CN108187917B - Aromatic phosphonic acid and salt collector thereof and application thereof - Google Patents
Aromatic phosphonic acid and salt collector thereof and application thereof Download PDFInfo
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- CN108187917B CN108187917B CN201810029330.1A CN201810029330A CN108187917B CN 108187917 B CN108187917 B CN 108187917B CN 201810029330 A CN201810029330 A CN 201810029330A CN 108187917 B CN108187917 B CN 108187917B
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- Prior art keywords
- cassiterite
- phenylphosphonic acid
- salts
- acid
- flotation
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- 150000003839 salts Chemical class 0.000 title claims abstract description 43
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims description 12
- 125000003118 aryl group Chemical group 0.000 title claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 102
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005188 flotation Methods 0.000 claims abstract description 39
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 28
- 239000011707 mineral Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000010453 quartz Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000010436 fluorite Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 22
- 239000004115 Sodium Silicate Substances 0.000 claims description 22
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 22
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 22
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 22
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 230000002000 scavenging effect Effects 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 2
- -1 aryl phosphonic acid Chemical compound 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B03D1/018—Mixtures of inorganic and organic compounds
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- 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
- B03D2201/06—Depressants
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Paper (AREA)
Abstract
The invention discloses an aryl phosphonic acid and salt collector thereof and application thereof, belonging to the technical field of flotation. The aryl phosphonic acid and salt collector thereof comprises phenylphosphonic acid and/or phenylphosphonic acid and salts thereof, and is applied to flotation separation of cassiterite and gangue minerals. The invention adopts the aryl phosphonic acid and salts thereof as the cassiterite collecting agent, not only improves the water solubility of the collecting agent, but also has better selectivity, can effectively separate cassiterite from gangue minerals such as quartz, fluorite, calcite and the like, and can realize the floatation of the cassiterite under the wider pH condition of ore pulp.
Description
Technical Field
The invention relates to the technical field of cassiterite flotation, in particular to an aromatic phosphonic acid and salt type collecting agent thereof and application thereof.
Background
Tin is one of the metal materials developed and utilized by human beings at the earliest, and has irreplaceable effects in the fields of medical appliances, chemical engineering, national defense, electronic and electric appliances, ocean engineering and the like today. The cassiterite is the only mineral which exists in the nature and can be used for smelting metallic tin, so that the flotation recovery of the cassiterite mineral has important significance for ensuring the national economic development. Because the specific gravity of the cassiterite is relatively large, the coarse cassiterite can be effectively recycled by adopting a gravity separation technology; however, the cassiterite is brittle, a large amount of fine mud is easily generated in the crushing and grinding process, when the granularity of the cassiterite is smaller than 20 mu m, the recovery rate of the cassiterite recovered by the gravity separation method is seriously insufficient, so that a large amount of micro-fine cassiterite is lost in tailings, and the effective separation and recovery of the micro-fine cassiterite can be ensured only by adopting a flotation technology.
Therefore, rational collector application is the key to successful flotation, and there are many types of collectors available for cassiterite flotation, including fatty acids, alkyl sulfosuccinates, hydroximic acids, arsenic acids, phosphonic acids, and the like. However, the selectivity of the fatty acid and alkyl sulfonated succinic acid collecting agents is extremely poor, the collecting capacity of hydroximic acid is insufficient, the arsenic acid collecting agent has toxicity and is forbidden to be used, only the phosphonic acid collecting agent can be widely applied in industry, and in the phosphonic acid collecting agents, although short-chain alkyl phosphonic acid can be used for floating and recovering cassiterite, the collecting capacity is insufficient, and the problems of cost rise, water source pollution and the like can be caused by the synergistic effect of a heavy metal salt (such as lead nitrate) activating agent; the long-chain alkyl phosphonic acid has strong collecting capacity, but poor water solubility, and the selectivity can be greatly reduced, thereby limiting the application of the long-chain alkyl phosphonic acid in the industry. Therefore, in order to solve the technical problems, a new cassiterite flotation collector needs to be provided.
