Preparation method of a ferberite flotation collector and application thereof

Abstract

The application discloses a preparation method of a ferrospinel floatation collector and application thereof, and belongs to the technical field of floatation collectors. First, ammonium halide is poured into water, and after being dissolved, nitrobenzene organic matter and a catalyst are added, and sufficient stirring is conducted to obtain a mixed solution A; an acyl halide compound, sodium carbonate and an organic solvent are sequentially added into the mixed solution A, and sufficient stirring is conducted, and reaction is carried out at a temperature of-20-20 DEG C to obtain the ferrospinel floatation collector. The preparation method of the ferrospinel floatation collector and application thereof have the advantages that the ferrospinel collector prepared by the application has good selective collecting effect on ferrospinel, can significantly reduce the content of pyrite and pyrrhotite in zinc concentrate, and improves the quality of the zinc concentrate.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flotation collector, in particular to a preparation method of a willemite flotation collector and application thereof. BACKGROUND

[0002] Willemite is a kind of sulfide mineral which is difficult to float, especially the willemite with high iron content. Xanthate is the most commonly used collector for willemite. The high-grade xanthate with strong collecting ability and long carbon chain is often used as the collector for unactivated willemite and iron willemite, and the low-grade xanthate with short carbon chain can be used only after activation. Xanthate has strong collecting ability and high recovery rate, but poor selectivity. Therefore, lime with strong inhibition performance and copper sulfate with strong activation performance are often used together, which results in high pH value of willemite flotation, large amount of copper sulfate, low recovery rate of associated metals, and excessive residual heavy metals in mineral processing wastewater. Cationic collectors represented by dodecylamine have the advantages of good selectivity and fast flotation speed. Under suitable potential conditions, willemite and gangue minerals can be well separated by lime slurry, but dodecylamine has strong collecting performance on pyrrhotite, and cannot realize effective separation of iron willemite and pyrrhotite. With the exploitation and utilization of zinc resources, easy-to-select ores are gradually exhausted, and more and more refractory ores are produced. Traditional single collector has strong collecting ability on iron willemite, but poor selectivity, and the flotation effect is not ideal, which cannot meet the demand of efficient utilization of increasingly lean mineral resources. In recent years, many mineral processing researchers have found that the combined collector composed of different collectors in a certain proportion has better collecting effect than the single collector, and can effectively improve the grade and recovery rate of iron willemite concentrate. At present, the research on combined collector in the field of iron willemite beneficiation has made some progress. Unfortunately, most of the developed combined collectors are combinations of traditional collectors, which can solve some problems in iron willemite beneficiation, but it is difficult to balance the beneficiation indexes, reagent cost, reagent system, and foam performance. Therefore, it is necessary to develop new and efficient iron willemite collectors with excellent performance for the development and utilization of iron willemite resources. SUMMARY

[0003] The present application aims to provide a preparation method of an iron willemite flotation collector and application thereof, and to prepare an iron willemite collector with stable operation, simple process, high conversion rate, and high selectivity, which has good collecting ability and selectivity, can well recover iron willemite from ores, and improve the resource utilization rate.

[0004] To achieve the above-mentioned purpose, the present application provides a preparation method of an iron willemite flotation collector, which comprises the following steps:

[0005] S1, according to weight parts, preparation nitrobenzene organic matter 10-30 parts, ammonium halide 10-30 parts, catalyst 10-20 parts; first ammonium halide is poured into water, dissolved after adding nitrobenzene organic matter and catalyst, fully stir, get mixed solution A;

[0006] S2, according to weight parts, preparation acyl halide compound 10-30 parts, sodium carbonate 10-30 parts, organic solvent 10-30 parts; acyl halide compound, sodium carbonate and organic solvent are successively added to mixed solution A, fully stir, reaction is carried out at-20-20 ℃ temperature, get iron flash zinc ore flotation collector.

[0007] Preferably, the nitrobenzene organic matter in the step S1 is an organic matter with formula 1 structure,

[0008]

[0009] Wherein, R is C n H 2n Alkyl, n≥1.

[0010] Preferably, the ammonium halide in the step S1 is one of ammonium chloride and ammonium bromide.

[0011] Preferably, the catalyst in the step S1 is zinc metal.

[0012] Preferably, the mass ratio of nitrobenzene organic matter to ammonium halide in the step S1 is 1:(1-2).

[0013] Preferably, the acyl halide compound in the step S2 is a compound with C n H 2n COX structure, wherein n≥1, X is one of chlorine, bromine and iodine.

[0014] Preferably, the organic solvent in the step S2 is one of pyrimidine, dichloromethane and diethyl ether.

[0015] Preferably, the mass ratio of acyl halide compound to sodium carbonate in the step S2 is 1:(1-2).

