CN108187917B - Aromatic phosphonic acid and salt collector thereof and application thereof - Google Patents

Abstract

The invention discloses an aromatic phosphonic acid and its salt collector and application thereof, belonging to the technical field of flotation. The aromatic phosphonic acid and its salt collectors include phenylphosphonic acid and/or phenylphosphonic acid and its salts, which are used in the flotation separation of cassiterite and gangue minerals. The invention adopts aromatic phosphonic acid and its salts as the cassiterite collector, which not only improves the water solubility of the collector, but also has better selectivity, and can effectively separate cassiterite from veins such as quartz, fluorite, and calcite. cassiterite, and the flotation of cassiterite can be realized under a wide range of pulp pH conditions.

Description

A kind of aromatic phosphonic acid and its salt collector and its application

technical field

The invention relates to the technical field of cassiterite flotation, in particular to an aromatic phosphonic acid and its salt collectors and applications thereof.

Background technique

Tin is one of the earliest metal materials developed and utilized by human beings. It plays an irreplaceable role in today's medical equipment, chemical industry, national defense, electronic appliances, marine engineering and other fields. Cassiterite is the only mineral in nature that can be used to smelt metal tin, so the flotation recovery of cassiterite minerals is of great significance to ensure the development of the national economy. Due to the large proportion of cassiterite, coarse-grained cassiterite can be effectively recovered by gravity separation technology; however, cassiterite is brittle, and a large amount of fine mud is easily produced during the crushing and grinding process. When the particle size of cassiterite is less than 20μm , the recovery rate of cassiterite recovered by gravity separation method is seriously insufficient, resulting in the loss of a large amount of fine-grained cassiterite in the tailings. At this time, only flotation technology can ensure the effective separation and recovery of fine-grained cassiterite.

Therefore, reasonable collector application is the key to the success of flotation. There are many types of collectors that can be used for cassiterite flotation, including fatty acids, alkyl sulfosuccinic acid, hydroxamic acid, arsenic acid, phosphonic acid, etc. Wait. However, the selectivity of fatty acid and alkyl sulfosuccinic acid collectors is extremely poor, the collection capacity of hydroxamic acid is insufficient, and the use of arsenic acid collectors is toxic, and only phosphonic acid collectors can be used in the industry. Among the phosphonic acid collectors, although short-chain alkyl phosphonic acids can be used to recover cassiterite by flotation, the collection capacity is insufficient, and the synergistic effect of heavy metal salts (such as lead nitrate) activators is required, which will Causes problems such as rising cost and water source pollution; long-chain alkylphosphonic acid has strong collecting ability, but poor water solubility and greatly reduced selectivity, which limits its application in industry. Therefore, in order to solve the above-mentioned technical problems, it is necessary to provide a new cassiterite flotation collector.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a collector that can interact with the surface of cassiterite, enhance the hydrophobicity of the surface of cassiterite, and can be applied to selectively separate cassiterite from gangue minerals in flotation, so as to solve the above problems. Problems with the prior art.

For achieving the above object, the present invention provides the following scheme:

The present invention provides an aromatic phosphonic acid and its salts collector, which is characterized in that it comprises phenylphosphonic acid and/or phenylphosphonic acid and its salts, and the structural formula of said phenylphosphonic acid and its salts is as follows: (I); the structural formula of the phenylphosphonic acid and its salts is shown in the formula (II),

Wherein, M ₁ and M ₂ are monovalent or divalent cations, respectively.

Preferably, the M ₁ and M ₂ are respectively H ⁺ , NH ⁴⁺ , Na ⁺ , Li ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , 1/2Sr ²⁺ , 1/2Be ²⁺ , 1/2Mg ² One of ⁺ , 1/2Ca ²⁺ , 1/2Ba ²⁺ , 1/2Zn ²⁺ and 1/2Mn ²⁺ .

The invention also provides the application of an aromatic phosphonic acid and its salt collector, which is characterized in that it is applied to the flotation separation of cassiterite and gangue minerals.

Preferably, the gangue minerals are quartz, fluorite and calcite.

Preferably, phenylphosphonic acid and/or phenylphosphonic acid and its salts are used as cassiterite collectors, methyl isobutyl methanol is used as foaming agent, and carboxymethyl cellulose and sodium silicate are used as gangue mineral inhibitors agent, flotation of cassiterite pulp to obtain cassiterite concentrate.

Preferably, the flotation process includes 1 roughing process, 2-3 sweeping processes and 3 beneficiation processes.

