Gold-bearing pyrite coarse particle flotation collector, and preparation method and application thereof

Abstract

The application provides a gold-bearing pyrite coarse particle flotation collector and a preparation method and application thereof. The gold-bearing pyrite coarse particle flotation collector has a general structure as shown in the specification, wherein R1 and R2 are independently selected from hydrogen, C1-C12 substituted or non-substituted alkyl, C1-C12 substituted or non-substituted saturated alkyl, C1-C12 substituted or non-substituted unsaturated hydrocarbon, and C1-C12 substituted or non-substituted cycloalkyl. The preparation method of the gold-bearing pyrite coarse particle flotation collector comprises the following steps: mixing raw materials including water, alkylamine, carbon disulfide, alkali, an oxidizing agent and EDTA, and reacting to obtain the gold-bearing pyrite coarse particle flotation collector. The gold-bearing pyrite coarse particle flotation collector is applied to gold-bearing pyrite flotation and tailing discarding. The gold-bearing pyrite coarse particle flotation collector provided by the application has multiple solid-philic groups, can make the mineral surface sufficiently hydrophobic, and can make coarse particle minerals float, so that the coarse particle mineral flotation and tailing discarding are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ore dressing, in particular to a coarse particle flotation collector for gold-bearing pyrite and a preparation method and application thereof. BACKGROUND

[0002] Gold is the basis of maintaining the confidence of the monetary system and monetary system of each country, so gold plays an important role in economic security and is the guarantee of economic security. The content of gold in ore is generally very low, and it is usually present in pyrite. The development and utilization of these gold resources require the extraction of gold from ore, which involves crushing and grinding the ore, and then using ore dressing methods for pre-concentration to separate gold from the ore.

[0003] To improve the economy of the separation and enrichment process and reduce the impact on the environment is the key to the development and utilization of low-grade resources. Pre-throwing tailings technology, as one of the main technical means to improve the technical and economic efficiency of low-grade ore development, has developed rapidly in recent years. This technology can reduce the grinding energy consumption and flotation reagent consumption by removing a large amount of gangue minerals before separation, and the coarse tailings removed are suitable for construction materials, thus improving the economy and environmental friendliness of low-grade ore development. At present, for +12mm particle size, photoelectric sorting and throwing waste technology has been rapidly popularized, and heavy medium throwing waste technology for +0.5-10mm particle size also shows obvious advantages, while the problem of throwing tailings for-0.5mm particles has been unsolved for a long time, which has become a blank area of tailings throwing technology.

[0004] Flotation is the most important method of gold-bearing pyrite beneficiation, and the feasibility of its application in tailings throwing operation has attracted attention at home and abroad. However, conventional flotation reagents have certain limitations in treating mineral particle size, and generally, it is difficult to float and recover coarse particles larger than 0.3mm, so it is necessary to develop a flotation collector suitable for coarse particle flotation process. SUMMARY

[0005] The present application aims to provide a coarse particle flotation collector for gold-bearing pyrite and a preparation method and application thereof to solve the above problems.

[0006] To achieve the above purpose, the present application adopts the following technical scheme:

[0007] A coarse particle flotation collector for gold-bearing pyrite, the general structure of which is:

[0008]

[0009] wherein R1, R2 are each independently selected from the group consisting of hydrogen, C1-C12 substituted or unsubstituted alkyl, C1-C12 substituted or unsubstituted saturated alkyl, C1-C12 substituted or unsubstituted unsaturated hydrocarbon, C1-C12 substituted or unsubstituted cycloalkyl.

[0010] The application also provides a preparation method of the gold-bearing pyrite coarse particle flotation collector, comprising:

[0011] Mixing raw materials including water, alkylamine, carbon disulfide, base, oxidizing agent and EDTA to obtain the gold-bearing pyrite coarse particle flotation collector.

[0012] Preferably, the mixing comprises:

[0013] Mixing the water, the alkylamine and the base, adding the carbon disulfide dropwise at a first temperature for reaction, after the reaction is completed, adding the oxidizing agent and the EDTA dropwise at a second temperature, stirring for reaction, and then filtering to obtain a solid;

[0014] After the solid is washed with water and dried, the gold-bearing pyrite coarse particle flotation collector is obtained.

[0015] Preferably, the alkylamine has a general structure of:

[0016]

[0017] The molar ratio of the alkylamine to the carbon disulfide is 1:(1.05-3.2), and the mass ratio of the alkylamine to the water is 1:(2-9).