Disclosure of Invention
The invention aims to provide a collecting agent which can act with the surface of cassiterite, enhance the hydrophobicity of the surface of the cassiterite and can be applied to flotation to realize selective separation of the cassiterite from gangue minerals so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides an aryl phosphonic acid and a salt collector thereof, which are characterized in that: the compound comprises phenylphosphonic acid and/or phenylphosphonic acid and salts thereof, wherein the structural formula of the phenylphosphonic acid and the salts thereof is shown as a formula (I); the structural formula of the phenylphosphonic acid and the salt thereof is shown as a formula (II),
wherein M is1And M2Respectively, a monovalent or divalent cation.
Preferably, said M1And M2Are respectively H+、NH4+、Na+、Li+、K+、Rb+、Cs+、1/2Sr2+、1/2Be2+、1/2Mg2+、1/2Ca2+、1/2Ba2+、1/2Zn2+And 1/2Mn2+One kind of (1).
The invention also provides application of the aromatic phosphonic acid and the salt collector thereof, which is characterized in that: the method is applied to flotation separation of cassiterite and gangue minerals.
Preferably, the gangue minerals are quartz, fluorite and calcite.
Preferably, benzene phosphonic acid and/or phenyl phosphonic acid and salts thereof are used as a cassiterite collecting agent, methyl isobutyl carbinol is used as a foaming agent, carboxymethyl cellulose and sodium silicate are used as gangue mineral inhibitors, and cassiterite ore pulp is subjected to flotation to obtain cassiterite concentrate.
Preferably, the flotation process comprises 1 roughing process, 2-3 scavenging processes and 3 concentrating processes.
Preferably, the aromatic radical phosphonic acid and salt collector and application thereof comprise the following steps:
(1) in the roughing process, adjusting the pH value of the cassiterite pulp to 4-7, sequentially adding a gangue mineral inhibitor carboxymethyl cellulose and sodium silicate, a cassiterite collector phenylphosphonic acid and/or phenylphosphonic acid and salts thereof, and a foaming agent methyl isobutyl carbinol, and roughing to obtain roughing concentrate and roughing tailings; the dosage of the carboxymethyl cellulose and the sodium silicate relative to the raw ore is 300-500 g/t, the dosage of the phenylphosphonic acid and/or the phenylphosphonic acid and the salts thereof relative to the raw ore is 1200-1500 g/t, and the dosage of the methyl isobutyl carbinol relative to the raw ore is 120 g/t;
(2) in the scavenging process, adding cassiterite collecting agent phenylphosphonic acid and/or phenylphosphonic acid and salts thereof and foaming agent methyl isobutyl carbinol into the obtained rough concentration tailings, and scavenging for 2-3 times to obtain scavenging concentrate; returning the scavenged concentrate to the last flotation operation in sequence; the dosage of the phenylphosphonic acid and/or phenylphosphonic acid and salts thereof relative to raw ore is 600-750 g/t, and the dosage of the methyl isobutyl carbinol relative to the raw ore is 80 g/t;
(3) in the concentration process, adding gangue mineral inhibitor carboxymethyl cellulose and sodium silicate into the obtained rough concentration concentrate, concentrating for 3 times to obtain concentrated concentrate and concentrated middlings, and returning the concentrated middlings to the last flotation operation in sequence; the dosage of the carboxymethyl cellulose and the sodium silicate relative to the raw ore is 150-250 g/t.
Preferably, the mass ratio of the carboxymethyl cellulose to the sodium silicate is 1: 1.
Preferably, the carboxymethyl cellulose and the sodium silicate are prepared into an aqueous solution with the mass percentage concentration of 20-25%, the phenylphosphonic acid and/or the phenylphosphonic acid and salts thereof are prepared into an aqueous solution with the mass percentage concentration of 10-15%, and the methyl isobutyl carbinol is prepared into an aqueous solution with the mass percentage concentration of 20%.