[0016] The application also provides the application of the collector prepared by the above preparation method in iron flash zinc ore flotation.

[0017] Preferably, the dosage of the collector in the iron flash zinc ore flotation is: when the iron content in the zinc ore is <6%, the dosage of the collector is 0-300 g / t; when the iron content in the zinc ore is 6-12%, the dosage of the collector is 100-500 g / t; when the iron content is 12-18%, the dosage of the collector is 200-800 g / t; when the iron content is >18%, the dosage of the collector is 300-1000 g / t.

[0018] Therefore, the application provides a preparation method of a smithsonite flotation collector and application thereof, and beneficial effects are as follows.

[0019] (1) The smithsonite flotation collector prepared by the application is safe, non-toxic, convenient to use, stable, has good selectivity, strong collecting capacity, and low dosage, is suitable for low-grade, poor floatability, and high-iron zinc sulfide ore, can effectively collect fine-grained iron-containing smithsonite, and has better secondary utilization effect.

[0020] (2) The smithsonite collector prepared by the application has good selective collecting effect on iron smithsonite, can significantly reduce the content of pyrite and pyrrhotite in zinc concentrate, and improve the quality of zinc concentrate.

[0021] (3) The smithsonite collector prepared by the application also has certain foaming property, can reduce the dosage of a foaming agent in the production process, and can significantly reduce the production cost.

[0022] (4) The raw material for preparing the smithsonite flotation collector is widely sourced and green and environmentally friendly, and the preparation process is simple. In the preparation of conventional zinc sulfide flotation reagents, lime is used to inhibit pyrite, and copper sulfate is used to activate smithsonite. However, the pure mineral test of pyrite by the zinc sulfide flotation collector of the application shows that the collecting capacity of the collector for pyrite is very weak, the adsorption amount on the surface of pyrite is very small, and the adsorption is not firm, so lime is not used to inhibit pyrite. At the same time, the reagent has strong collecting capacity for zinc sulfide, so copper sulfate is not used to activate smithsonite. The application realizes efficient flotation recovery of zinc sulfide without lime and copper sulfate, and has practical application value.

[0023] The technical solutions of the application are further described in detail through examples. DETAILED DESCRIPTION

[0024] The application provides a preparation method of a smithsonite flotation collector, comprising the following steps.

[0025] S1, according to the weight fraction, 10-30 parts of nitrobenzene organic matter, 10-30 parts of halide, and 10-20 parts of catalyst are prepared; first, the halide is poured into water, and after dissolution, the nitrobenzene organic matter and the catalyst are added, and fully stirred to obtain a mixed solution A;

[0026] In the application, the nitrobenzene organic matter is an organic matter with the structure of formula 1,

[0027]

[0028] wherein, R is C n H 2nalkyl, n≥1, preferably 2-8, further preferably 2-4, and more preferably 2-3; the ammonium halide is one of ammonium chloride and ammonium bromide, and preferably ammonium chloride; and the catalyst is zinc metal. Preferably, the mass ratio of the nitrobenzene organic compound to the ammonium halide is 1:(1-2), and further preferably 1:1.5, and the stirring time is greater than or equal to 10 min.

[0029] S2, by weight, the acyl halide compound is 10-30 parts, sodium carbonate is 10-30 parts, and an organic solvent is 10-30 parts; the acyl halide compound, the sodium carbonate, and the organic solvent are sequentially added to the mixed solution A, and are fully stirred and reacted at a temperature of-20-20℃ to obtain the floatation collector of marmatite.

[0030] In the present application, the acyl halide compound is a compound having a C n H 2n COX structure, wherein n≥1, preferably 2-8, further preferably 2-4, and more preferably 2-3; and X is one of chlorine, bromine, and iodine, and preferably chlorine. Preferably, the mass ratio of the acyl halide compound to the sodium carbonate is 1:(1-2), and further preferably 1:1.5. The organic solvent is one of pyrimidine, dichloromethane, and diethyl ether, and preferably dichloromethane.

[0031] The reaction temperature is kept between-20℃ and 20℃, preferably between-10℃ and 0℃, and further preferably between-5℃ and 0℃, and the stirring time is greater than or equal to 10 min.

[0032] The present application also provides the use of the floatation collector prepared by the above preparation method in the floatation of marmatite. The dosage of the floatation collector in the floatation of marmatite is as follows: when the iron content in the marmatite is less than 6%, the dosage of the floatation collector is 0-300 g / t; when the iron content is 6-12%, the dosage is 100-500 g / t; when the iron content is 12-18%, the dosage is 200-800 g / t; and when the iron content is greater than 18%, the dosage is 300-1000 g / t.