[0018] Preferably, the base comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

[0019] The molar ratio of the base to the carbon disulfide is (1.05-3.2):1.

[0020] Preferably, the first temperature is 20-60°C, and the reaction time at the first temperature is 0.5-8h.

[0021] Preferably, the oxidizing agent consists of an acid and hydrogen peroxide.

[0022] The acid comprises one or more of hydrochloric acid, sulfuric acid and phosphoric acid.

[0023] The molar ratio of the acid to the hydrogen peroxide is 1:(0.7-1.5).

[0024] The molar ratio of the alkylamine to the hydrogen peroxide in the oxidizing agent is 1:(0.4-0.8).

[0025] Preferably, the molar ratio of the EDTA to the alkyl amine is 1: (1000-2000).

[0026] Preferably, the second temperature is 40-60℃.

[0027] The time of the stirring reaction is 15-120 min.

[0028] The application also provides an application of the gold-bearing pyrite coarse particle flotation collector.

[0029] Compared with the prior art, the application has the beneficial effects including:

[0030] The gold-bearing pyrite coarse particle flotation collector provided by the application has multiple solid-philic groups, can be effectively adsorbed on the surface of pyrite, and can make the mineral surface hydrophobic, so that the mineral particles are floated, the recovery rate of the coarse particle gold-bearing pyrite is improved, and the collecting capacity is strong.

[0031] The preparation method of the gold-bearing pyrite coarse particle flotation collector provided by the application is simple to operate, the raw materials are widely sourced, the product quality is stable, and the method is suitable for large-scale industrial production.

[0032] The gold-bearing pyrite coarse particle collector provided by the application can improve the recovery rate of the gold-bearing pyrite under the condition of coarse particles, improve the economy of the separation and enrichment process, reduce the influence on the environment in the process of developing and utilizing low-grade resources, improve the comprehensive utilization rate of resources in minerals, and can be widely applied in the field of mineral flotation. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope of the application.

[0034] Figure 1 The H spectrum of the gold-bearing pyrite coarse particle collector obtained in Example 1;

[0035] Figure 2 The H spectrum of the gold-bearing pyrite coarse particle collector obtained in Example 2;

[0036] Figure 3 The H spectrum of the gold-bearing pyrite coarse particle collector obtained in Example 3;

[0037] Figure 4 The H spectrum of the gold-bearing pyrite coarse particle collector obtained in Example 4;

[0038] Figure 5 The H spectrum of the gold-bearing pyrite coarse particle collector obtained in Example 5. DETAILED DESCRIPTION

[0039] As used in this article:

[0040] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0041] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0042] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0043] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0044] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (K is any number representing a multiplier). It is important to understand that, unlike the number of parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0045] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0046] A rough gold-bearing pyrite flotation collector, a general structure of which is as follows:

[0047]

[0048] R1, R2 are each independently selected from hydrogen, C1-C12 substituted or unsubstituted alkyl, C1-C12 substituted or unsubstituted saturated alkyl, C1-C12 substituted or unsubstituted unsaturated hydrocarbon group, C1-C12 substituted or unsubstituted cycloalkyl.

[0049] The application also provides a preparation method of the rough gold-bearing pyrite flotation collector, comprising:

[0050] Mixing raw materials including water, alkylamine, carbon disulfide, alkali, oxidizing agent and EDTA to obtain the rough gold-bearing pyrite flotation collector.

[0051] In an optional embodiment, the mixing comprises:

[0052] Mixing the water, the alkylamine and the alkali, adding the carbon disulfide dropwise at a first temperature to react, after the reaction is completed, adding the oxidizing agent and the EDTA dropwise at a second temperature, stirring to react, and then filtering to obtain a solid;

[0053] After the solid is washed with water and dried, the rough gold-bearing pyrite flotation collector is obtained.

[0054] In an optional embodiment, a general structure of the alkylamine is as follows:

[0055]

[0056] The molar ratio of the alkylamine to the carbon disulfide is 1:(1.05-3.2), and the mass ratio of the alkylamine to the water is 1:(2-9).

[0057] Optionally, the molar ratio of the alkylamine to the carbon disulfide can be 1:1.05, 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.2 or any value between 1:(1.05-3.2), and the mass ratio of the alkylamine to the water can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or any value between 1:(2-9).