The invention discloses the following technical effects:
1. the phenylphosphonic acid and/or phenylphosphonic acid and salts thereof provided by the invention are phosphonic acid collecting agents containing benzene ring structures, polar groups in the phenylphosphonic acid and the phenylphosphonic acid are phosphinic acid groups and phosphonic acid groups respectively, and phosphorus atoms and oxygen atoms in the phenylphosphonic acid and the phenylphosphonic acid can chemically react with tin metal atoms on the surface of cassiterite so as to be adsorbed on the surface of the cassiterite; the nonpolar groups in the phenylphosphonic acid and the phenylphosphonic acid are benzene ring structures, and the introduction of the benzene rings can improve the selectivity, collecting capability, strong hydrophobicity and water solubility of the phosphonic acid collecting agent, effectively separate cassiterite from gangue minerals such as quartz, fluorite, calcite and the like, and can realize the flotation of the cassiterite under the wider pH condition of ore pulp.
2. The collecting agent provided by the invention is environment-friendly, non-toxic, harmless, strong in water solubility and suitable for large-scale industrial application.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.
Example 1
Flotation of artificial mixed ore
(1) Preparing the cassiterite pure mineral, the quartz pure mineral, the fluorite pure mineral and the calcite pure mineral into an artificial mixed mineral according to the mass ratio of 1:1, wherein the granularity of all the pure minerals is-45 mu m;
(2) placing 2g of artificial mixed ore and 20mL of distilled water in a 30mL tank-hanging flotation machine, and carrying out size mixing for 3min at a stirring rotating speed of 1992r/min to obtain cassiterite pulp;
(3) adjusting the pH value of the cassiterite pulp to 7 by using sodium hydroxide and sulfuric acid, adding a cassiterite collecting agent (phenylphosphonic acid and/or phenylphosphonic acid and salts thereof) with the concentration of 60mg/L, stirring for 3min, adding a foaming agent (methyl isobutyl carbinol) with the concentration of 100mg/L, stirring for 3min, and then performing air flotation to obtain a foam product and the residual tailings in the cell;
(4) and respectively drying, weighing and sampling the foam product and the tailings, testing the grade of tin in the foam product and the tailings, and calculating the yield and the recovery rate.
The flotation results of the artificial mixed ore are shown in table 1 below. The results show that the phenylphosphonic acid and the salt thereof, and the phenylphosphonic acid and the salt thereof collecting agent can effectively separate the cassiterite from quartz, fluorite and calcite, and the flotation indexes are not greatly different.
TABLE 1 results of artificial commingled ore flotation
Example 2
Selecting raw cassiterite ore of inner Mongolia as raw material, wherein the grade of tin in the raw ore is 0.37%, and gangue minerals comprise quartz, feldspar, mica, calcite and kaolin.
The dosage of the traditional Chinese medicine in the flotation process is as follows: in the roughing process, the addition amount of the carboxymethyl cellulose relative to the raw ore is 250g/t, the addition amount of the sodium silicate relative to the raw ore is 250g/t, the addition amount of the phenylphosphonic acid and the salt thereof relative to the raw ore is 1500g/t, and the addition amount of the methyl isobutyl carbinol relative to the raw ore is 120 g/t; in the scavenging process, the adding amount of phenylphosphonic acid and salts thereof relative to raw ore is 750g/t, and the using amount of methyl isobutyl carbinol relative to raw ore is 80 g/t; in the concentration process, the addition amount of the carboxymethyl cellulose relative to the raw ore is 100g/t, and the addition amount of the sodium silicate relative to the raw ore is 100 g/t.
