CN107350084B - A kind of triquaternary ammonium compound used in mineral flotation - Google Patents

Abstract

The invention provides a triquaternary ammonium salt compound used in mineral flotation, belonging to the technical field of mineral processing. The three quaternary ammonium salt compounds shown in formula I are used in phosphate rock, iron ore, bauxite reverse flotation desiliconization and impurity removal, lepidolite ore flotation or potassium chloride and sodium chloride flotation separation as a collector. In formula I: R ¹ and R ² are hydrocarbon groups with 7 to 20 carbons; R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are selected from methyl, ethyl, —(CH ₂ CH ₂ O) _n H or—(CH(CH ₃ )CH ₂ O) _n H, wherein n=1～6; R ⁹ and R ¹⁰ are alkylene groups with 2 to 6 carbon atoms; X is Cl, Br or I . As a collector, the triquaternary ammonium salt compound has three mineral-friendly groups in its molecule, which has stronger electrostatic interaction ability with the mineral surface and better selectivity to target minerals; it has multiple hydrophobic groups, increasing The hydrophobic ability of the collector has a stronger ability to collect target minerals; compared with the commonly used flotation collectors in the prior art, it can effectively improve the flotation efficiency and recovery rate.

Description

A kind of triquaternary ammonium compound used in mineral flotation

technical field

The invention relates to the technical field of mineral processing, in particular to a triquaternary ammonium salt compound used in mineral flotation

Background technique

Quaternary ammonium salt compounds are a class of cationic collectors with good selectivity, widely used in phosphate rock, iron ore, bauxite reverse flotation desiliconization and impurity removal, lepidolite ore flotation or potassium chloride and potassium chloride The flotation separation of sodium chloride has achieved a relatively ideal separation effect, and it is a cationic flotation collector with development prospects.

The quaternary ammonium salt compounds used as flotation agents are mainly alkyl quaternary ammonium salts. Zhong Hong and others systematically studied the reverse flotation desilication behavior and mechanism of quaternary ammonium compound dodecyltrimethylammonium chloride and dodecylamine cationic collectors on bauxite. The results show that the effect of dodecyltrimethylammonium chloride on bauxite reverse flotation desilication is better than dodecylamine, and the effect of dodecyltrimethylammonium chloride on aluminosilicate minerals is mainly Electrostatic interaction. (Minerals Engineering, 2008, 21:1055-1061). Wang Yuhua and others used hexadecyltrimethylammonium bromide as a collector to perform reverse flotation desiliconization on bauxite. Under the conditions of collector dosage of 500g/t and pulp pH of 6-7, the A concentrate with an aluminum-silicon ratio exceeding 9.3 is obtained, and the recovery rate of alumina can reach 76% (Journal of Central South University of Technology, 2003, 10(4): 324-328). Huang Zhiqiang et al. used a new type of bisquaternary ammonium compound, ethane-1,2-bis(dodecyldimethylammonium bromide), to desilicate iron ore by reverse flotation, and compared it with traditional collectors. Differences in dodecylamine flotation performance. Studies have shown that the reverse flotation desiliconization effect of the new bisquaternary ammonium compound ethane-1,2-bis(dodecyldimethylammonium bromide) on iron ore is stronger than that of dodecylamine. The polar group of the diquaternary ammonium collector - CH ₂ N ⁺ (CH ₃ ) ₂ (CH ₂ ) ₂ (CH ₃ ) ₂ N ⁺ CH ₂ - has a very high positive net charge value and strong surface activity , so that it has better reverse flotation desilication ability for iron ore (Chemical Engineering Journal, 2014, 257: 218-228). U.S. Patent No. 4,737,273A discloses a method for reverse flotation desiliconization and impurity removal of phosphate rock, using a quaternary ammonium salt compound containing a hydrophobic group as a collector, wherein each hydrophobic group contains at least 6 carbons atom. This quaternary ammonium salt collector is combined with fuel oil as a collector for reverse flotation desiliconization of phosphate rock, and phosphate ester salt is used as an inhibitor. Selective floatation of siliceous minerals. Choi et al. reported the flotation separation of quaternary ammonium compound octadecyltrimethylammonium chloride on quartz, feldspar and lepidolite (Materials Transactions, 2012, 53(12): 2191-2194). Deng Haibo et al. studied the effects of three kinds of alkyl quaternary ammonium salts and dodecylamine on the flotation behavior of lepidolite (Nonmetallic Minerals, 2012, 35(6): 23-25). Patent CN102259062A discloses a preparation method of a quaternary ammonium salt compound trimethylsilyl octadecyl ammonium chloride collector and its application in the flotation separation of potassium chloride and sodium chloride. The results show that for a salt mine in Qinghai, the ore contains 7.84% potassium chloride and 73.56% sodium chloride. The flotation process of one roughing and two refining is adopted, and the quaternary ammonium compound trimethylsilyl is added to the roughing. Octadecyl ammonium chloride 150g/t, the obtained concentrate contains potassium chloride 92.07%, and the recovery rate of potassium chloride is 91.71%.

There are few studies on the three quaternary ammonium compounds shown in formula I. Esumi et al. reported three quaternary ammonium compounds tribromide-bis(ethyl-2-dimethyldodecyl ammonium)-dodecane Synthesis, surface activity and adsorption behavior on silica/water interface (Journal of Colloid and Interface Science, 1996, 183(2): 539-545). At present, its application as a flotation collector in flotation has not been reported in the prior art.

Contents of the invention

The technical problem to be solved by the present invention is to provide a triquaternary ammonium salt compound for mineral flotation.

The structure of the three quaternary ammonium salt compounds is shown in formula I:

In formula I: R ¹ and R ² are hydrocarbon groups with 7 to 20 carbons; R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are selected from methyl, ethyl, —(CH ₂ CH ₂ O) _n H or—(CH(CH ₃ )CH ₂ O) _n H, wherein n=1～6; R ⁹ and R ¹⁰ are alkylene groups with 2 to 6 carbon atoms; X is Cl, Br or I .

Triquaternary ammonium salt compounds are used as collectors in phosphate rock, iron ore, bauxite reverse flotation desiliconization and impurity removal, lepidolite ore flotation or flotation separation of potassium chloride and sodium chloride.

When the triquaternary ammonium compound is used as a collector, the pH value of the flotation pulp is 3-13; the dosage range of the triquaternary ammonium compound is 40-1600g/t.

The beneficial effects of above-mentioned technical scheme of the present invention are as follows:

In the present invention, three quaternary ammonium salt compounds are used as flotation collectors for the first time, and its advantages are: (1) there are three mineral-friendly groups in its molecule, and the electrostatic interaction ability with the mineral surface is stronger, and the selectivity to the target mineral is Better; (2) It has multiple hydrophobic groups in its molecule, which increases the hydrophobicity of the collector and has a stronger ability to collect target minerals, which can strengthen the anti-floating of phosphate rock, iron ore, and bauxite Separation of silicon and impurities, lepidolite ore flotation or potassium chloride and sodium chloride flotation separation effect.

Description of drawings

Fig. 1 is the process flow chart that tribromide-bis(ethyl-2-dimethyl dodecyl ammonium)-dodecyl methyl ammonium is applied in phosphate rock reverse flotation desiliconization and impurity removal;

Fig. 2 is the process flow diagram of trichloride-bis(butyl-2-dimethyldodecyl ammonium)-tetradecyl methyl ammonium applied in iron ore reverse flotation desiliconization and impurity removal;

Fig. 3 is the process flow diagram of trichloride-bis(propyl-2-diethyltetradecylammonium)-hexadecylethylammonium applied in bauxite reverse flotation desiliconization and impurity removal;

Fig. 4 is the process flow sheet that tribromide-bis(butyl-2-diethyltetradecyl ammonium)-dodecyl ethyl ammonium is applied in lepidolite ore flotation;

Fig. 5 is the technological flow chart that tribromide-bis(ethyl-2-diethylhexadecyl ammonium)-tetradecyl methyl ammonium is applied in the flotation separation of potassium chloride and sodium chloride.

Detailed ways

In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following will describe in detail with reference to the drawings and specific embodiments.

The present invention provides a kind of triquaternary ammonium salt compound for mineral flotation, the structure of the triquaternary ammonium salt compound is shown in formula I:

In formula I: R ¹ and R ² are hydrocarbon groups with 7 to 20 carbons; R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are selected from methyl, ethyl, —(CH ₂ CH ₂ O) _n H or—(CH(CH ₃ )CH ₂ O) _n H, wherein n=1～6; R ⁹ and R ¹⁰ are alkylene groups with 2 to 6 carbon atoms; X is Cl, Br or I .

The application of the triquaternary ammonium salt compound as a collector will be described below in conjunction with specific examples.