[0058] In an optional embodiment, the alkali comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

[0059] The molar ratio of the alkali to the carbon disulfide is (1.05-3.2):1.

[0060] Optionally, the molar ratio of the base to the carbon disulfide can be 1.05:1, 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.2:1, or any value between (1.05-3.2):1.

[0061] In an optional embodiment, the first temperature is 20°C-60°C, and the reaction time at the first temperature is 0.5h-8h.

[0062] Optionally, the first temperature can be 20°C, 30°C, 40°C, 50°C, 60°C, or any value between 20°C-60°C, and the reaction time at the first temperature can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, or any value between 0.5h-8h.

[0063] In an optional embodiment, the oxidizing agent consists of an acid and hydrogen peroxide;

[0064] The acid comprises one or more of hydrochloric acid, sulfuric acid, and phosphoric acid;

[0065] The molar ratio of the acid to the hydrogen peroxide is 1:(0.7-1.5);

[0066] The molar ratio of the alkyl amine to the hydrogen peroxide in the oxidizing agent is 1:(0.4-0.8).

[0067] Optionally, the molar ratio of the acid to the hydrogen peroxide can be 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or any value between 1:(0.7-1.5); and the molar ratio of the alkyl amine to the hydrogen peroxide in the oxidizing agent can be 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, or any value between 1:(0.4-0.8).

[0068] In an optional embodiment, the molar ratio of the EDTA to the alkyl amine is 1:(1000-2000).

[0069] Optionally, the molar ratio of the EDTA to the alkyl amine can be 1:1000, 1:1100, 1:1200, 1:1300, 1:1400, 1:1500, 1:1600, 1:1700, 1:1800, 1:1900, 1:2000, or any value between 1:(1000-2000).

[0070] In an optional embodiment, the second temperature is 40°C-60°C;

[0071] The stirring reaction time is 15 min to 120 min.

[0072] Optionally, the second temperature can be 40℃, 50℃, 60℃, or any value between 40℃ and 60℃; and the stirring reaction time can be 15 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, or any value between 15 min and 120 min.

[0073] The application also provides the use of the gold-bearing pyrite coarse particle flotation collector for gold-bearing pyrite flotation and tailings discarding.

[0074] The embodiments of the application will be described in detail below with specific examples, but those skilled in the art will understand that the following examples are only for illustration of the application and should not be regarded as limiting the scope of the application. If no specific conditions are indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If no manufacturer of the reagent or instrument is indicated, it is a conventional product that can be obtained by market purchase.

[0075] Example 1

[0076] The embodiment provides a gold-bearing pyrite coarse particle flotation collector, and a preparation method thereof is specifically as follows:

[0077] 100 g of water is added to a four-necked flask, then 14.6 g (0.2 mol) of diethylamine is added to the flask, followed by 8.1 g of sodium hydroxide, the temperature is raised to 35℃, then 16 g of carbon disulfide is gradually added dropwise, the reaction is carried out, after the dropwise addition is completed, stirring is carried out for 4 hours, then the temperature is raised to 50℃, and then an oxidant (prepared from 24.5 g of 40% sulfuric acid and 12 g of 25% hydrogen peroxide solution) and 0.05 g of EDTA are added dropwise, the reaction is completed, then the reaction solution is filtered, the filter cake is washed with water and dried, and finally a gold-bearing pyrite coarse particle flotation collector YJ-01 is obtained.

[0078] The structural formula is as shown in the following:

[0079]

[0080] The H spectrum of the obtained gold-bearing pyrite coarse particle collector is as shown in the following: Figure 1

[0081] Example 2

[0082] The embodiment provides a gold-bearing pyrite coarse particle flotation collector, and a preparation method thereof is specifically as follows:

[0083] ​Into a four-necked flask was added 100 g of water, then 25.8 g (0.2 mol) of dibutylamine was added into the flask, then 8.1 g of sodium hydroxide was added, the temperature was raised to 40°C, then 32 g of carbon disulfide was added dropwise, the reaction was carried out, after the dropwise addition was completed, stirring was carried out for 5 hours, then the temperature was raised to 40°C, then an oxidizing agent (prepared from 19.6 g of 40% sulfuric acid and 10 g of 25% hydrogen peroxide solution) and 0.05 g of EDTA were added dropwise, the reaction was completed, then the reaction solution was filtered, the filter cake was washed with water and dried, and the final product, a coarse pyrite collector YJ-02, was obtained.