Preferably, a kind of aromatic phosphonic acid and its salts collector and application thereof, comprise the following steps:

(1) During the roughing process, adjust the pH value of the cassiterite pulp to 4 to 7, and sequentially add the gangue mineral inhibitor carboxymethyl cellulose and sodium silicate, the cassiterite collector phenylphosphonic acid and/or phenyl Phosphonic acid and its salts, and methyl isobutyl methanol as a foaming agent, are subjected to rough selection to obtain rough concentrate and rough tail; /t, the amount of phenylphosphonic acid and/or phenylphosphonic acid and its salts relative to the raw ore is 1200-1500g/t, and the amount of methyl isobutyl methanol relative to the raw ore is 120g/t;

(2) in the sweeping process, add the cassiterite collector phenylphosphonic acid and/or phenylphosphonic acid and its salts, the foaming agent methyl isobutyl methanol in the gained roughing tailings, and carry out sweeping, Sweep 2 to 3 times to obtain sweep concentrate; sweep concentrate to return to the last flotation operation in sequence; the dosage of phenylphosphonic acid and/or phenylphosphonic acid and its salts relative to the original ore is 600-750g/t , the amount of methyl isobutyl methanol relative to the original ore is 80g/t;

(3) During the beneficiation process, the gangue mineral inhibitor carboxymethyl cellulose and sodium silicate are added to the obtained rougher concentrate, and the beneficiation is performed 3 times to obtain the beneficiated concentrate and the beneficiary medium. The ore sequence returns to the last flotation operation; the dosage of carboxymethyl cellulose and sodium silicate relative to the original ore is 150-250g/t.

Preferably, the mass ratio of the carboxymethyl cellulose and sodium silicate is 1:1.

Preferably, the carboxymethyl cellulose and sodium silicate are prepared into an aqueous solution with a mass percentage concentration of 20% to 25%, and the phenylphosphonic acid and/or phenylphosphonic acid and its salts are prepared with a mass percentage concentration of 10%-15% aqueous solution, the methyl isobutyl methanol is prepared into an aqueous solution whose mass percentage concentration is 20%.

The present invention discloses the following technical effects:

1. phenylphosphonic acid provided by the invention and/or phenylphosphonic acid and salts thereof are phosphonic acid collectors containing benzene ring structure, and the polar groups in phenylphosphonic acid and phenylphosphonic acid are respectively phosphines Acid groups and phosphonic acid groups, in which phosphorus atoms and oxygen atoms can chemically react with tin metal atoms on the surface of cassiterite, thereby being adsorbed on the surface of cassiterite; the non-polar groups in phenylphosphonic acid and phenylphosphonic acid are Benzene ring structure, and the introduction of benzene ring can improve the selectivity, collection ability, strong hydrophobicity and water solubility of phosphonic acid collectors, and can effectively separate cassiterite from gangue minerals such as quartz, fluorite, and calcite, and can The flotation of cassiterite is realized under a wide range of pulp pH conditions.

2. The collector provided by the present invention is environmentally friendly, non-toxic and harmless, and has strong water solubility, and is suitable for large-scale industrial application.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

In order to make the above objects, features and advantages of the present invention more clearly understood, the present invention will be described in further detail below with reference to specific embodiments.

Example 1

Flotation of artificial mixed ore

(1) The cassiterite pure mineral is mixed with the quartz pure mineral, the fluorite pure mineral, and the calcite pure mineral respectively according to the mass ratio of 1:1 to prepare an artificial mixed ore, and the particle size of all the pure minerals is -45 μm;

(2) Take 2 g of artificial mixed ore and 20 mL of distilled water and place it in a 30 mL hanging tank flotation machine, and adjust the slurry for 3 min at a stirring speed of 1992 r/min to obtain cassiterite slurry;

(3) adjust the pH value of cassiterite pulp to 7 with sodium hydroxide and sulfuric acid, add cassiterite collector (phenylphosphonic acid and/or phenylphosphonic acid and its salts), and the cassiterite collector concentration is 60mg /L, after stirring for 3min, add a foaming agent (methyl isobutyl methanol), the concentration of the foaming agent is 100mg/L, after stirring for 3min, aerated flotation to obtain foam products and the remaining tailings in the tank;

(4) The foam product and tailings are respectively dried, weighed, and tested for tin grade after sample preparation, and the yield and recovery rate are calculated.

The flotation results of artificial mixed ore are shown in Table 1 below. The results show that phenylphosphonic acid and its salts and phenylphosphonic acid and its salts collectors can effectively separate cassiterite from quartz, fluorite and calcite, and the flotation index is not much different.

Table 1 Flotation results of artificial mixed ore

Example 2

The raw ore of a cassiterite mine in Inner Mongolia was selected as the raw material. The tin grade in the raw ore was 0.37%, and the gangue minerals were quartz, feldspar, mica, calcite and kaolin.

The dosage of chemicals in the flotation process is: in the roughing process, the addition amount of carboxymethyl cellulose relative to the original ore is 250g/t, the addition amount of sodium silicate relative to the original ore is 250g/t, phenylphosphonic acid and its salts The addition amount relative to the original ore is 1500g/t, the addition amount of methyl isobutyl methanol relative to the original ore is 120g/t; during the sweeping process, the addition amount of phenylphosphonic acid and its salts relative to the original ore is 750g/t , the amount of methyl isobutyl methanol relative to the original ore is 80g/t; in the selection process, the addition amount of carboxymethyl cellulose relative to the original ore is 100g/t, and the amount of sodium silicate relative to the original ore is 100g/t t.

The flotation operation steps are:

(1) The raw ore is crushed and ground to achieve monomer dissociation. It is prepared into pulp in the flotation tank, and the pH value is adjusted to 4-7 with sodium hydroxide and sulfuric acid, and the gangue mineral inhibitor (carboxymethyl Cellulose and sodium silicate), cassiterite collector (phenylphosphonic acid and its salts), foaming agent (methyl isobutyl methanol), roughing to obtain roughing concentrate and roughing tailings;

(2) adding cassiterite collector (phenylphosphonic acid and its salts) and foaming agent (methyl isobutyl methanol) to the obtained roughing tailings, and performing sweep selection, and sweep selection is carried out 3 times to obtain sweep selection. Concentrate, sweep the concentrate and return to the last flotation operation;

(3) Add gangue mineral inhibitor (carboxymethyl cellulose and sodium silicate) to the obtained rougher concentrate, and select three times to obtain a select concentrate and a select medium ore, and the selected medium ore is returned in order to the last flotation operation.

The cassiterite concentrate with a grade of 38.03% and a recovery rate of 73.15% was obtained after the crude ore with a grade of 0.37% was subjected to one-coarse, three-sweep and three-fine flotation.

Example 3

The raw ore of a cassiterite mine in Jiangxi Province was selected as the raw material. The tin grade in the raw ore was 0.34%, and the gangue minerals were quartz, feldspar, mica and fluorite.

The dosage of chemicals in the flotation process is: in the roughing process, the addition amount of carboxymethyl cellulose relative to the original ore is 200g/t, the addition amount of sodium silicate relative to the original ore is 200g/t, phenylphosphonic acid and its salts The addition amount of phenylphosphonic acid and its salts relative to the original ore is 1200g/t, and the addition amount of methyl isobutyl methanol relative to the original ore is 120g/t; during the sweeping process, the addition amount of phenylphosphonic acid and its salts relative to the original ore is 600g /t, the amount of methyl isobutyl methanol relative to the raw ore is 80g/t; during the beneficiation process, the amount of carboxymethyl cellulose added to the raw ore is 100g/t, and the amount of sodium silicate relative to the raw ore is 100g/t 100g/t.

The flotation operation steps are:

(1) The raw ore is crushed and ground to achieve monomer dissociation. It is prepared into pulp in the flotation tank, and the pH value is adjusted to 4-7 with sodium hydroxide and sulfuric acid, and the gangue mineral inhibitor (carboxymethyl Cellulose and sodium silicate), cassiterite collector (phenylphosphonic acid and its salts), foaming agent (methyl isobutyl methanol), and roughing to obtain roughing concentrate and roughing tailings ;

(2) adding cassiterite collector (phenylphosphonic acid and its salts) and foaming agent (methyl isobutyl methanol) to the obtained roughing tailings, and performing sweep selection, and sweep selection is carried out twice to obtain Sweep the concentrate, and return to the last flotation operation in sequence;

(3) Add gangue mineral inhibitor (carboxymethyl cellulose and sodium silicate) to the obtained rougher concentrate, and select three times to obtain a select concentrate and a select medium ore, and the selected medium ore is returned in order to the last flotation operation.

The cassiterite concentrate with a grade of 34.49% and a recovery rate of 75.86% is obtained after the crude ore with a grade of 0.34% is subjected to one-coarse, two-sweep and three-fine flotation.

The above-mentioned embodiments are only to describe the preferred modes of the present invention, but not to limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.

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%.