[0033] In order to make the purpose, technical scheme and advantages of the present application clearer and more apparent, the present application is further described in detail below with specific examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not intended to limit the scope of the claimed present application, but only represent selected embodiments of the present application. Based on the examples in the present application, all other examples obtained by those of ordinary skill in the art without making creative efforts fall within the scope of the present application.

[0034] Example 1

[0035] The embodiment provides a preparation method of a smithsonite flotation collector, and the preparation method is as follows: 10 parts of p-ethyl nitrobenzene, 10 parts of ammonium chloride and 10 parts of zinc single element are prepared according to weight parts; after the ammonium chloride is fully dissolved in water, the p-ethyl nitrobenzene and the zinc single element are added; after sufficient stirring until complete reaction (the reaction time is 2 hours), 10 parts of acetyl chloride, 10 parts of sodium carbonate and 10 parts of diethyl ether are added; the stirring is continuously carried out at-5 DEG C for 8 hours until the solution is a brown liquid, and the collector is obtained, and the collector is recorded as a test reagent 1.

[0036] Example 2

[0037] The embodiment provides a preparation method of a smithsonite flotation collector, and the preparation method is as follows: 10 parts of p-ethyl nitrobenzene, 10 parts of ammonium chloride and 10 parts of zinc single element are prepared according to weight parts; after the ammonium chloride is fully dissolved in water, the p-ethyl nitrobenzene and the zinc single element are added; after sufficient stirring until complete reaction (the reaction time is 2 hours), 10 parts of acetyl chloride, 10 parts of sodium carbonate and 10 parts of diethyl ether are added; the stirring is continuously carried out at-5 DEG C for 8 hours until the solution is a brown liquid, and the collector is obtained, and the collector is recorded as a test reagent 1.

[0038] Example 3

[0039] The embodiment provides a preparation method of a smithsonite flotation collector, and the preparation method is as follows: 10 parts of p-ethyl nitrobenzene, 10 parts of ammonium chloride and 10 parts of zinc single element are prepared according to weight parts; after the ammonium chloride is fully dissolved in water, the p-ethyl nitrobenzene and the zinc single element are added; after sufficient stirring until complete reaction (the reaction time is 2 hours), 10 parts of acetyl chloride, 10 parts of sodium carbonate and 10 parts of diethyl ether are added; the stirring is continuously carried out at-5 DEG C for 8 hours until the solution is a brown liquid, and the collector is obtained, and the collector is recorded as a test reagent 1.

[0040] Comparative Example 1

[0041] The comparative example is identical with the example 2 except that no nitrobenzene organic matter is added; and the obtained product is recorded as a comparative reagent 1.

[0042] Comparative Example 2

[0043] The comparative example is identical with the example 1 except that no halide ammonium is added; and the obtained product is recorded as a comparative reagent 2.

[0044] Comparative Example 3

[0045] The comparative example is identical with the example 1 except that no catalyst is added; and the obtained product is recorded as a comparative reagent 3.

[0046] Comparative Example 4

[0047] The comparative example is identical with the example 1 except that no acyl halide compound is added; and the obtained product is recorded as a comparative reagent 4.

[0048] Comparative Example 5

[0049] The other conditions of this comparative example are consistent with Example 1, except that no sodium carbonate is added; the product obtained is denoted as Comparative Reagent 5.

[0050] Comparative Example 6

[0051] The other conditions of this comparative example are consistent with Example 1, except that no organic solvent is added; the product obtained is denoted as Comparative Reagent 6.

[0052] Comparative Example 7

[0053] The other conditions of this comparative example are consistent with Example 1, except that all the reactants are added to the container at the same time and stirred to mix; the product obtained is denoted as Comparative Reagent 7.

[0054] Comparative Example 8

[0055] The other conditions of this comparative example are consistent with Example 1, except that the amount of ethyl nitrobenzene is 100 parts; the product obtained is denoted as Comparative Reagent 8.

[0056] Comparative Example 9

[0057] The other conditions of this comparative example are consistent with Example 1, except that the amount of ammonium chloride is 100 parts; the product obtained is denoted as Comparative Reagent 9.

[0058] Comparative Example 10

[0059] The other conditions of this comparative example are consistent with Example 1, except that the amount of acetyl chloride is 100 parts; the product obtained is denoted as Comparative Reagent 10.

[0060] Comparative Example 11

[0061] The other conditions of this comparative example are consistent with Example 1, except that the amount of sodium carbonate is 100 parts; the product obtained is denoted as Comparative Reagent 11.

[0062] Comparative Example 12

[0063] The other conditions of this comparative example are consistent with Example 1, except that the reaction temperature is 50°C; the product obtained is denoted as Comparative Reagent 12.

[0064] Comparative Example 13

[0065] The other conditions of this comparative example are consistent with Example 1, except that the reaction temperature is -50°C; the product obtained is denoted as Comparative Reagent 13.

[0066] Comparative Example 14

[0067] The comparative example Comparative Example 14 uses butyl xanthate as a collector.

[0068] Comparative Example 15

[0069] The comparative example Comparative Example 15 uses ethylthiuram disulfide as a collector.

[0070] Flotation experiment

[0071] 1. Raw material

[0072] The ore raw material is taken from tailings after lead selection of a lead-zinc mine in Chenzhou, Hunan, containing about 5.3% zinc, about 11.5% iron, and about 14.2% sulfur. The collector used in the experiment is the collector obtained in Examples 1-3 and Comparative Examples 1-15, the depressant is sodium sulfite; when the collector is the collector described in Comparative Example 14 and Comparative Example 15, the depressant is lime, and the activator is copper sulfate.

[0073] 2. Operation steps and technical conditions

[0074] Take 500 grams of material and add water to adjust the pulp concentration to 30-45%, add the collector described in the application at a dosage of 150 g / t, stir for 3 minutes, then perform roughing operation to obtain rough concentrate and tailings; add 50 g / t of the collector described in the application to the tailings of the roughing operation, perform 2 times of scavenging operation, and return the scavenging concentrate to the previous flotation operation in sequence; perform once blank cleaning on the roughing concentrate to obtain concentrate, and return the middlings of the cleaning operation to the roughing operation in sequence; the experimental comparison results are shown in Table 1.

[0075] Table 1

[0076]

[0077]

[0078]

[0079] From the flotation experiment results of the collectors obtained in Examples 1-3 and Comparative Examples 1-15, it can be seen that the collector prepared in the application has good collecting effect and better selectivity for marmatite. Under the same raw material and beneficiation system, compared with traditional collectors such as xanthate and ethylthiuram disulfide, the collector prepared in the application can obtain higher recovery rate and better beneficiation index. At the same time, from the flotation experiment results of the collectors obtained in Comparative Examples 1-13, it can be seen that the collector prepared by synthesis of the reagents outside the protection scope of the application or the single-component reagent cannot achieve good collection of marmatite.

[0080] It should be pointed out finally that the above examples are only used to illustrate the technical solutions of the present application but not to limit it, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present application can still be modified or replaced equivalently, and these modifications or equivalent replacements should not make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A process for the preparation of a ferberite flotation collector, characterized by, The method comprises the following steps: S1, according to the weight fraction, 10-30 parts of nitrobenzene organic matter, 10-30 parts of ammonium halide, 10-20 parts of catalyst; first, pour the ammonium halide into water, dissolve, then add the nitrobenzene organic matter and the catalyst, fully stir, to obtain a mixed solution A; S2, according to the weight fraction, 10-30 parts of acyl halide compound, 10-30 parts of sodium carbonate, 10-30 parts of organic solvent; acyl halide compound, sodium carbonate and organic solvent are added to the mixed solution A in sequence, fully stirred, reacted at a temperature of-20-20℃, to obtain a ferrospinel flotation collector; The nitrobenzene organic matter in the step S1 is an organic matter with the structure of formula 1, Formula 1 wherein R is C n H 2n alkyl, n > 1; The catalyst in the step S1 is zinc metal; The mass ratio of the nitrobenzene organic matter to the ammonium halide in the step S1 is 1:(1-2); The acyl halide compound in the step S2 is a compound having C n H 2n a compound of COX structure, wherein n≥1, X is one of chlorine, bromine, iodine.

2. A process for the preparation of a ferberite flotation collector according to claim 1, characterized by: The ammonium halide in the step S1 is one of ammonium chloride and ammonium bromide.

3. A process for the preparation of a ferberite flotation collector as claimed in claim 1, wherein the process comprises the steps of: The organic solvent in the step S2 is one of pyrimidine, dichloromethane and diethyl ether.

4. A process for the preparation of a ferberite flotation collector as claimed in claim 1, wherein: The mass ratio of the acyl halide compound to the sodium carbonate in the step S2 is 1:(1-2).

5. A flotation collector produced by the method according to any one of claims 1 to 4, characterized by: The flotation collector is applied to ferrospinel flotation.

6. The flotation collector according to claim 5, characterised in that, The dosage of the flotation collector in the ferrospinel flotation is: when the iron content in the ferrospinel is <6%, the dosage of the flotation collector is 0-300g / t; when the iron content in the ferrospinel is 6-12%, the dosage of the flotation collector is 100-500g / t; when the iron content is 12-18%, the dosage of the flotation collector is 200-800g / t; when the iron content is >18%, the dosage of the flotation collector is 300-1000g / t.

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