[0084] The structural formula is as shown below:

[0085]

[0086] The H spectrum of the obtained coarse pyrite collector is as shown in Figure 2 .

[0087] Example 3

[0088] The present example provides a coarse pyrite collector, and the preparation method thereof is specifically as follows:

[0089] Into a four-necked flask was added 100 g of water, then 19.8 g (0.2 mol) of cyclohexylamine was added into the flask, then 16.2 g of sodium hydroxide was added, the temperature was raised to 25°C, then 20 g of carbon disulfide was added dropwise, the reaction was carried out, after the dropwise addition was completed, stirring was carried out for 8 hours, then the temperature was raised to 60°C, then an oxidizing agent (prepared from 24.5 g of 40% sulfuric acid and 12 g of 25% hydrogen peroxide solution) and 0.05 g of EDTA were added dropwise, the reaction was completed, then the reaction solution was filtered, the filter cake was washed with water and dried, and the final product, a coarse pyrite collector YJ-03, was obtained.

[0090] The structural formula is as shown below:

[0091]

[0092] The H spectrum of the obtained coarse pyrite collector is as shown in Figure 3 .

[0093] Example 4

[0094] The present example provides a coarse pyrite collector, and the preparation method thereof is specifically as follows:

[0095] Into a four-necked flask was added 100 g of water, then 25.8 g (0.2 mol) of diisobutylamine was added into the flask, then 10.5 g of sodium hydroxide was added, the temperature was raised to 35°C, then 25 g of carbon disulfide was added dropwise, the reaction was carried out, after the dropwise addition was completed, stirring was carried out for 0.5 hours, then the temperature was raised to 45°C, then an oxidizing agent (prepared from 39.2 g of 40% sulfuric acid and 25 g of 25% hydrogen peroxide solution) and 0.08 g of EDTA were added dropwise, after the reaction was completed, the reaction solution was filtered, the filter cake was washed with water and dried, and the final product, a pyrite coarse particle flotation collector YJ-04, was obtained.

[0096] The structural formula is as shown below:

[0097]

[0098] The H spectrum of the obtained pyrite coarse particle collector is as shown in Figure 4 .

[0099] Example 5

[0100] The present example provides a pyrite coarse particle flotation collector, and a preparation method thereof is specifically as follows:

[0101] Into a four-necked flask was added 100 g of water, then 19.4 g (0.1 mol) of diallylamine was added into the flask, then 5.0 g of sodium hydroxide was added, the temperature was raised to 55°C, then 16 g of carbon disulfide was added dropwise, the reaction was carried out, after the dropwise addition was completed, stirring was carried out for 6 hours, then the temperature was raised to 60°C, then an oxidizing agent (prepared from 17.29 g of 40% sulfuric acid and 7.2 g of 25% hydrogen peroxide solution) and 0.07 g of EDTA were added dropwise, after the reaction was completed, the reaction solution was filtered, the filter cake was washed with water and dried, and the final product, a pyrite coarse particle flotation collector YJ-05, was obtained.

[0102] The structural formula is as shown below:

[0103]

[0104] The H spectrum of the obtained pyrite coarse particle collector is as shown in Figure 5 .

[0105] Comparative Example 1

[0106] The present comparative example is pentyl xanthate, which is commercially available. The manufacturer is TieLing ore dressing reagent factory, and the content is 95%.

[0107] Comparative Example 2

[0108] The present comparative example is mercaptobenzothiazole, which is commercially available. The manufacturer is Aladdin, and the content is 98%.

[0109] The sulphide ore collectors provided by Examples 1-5 and Comparative Examples 1-2 are used for pre-throwing tailings flotation experiments on a large gold-bearing pyrite in central China.

[0110] The raw ore contains 41.04% quartz, 17.07% albite, 15.01% potassium feldspar, 12.10% mica, 6.56% plagioclase, 2.10% pyrite, 1.63% calcite, 0.87% garnet, 0.78% limonite, and 2.84% other minerals. Gold mainly occurs in pyrite, which accounts for 2.10% of the total amount. Pyrite is intergrown with chalcopyrite, quartz, feldspar, mica, calcite, garnet, limonite, augite, dolomite and other minerals, among which the intergrowth relationship with quartz is the closest.

