A flotation desulfurization activator, its preparation method and application

Abstract

The application relates to the technical field of recycling of mineral soil resources, in particular to a flotation desulfurization activator as well as a preparation method and application thereof; in terms of 1 mol of phytic acid, raw materials of the flotation desulfurization activator satisfy: copper hydroxide: 0-6 mol, ammonium carbonate: 0-6 mol; the flotation desulfurization activator satisfies: (2m+2n):q=12:1, wherein q is the amount of substance of phytic acid; m is the amount of substance of copper hydroxide; and n is the amount of substance of ammonium carbonate. The flotation desulfurization activator can reduce the content of hydrophilic substances wrapped on the surface of pyrite in high-sulfur bauxite, so as to expose the fresh surface of the high-sulfur bauxite, and in addition, the copper ions of the copper hydroxide can be directly adsorbed on the sulfur atoms of the pyrite in the high-sulfur bauxite with the fresh surface exposed through the ammonium carbonate, so that the number of active sites on the surface of the high-sulfur bauxite can be increased, and then the activation performance of the activator on the high-sulfur bauxite can be improved.

Description

Technical Field

[0001] This application relates to the field of mineral resource recycling technology, and in particular to a flotation desulfurization activator, its preparation method and application. Background Technology

[0002] Domestic bauxite deposits are mainly monohydrate gibbsite-type high-sulfur bauxite. Although most of these bauxite deposits have high grades, their sulfur content is also very high. Therefore, desulfurization treatment must be carried out before the development and utilization of these bauxite resources. At present, the most effective desulfurization method is flotation. Traditional flotation methods generally use activators such as sulfuric acid or copper sulfate for activation.

[0003] However, when encountering high-sulfur bauxite slurry with high mud content, the activation performance of these activators is poor, which will affect the indicators of the bauxite concentrate after flotation. Summary of the Invention

[0004] This application provides a flotation desulfurization activator and its preparation method to solve the following technical problem: how to improve the activation performance of the activator on high-sulfur bauxite slurry with high mud content.

[0005] In a first aspect, this application provides a flotation desulfurization activator, wherein the raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following conditions: copper hydroxide: 0-6 mol, ammonium carbonate: 0-6 mol; the flotation desulfurization activator satisfies the following conditions:

[0006] (2m+2n):q=12:1,

[0007] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide; and n is the amount of ammonium carbonate.

[0008] Optionally, the amount of copper hydroxide is 1 mol to 6 mol, and the amount of ammonium carbonate is 1 mol to 6 mol.

[0009] Optionally, the amount of copper hydroxide is 3 mol to 6 mol, and the amount of ammonium carbonate is 1 mol to 3 mol.

[0010] Optionally, the flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0011]

[0012] In Formula 1, m is the amount of copper hydroxide; n is the amount of ammonium carbonate.

[0013] The amount of copper hydroxide, m, and the amount of ammonium carbonate, n, satisfy: (2m + 2n) = 12.

[0014] Secondly, this application provides a method for preparing the flotation desulfurization activator described in the first aspect, the method comprising:

[0015] Phytic acid, copper hydroxide, and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide, and ammonium carbonate, thereby obtaining a flotation desulfurization activator.

[0016] Optionally, the final temperature of the heating is 25℃ to 90℃, and the heating time is 0.5h to 6h.

[0017] Thirdly, this application provides an application of a flotation desulfurization activator, the application including using the flotation desulfurization activator described in the first aspect as a desulfurization reagent for the desulfurization treatment of high-sulfur bauxite.

[0018] Fourthly, this application provides a desulfurization method for high-sulfur bauxite, the method comprising:

[0019] The high-sulfur bauxite is crushed and then ground to obtain high-sulfur bauxite powder.

[0020] Sodium silicate inhibitors are added to the high-sulfur bauxite powder for the first slurry preparation to obtain the first slurry.

[0021] The flotation desulfurization activator described in the first aspect is added to the first slurry for a second slurry preparation to obtain a second slurry;

[0022] Xanthate-based desulfurization collectors and frothers are added to the second slurry to obtain flotation slurry;

[0023] Acidic gas is introduced into the flotation pulp to prevent it from being oxidized. The flotation pulp after the acidic gas is introduced is then subjected to flotation skimming to obtain a flotation mixture.

[0024] The flotation mixture is subjected to roughing, cleaning, and scavenging to obtain aluminum concentrate and sulfur concentrate, respectively.

[0025] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥5×10 -5 :1;

[0026] The xanthate-based desulfurizing collector includes at least one of the following:

[0027] Ethyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate and isopentyl xanthate.

[0028] Optionally, the weight m3 of the fine-grained high-sulfur bauxite powder and the weight m4 of the high-sulfur bauxite powder satisfy the relationship: m3:m4=(0.75:1)~(0.85:1), and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0029] Optionally, the flotation skimming time is 13 min to 18 min.

[0030] The technical solutions provided in this application have the following advantages compared with the prior art:

[0031] This application provides a flotation desulfurization activator. Based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following: copper hydroxide: 0-6 mol, ammonium carbonate: 0-6 mol. The flotation desulfurization activator satisfies the following ratio: (2m+2n):q = 12:1, where q is the amount of phytic acid; m is the amount of copper hydroxide; and n is the amount of ammonium carbonate. The amount of phytic acid in the raw materials of the flotation activator is generally 1 mol, which ensures sufficient phytic acid in the flotation activator. Sufficient phytic acid can increase the oxidation potential of pyrite surface in high-sulfur bauxite. With an increased surface oxidation potential, the hydrophilic substances in pyrite in high-sulfur bauxite are easily removed, thereby reducing the sulfur content. The content of hydrophilic substances coating the surface of pyrite in bauxite is increased to expose the fresh surface of high-sulfur bauxite. In addition, the amount of copper hydroxide and ammonium carbonate is generally 0-6 mol, and the flotation desulfurization activator can meet the ratio of the sum of the amount of copper hydroxide (m) and the amount of ammonium carbonate (n) to the amount of phytic acid = 12:1. Ammonium carbonate can promote the direct adsorption of copper ions of copper hydroxide onto the sulfur atoms of pyrite in the exposed fresh surface of high-sulfur bauxite, so as to avoid the sulfur atoms on the surface of high-sulfur bauxite occupying other active sites, thereby increasing the number of active sites on the surface of high-sulfur bauxite, and thus improving the activation performance of the activator on high-sulfur bauxite. Attached Figure Description

[0032] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0033] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 A microscopic schematic diagram of a flotation desulfurization activator provided in an embodiment of this application;

[0035] Figure 2 This is a schematic flowchart of a method for preparing the flotation desulfurization activator provided in an embodiment of this application;

[0036] