 2-4; preferably, the defoaming agent is a mixture of tributyl phosphate, polysiloxane and sodium oleate which are compounded according to a ratio of 2:1: 2.
9. The method for recycling the separated quality of the wastewater generated in the double reverse flotation process of collophanite according to claim 6, wherein the amount of water supplied from the water return tank 2 to the water return tank 1 is controlled within 5% of the total amount of water; the dosage of the defoaming agent is 0.05-0.2kg/m3Preferably 0.1kg/m3。
10. The method for recycling the waste water in the double reverse flotation process of collophanite according to claim 6, characterized in that the reverse flotation for removing carbonate minerals in the step (1) is carried out in an acidic condition with pH of 4.0-5.0, and a fatty acid anion collector is added, wherein the fatty acid anion collector is a mixed fatty acid soap of palmitic acid and linoleic acid in any proportion, and the addition amount is 1.0-1.5kg/t raw ore; the reverse flotation for removing silicate minerals is carried out under the alkaline condition that the pH value is 8.5-9.5, and an amine cationic collector is added, wherein the amine cationic collector is dodecylamine, and the addition amount is 0.2-0.4kg/t of raw ore.
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| CN115259459B (en) * | 2022-05-05 | 2024-02-02 | 中国矿业大学(北京) | Method for recycling in-process wastewater of sectional quality-dividing branch of concentrating mill |
| CN115594353A (en) * | 2022-10-28 | 2023-01-13 | 矿冶科技集团有限公司（Cn） | Method for treating collophanite double-reverse flotation wastewater |
| CN115594353B (en) * | 2022-10-28 | 2024-06-04 | 矿冶科技集团有限公司 | Treatment method of collophanite double reverse flotation wastewater |
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