Example 1: Application of tribromide-bis(ethyl-2-dimethyldodecylammonium)-dodecylmethylammonium in reverse flotation desiliconization and impurity removal of phosphate rock

A phosphate rock raw ore contains 22.32% of P ₂ O ₅ and 17.81% of SiO ₂ . Grind the ore to -0.074mm to account for 85%, add water to adjust the slurry to a mass concentration of 30%, add sulfuric acid 2500g/t, phosphoric acid 1500g/t , three quaternary ammonium salts compound tribromide-bis(ethyl-2-dimethyl dodecyl ammonium)-dodecyl methyl ammonium dosage 380g/t for roughing flotation, sweeping and adding three quaternary ammonium salts Compound tribromide-bis(ethyl-2-dimethyldodecylammonium)-dodecylmethylammonium 120g/t, add sulfuric acid 500g/t for the first selection, add sulfuric acid 200g/t for the second selection , flotation process flow chart shown in Figure 1. Three quaternary ammonium salt compound tribromide-bis(ethyl-2-dimethyl dodecyl ammonium)-dodecyl methyl ammonium in the present invention and conventional collector dodecylamine are to the flotation of phosphate rock See Table 1 for the selection results. As can be seen from Table 1, compared with conventional collector dodecylamine, when adopting three quaternary ammonium salt compound tribromide-bis(ethyl-2-dimethyl dodecyl ammonium)-dodecyl methyl ammonium , the recovery rate of P ₂ O ₅ in phosphorus concentrate increased by 4.88 percentage points, the grade of P ₂ O ₅ increased by 0.65 percentage points, and the grade of SiO ₂ decreased by 0.35 percentage points.

Table 1 Comparative test results of collector flotation phosphate rock

Example 2: Application of trichloride-bis(butyl-2-dimethyldodecylammonium)-tetradecylmethylammonium in iron ore reverse flotation desiliconization and impurity removal

A certain iron ore magnetic separation concentrate contains Fe 63.57%, SiO ₂ 9.75%, ore grinding to -0.037mm, accounting for 90%, flotation slurry concentration 30%, adding 1000g/t sodium hydroxide, starch 900g/t, The amount of collector is 120g/t, carry out roughing flotation, add 80g/t collector for sweeping, add 300g/t starch for the first selection, add 200g/t starch for the second selection, add 200g/t starch for the third selection t, the flow chart of the flotation process is shown in Figure 2. Three quaternary ammonium salt compounds trichloride-bis(butyl-2-dimethyl dodecyl ammonium)-tetradecyl methyl ammonium among the present invention and the flotation comparative test of commonly used collector dodecylamine The results are shown in Table 2. As can be seen from Table 2, compared with common collector dodecylamine, adopt triquaternary ammonium compound trichloride-bis(butyl-2-dimethyl dodecyl ammonium)-tetradecyl methyl ammonium, The recovery rate of Fe in iron concentrate increased by 3.28 percentage points, the grade of Fe increased by 0.98 percentage points, and the grade of _SiO2 decreased by 1.04 percentage points.

Table 2 Contrast test results of collector flotation iron ore

Example 3: Application of trichloride-bis(propyl-2-diethyltetradecylammonium)-hexadecylethylammonium in bauxite reverse flotation desiliconization and impurity removal

A bauxite ore sample, raw ore contains Al ₂ O ₃ 63.03%, SiO ₂ 11.05%, aluminum-silicon ratio A/S 5.70, the ore is ground to -0.074mm to account for 70%, flotation pulp concentration is 30%, in starch Under the condition of dosage of 3500g/t and collector dosage of 150g/t, roughing flotation of bauxite is carried out, starch 2500g/t and collector 100g/t are added in the first sweep, and starch 2000g/t is added in the second sweep. The collector is 100g/t, and the flow chart of the flotation process is shown in Figure 3. The flotation contrast test of three quaternary ammonium salt compounds trichloride-bis(propyl-2-diethyltetradecylammonium)-hexadecylethylammonium and commonly used collector dodecylamine in the present invention The results are shown in Table 3. As can be seen from Table 3, compared with the commonly used collector dodecylamine, using triquaternary ammonium compound trichloride-bis(propyl-2-diethyltetradecylammonium)-hexadecylethylammonium At this time, the recovery rate of Al ₂ O ₃ in bauxite concentrate increased by 6.05 percentage points, and the aluminum-silicon ratio A/S increased by 0.42.