The flotation operation steps are as follows:
(1) crushing and grinding raw ore to achieve monomer dissociation, preparing ore pulp in a flotation tank, adjusting the pH value to 4-7 by using sodium hydroxide and sulfuric acid, sequentially adding gangue mineral inhibitors (carboxymethyl cellulose and sodium silicate), cassiterite collectors (phenylphosphonic acid and salts thereof) and foaming agents (methyl isobutyl carbinol), and performing roughing to obtain roughed concentrate and roughed tailings;
(2) adding a cassiterite collecting agent (phenylphosphonic acid and salts thereof) and a foaming agent (methyl isobutyl carbinol) into the obtained rough tailings, carrying out scavenging for 3 times to obtain scavenged concentrate, and returning the scavenged concentrate to the last flotation operation in sequence;
(3) adding gangue mineral inhibitors (carboxymethyl cellulose and sodium silicate) into the obtained rough concentration concentrate, concentrating for 3 times to obtain concentrated concentrate and concentrated middlings, and returning the concentrated middlings to the last flotation operation in sequence.
After the raw ore with the grade of 0.37% is subjected to one-rough three-sweep three-fine flotation, the cassiterite concentrate with the grade of 38.03% and the recovery rate of 73.15% is obtained.
Example 3
The raw ore of a certain cassiterite ore in Jiangxi province is selected as a raw material, the grade of tin in the raw ore is 0.34%, and gangue minerals are quartz, feldspar, mica and fluorite.
The dosage of the traditional Chinese medicine in the flotation process is as follows: in the roughing process, the addition amount of the carboxymethyl cellulose relative to the raw ore is 200g/t, the addition amount of the sodium silicate relative to the raw ore is 200g/t, the addition amount of the phenylphosphonic acid and the salts thereof relative to the raw ore is 1200g/t, and the addition amount of the methyl isobutyl carbinol relative to the raw ore is 120 g/t; in the scavenging process, the adding amount of phenylphosphonic acid and salts thereof relative to raw ore is 600g/t, and the using amount of methyl isobutyl carbinol relative to raw ore is 80 g/t; in the concentration process, the addition amount of the carboxymethyl cellulose relative to the raw ore is 100g/t, and the addition amount of the sodium silicate relative to the raw ore is 100 g/t.
The flotation operation steps are as follows:
(1) crushing and grinding raw ore to achieve monomer dissociation, preparing ore pulp in a flotation tank, adjusting the pH value to 4-7 by using sodium hydroxide and sulfuric acid, sequentially adding gangue mineral inhibitors (carboxymethyl cellulose and sodium silicate), cassiterite collectors (phenyl phosphonic acid and salts thereof) and foaming agents (methyl isobutyl carbinol), and performing roughing to obtain roughed concentrate and roughed tailings;
(2) adding a cassiterite collecting agent (phenylphosphonic acid and salts thereof) and a foaming agent (methyl isobutyl carbinol) into the obtained rough tailings, scavenging, and scavenging for 2 times to obtain scavenged concentrate, wherein the scavenged concentrate returns to the last flotation operation in sequence;
(3) adding gangue mineral inhibitors (carboxymethyl cellulose and sodium silicate) into the obtained rough concentration concentrate, concentrating for 3 times to obtain concentrated concentrate and concentrated middlings, and returning the concentrated middlings to the last flotation operation in sequence.