[0111] The raw ore is ground to a fineness of greater than 1 mm and less than 3 mm, and the pulp concentration is 27%. Under the condition that the gold-bearing pyrite coarse particle collector is added, the addition amount of the gold-bearing pyrite coarse particle collector is 160 g / t, and the flotation results are shown in Table 1.

[0112] Table 1 Performance data table of gold-bearing pyrite coarse particle collector flotation concentrate

[0113] Yield % Gold grade / (g / t) Gold recovery / % Example 1 2.85 36.02 71.91 Example 2 2.68 38.28 75.07 Example 3 2.75 38.58 72.28 Example 4 2.84 36.88 75.97 Example 5 2.86 36.51 73.88 Comparative Example 1 2.08 43.51 67.75 Comparative Example 2 1.88 48.48 66.88

[0114] As can be seen from the results in Table 1, compared with the use of amyl xanthate and mercaptobenzothiazole as collectors, the gold-bearing pyrite coarse particle collector provided by the present application has good effect in the pre-throwing tailings process of gold mine. In the flotation process, gangue is effectively thrown out, reducing the grinding amount, and the gold grade obtained by one rough flotation is as high as about 39.78 g / t, and the gold recovery rate is as high as 76.11%. Therefore, the gold-bearing pyrite coarse particle collector provided by the present application has good collecting performance for coarse particles, can realize pre-throwing tailings in the flotation process, reduce the grinding amount, improve the economic efficiency of separation and enrichment, reduce the impact on the environment in the development and utilization process of low-grade resources, improve the comprehensive utilization rate of mineral resources, and can be widely applied in the field of mineral flotation.

[0115] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0116] Furthermore, to the extent that the terms "comprises", "comprising", "includes", "including" and "has" or any variation thereof are used in the following description and / or claims, such terms are intended to include a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Also, where appropriate to context, the above description and / or claims can refer to actions to be taken by a person or apparatus. Such actions are sometimes referred to as being taken "by the person" or "by the apparatus". Although some embodiments can be described in one preferred embodiment, it is intended that the scope of the application be defined by the claims and their equivalents.

Claims

1. A coarse-grained flotation collector containing pyrite, characterized in that, Its general structural formula is as follows: (This is used for tailings removal in the flotation of pyrite-bearing ore.) ； Wherein, R1 and R2 are both ethyl; or, R1 and R2 are both n-butyl; or, R1 is cyclohexyl and R2 is H; or, R1 and R2 are both isobutyl; or, R1 and R2 are both allyl.

2. A method for preparing the coarse-grained flotation collector containing pyrite as described in claim 1, characterized in that, include: The raw materials, including water, alkylamine, carbon disulfide, alkali, oxidant and EDTA, are mixed and reacted to obtain the coarse flotation collector containing pyrite.

3. The preparation method according to claim 2, characterized in that, The mixture includes: The water, the alkylamine, and the base are mixed, and the carbon disulfide is added dropwise at a first temperature to carry out the reaction. After the reaction is completed, the oxidant and the EDTA are added dropwise at a second temperature, the reaction is stirred, and then the mixture is filtered to obtain a solid. The solid material is washed with water and dried to obtain the coarse flotation collector containing yuppy ore.

4. The preparation method according to claim 2, characterized in that, The general structural formula of the alkylamine is: ； The molar ratio of the alkylamine to the carbon disulfide is 1:(1.05-3.2), and the mass ratio of the alkylamine to the water is 1:(2-9).

5. The preparation method according to claim 2, characterized in that, The alkali includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. The molar ratio of the alkali to the carbon disulfide is (1.05-3.2):

1.

6. The preparation method according to claim 3, characterized in that, The first temperature is 20℃-60℃, and the reaction time under the first temperature condition is 0.5h-8h.

7. The preparation method according to claim 2, characterized in that, The oxidant consists of an acid and hydrogen peroxide; The acid includes one or more of hydrochloric acid, sulfuric acid, and phosphoric acid; The molar ratio of the acid to the hydrogen peroxide is 1:(0.7-1.5). The molar ratio of the alkylamine to the hydrogen peroxide in the oxidant is 1:(0.4-0.8).

8. The preparation method according to claim 2, characterized in that, The molar ratio of EDTA to the alkylamine is 1:(1000-2000).

9. The preparation method according to claim 3, characterized in that, The second temperature is 40℃-60℃; The stirring reaction time is 15 min - 120 min.

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