Table 3 Collector flotation bauxite comparative test results

Embodiment 4: Application of tribromide-bis(butyl-2-diethyltetradecylammonium)-dodecylethylammonium in lepidolite ore flotation

The main useful mineral for the gravity separation tailings of a tantalum-niobium mine is lepidolite, containing 1.19% Li ₂ O, and the particle size is -0.074mm, accounting for 21%. Add water to adjust the slurry to a mass concentration of 30%, and add 140g/t tribromine Chloride-bis(butyl-2-diethyltetradecylammonium)-dodecylethylammonium, carry out rough separation and flotation of lepidolite ore, sweep and add 70g/t tribromide-bis(butyl- 2-diethyltetradecylammonium)-laurylethylammonium, adopts a flotation process flow of once roughing, once sweeping, and once selected, and the flotation process flow chart is shown in Figure 4. Three quaternary ammonium salt compounds tribromide-bis(butyl-2-diethyltetradecyl ammonium)-dodecyl ethyl ammonium in the present invention and the flotation comparative test of commonly used collector coconut oil amine The results are shown in Table 4. As can be seen from Table 4, compared with commonly used collector coconut oil amine, adopt three quaternary ammonium salt compound tribromide-bis(butyl-2-diethyltetradecyl ammonium)-dodecyl ethyl ammonium, The recovery rate of Li ₂ O in lepidolite concentrate increased by 5.28 percentage points, and the grade of Li ₂ O increased by 0.17 percentage points.

Table 4 Collector flotation lepidolite comparison test results

Embodiment 5: Application of tribromide-bis(ethyl-2-diethylhexadecylammonium)-tetradecylmethylammonium in the flotation separation of potassium chloride and sodium chloride

A potash rock salt mine sample, the original ore contains KCl 11.24%, NaCl 40.87%, adding saturated brine to grind the ore to -1mm to account for 90%, the concentration of the flotation pulp is 20%, and the dosage of sodium carboxymethyl cellulose is 130g/t , the amount of collector is 90g/t, and the amount of foaming agent No. 2 oil is 60g/t, carry out roughing flotation of potassium halite, add collector 30g/t for sweeping, and add carboxymethyl fiber for one-time selection The dosage of plain sodium is 50g/t, and the dosage of sodium carboxymethyl cellulose is 40g/t in the second beneficiation. The flow chart of the flotation process is shown in Figure 5. Three quaternary ammonium salt compounds tribromide-bis(ethyl-2-diethylhexadecyl ammonium)-tetradecylmethyl ammonium in the present invention and the flotation contrast test of common collector octadecylamine The results are shown in Table 5. As can be seen from Table 5, compared with the collector octadecylamine commonly used, use three quaternary ammonium compound tribromide-bis(ethyl-2-diethylhexadecyl ammonium)-tetradecyl methyl ammonium , the recovery rate of KCl in potassium chloride concentrate increased by 5.98 percentage points, the grade of KCl increased by 2.29 percentage points, and the grade of NaCl decreased by 1.05 percentage points.

Table 5 Comparative test results of collector flotation potash rock salt ore

The above description is a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvements and modifications It should also be regarded as the protection scope of the present invention.

Claims (2)

1. a three-quaternary ammonium compound for mineral flotation, characterized in that: the three-quaternary ammonium compound structure is as shown in formula I: Specifically, formula I is tribromide-bis(ethyl-2-dimethyldodecyl ammonium)-dodecyl methyl ammonium, trichloride-bis(butyl-2-dimethyl dodecyl ammonium) Alkyl ammonium)-tetradecylmethylammonium, trichloride-bis(propyl-2-diethyltetradecylammonium)-hexadecylethylammonium, tribromide-bis(butyl-2 One of -diethyltetradecylammonium)-dodecylethylammonium, tribromide-bis(ethyl-2-diethylhexadecylammonium)-tetradecylmethylammonium, When the triquaternary ammonium compound is used as a collector, the pH value of the flotation pulp is 3-13; the dosage range of the triquaternary ammonium compound is 40-1600 g/t. 2. the three quaternary ammonium salt compounds for mineral flotation according to claim 1, characterized in that: the three quaternary ammonium salt compounds are used as collectors in phosphate rock, iron ore, bauxite anti-floating It is used in desiliconization and impurity removal, lepidolite ore flotation or flotation separation of potassium chloride and sodium chloride.