After the raw ore with the grade of 0.34% is subjected to one-rough two-sweep three-fine flotation, the cassiterite concentrate with the grade of 34.49% and the recovery rate of 75.86% is obtained.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (1)
1. The application of the collector of aromatic radical phosphonic acid and its salts is characterized in that: the method is applied to flotation separation of cassiterite and gangue minerals, and the flotation process comprises 1 roughing, 2-3 scavenging and 3 concentrating;
the flotation process comprises the following steps:
(1) in the roughing process, adjusting the pH value of the cassiterite pulp to 4-7, sequentially adding a gangue mineral inhibitor carboxymethyl cellulose and sodium silicate, a cassiterite collector phenylphosphonic acid and/or phenylphosphonic acid and salts thereof, and a foaming agent methyl isobutyl carbinol, and roughing to obtain roughing concentrate and roughing tailings; the dosage of the carboxymethyl cellulose and the sodium silicate relative to the raw ore is 300-500 g/t, the dosage of the phenylphosphonic acid and/or the phenylphosphonic acid and the salts thereof relative to the raw ore is 1200-1500 g/t, and the dosage of the methyl isobutyl carbinol relative to the raw ore is 120 g/t;
(2) in the scavenging process, adding cassiterite collecting agent phenylphosphonic acid and/or phenylphosphonic acid and salts thereof and foaming agent methyl isobutyl carbinol into the obtained rough concentration tailings, and scavenging for 2-3 times to obtain scavenging concentrate; returning the scavenged concentrate to the last flotation operation in sequence; the dosage of the phenylphosphonic acid and/or phenylphosphonic acid and salts thereof relative to raw ore is 600-750 g/t, and the dosage of the methyl isobutyl carbinol relative to the raw ore is 80 g/t;
(3) in the concentration process, adding gangue mineral inhibitor carboxymethyl cellulose and sodium silicate into the obtained rough concentration concentrate, concentrating for 3 times to obtain concentrated concentrate and concentrated middlings, and returning the concentrated middlings to the last flotation operation in sequence; the dosage of the carboxymethyl cellulose and the sodium silicate relative to the raw ore is 150-250 g/t;
the aromatic radical phosphonic acid and salt collector thereof comprises benzene phosphonic acid and/or phenyl phosphonic acid and salt thereof, wherein the structural formula of the benzene phosphonic acid and the salt thereof is shown as a formula (I); the structural formula of the phenylphosphonic acid and the salt thereof is shown as a formula (II),
wherein M is1And M2Are respectively divalent cations;
the M is1And M2Are respectively 1/2Sr2+、1/2Be2+、1/2Mg2+、1/2Ca2+、1/2Ba2+、1/2Zn2+And 1/2Mn2+One of (1);
the gangue minerals are quartz, fluorite and calcite;
adopting phenylphosphonic acid and/or phenylphosphonic acid and salts thereof as a cassiterite collecting agent, methyl isobutyl carbinol as a foaming agent, and carboxymethyl cellulose and sodium silicate as gangue mineral inhibitors, and carrying out flotation on cassiterite pulp to obtain cassiterite concentrate;
the mass ratio of the carboxymethyl cellulose to the sodium silicate is 1: 1;
the carboxymethyl cellulose and the sodium silicate are prepared into an aqueous solution with the mass percentage concentration of 20-25%, the phenylphosphonic acid and/or the phenylphosphonic acid and salts thereof are prepared into an aqueous solution with the mass percentage concentration of 10-15%, and the methyl isobutyl carbinol is prepared into an aqueous solution with the mass percentage concentration of 20%.
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| CN109225649B (en) * | 2018-10-29 | 2020-06-30 | 贵州川恒化工股份有限公司 | Phosphorite layer a ore reverse flotation composite collecting agent and preparation method thereof |
| CN111068926B (en) * | 2019-11-12 | 2021-06-29 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111482278B (en) * | 2020-06-03 | 2022-03-22 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN117732597B (en) * | 2024-02-21 | 2024-05-31 | 中国矿业大学(北京) | Flotation recovery method and flotation recovery device for micro-fine cassiterite |
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| SU638378A1 (en) * | 1977-03-11 | 1978-12-25 | Центральный Научно-Исследовательский Институт Оловянной Промышленности "Цнииолово" Министерства Цветной Металлургии Ссср | Collector for flotation cassiterite from ores |
| CN105772226A (en) * | 2016-03-16 | 2016-07-20 | 云南缘矿科技开发有限公司 | Flotation activating agent for fine-grain cassiterite and preparing method of flotation activating agent |
| CN206635377U (en) * | 2017-03-24 | 2017-11-14 | 南昌专腾科技有限公司 | A kind of Tin concentrate ore-sorting system |
| CN106733217A (en) * | 2017-04-07 | 2017-05-31 | 安徽工业大学 | A kind of calcareous Scheelite Flotation collecting agent high and its preparation method and application method |
| CN107520062A (en) * | 2017-10-11 | 2017-12-29 | 江西理工大学 | A kind of preparation method and applications of tin fines stone ore flotation collector |
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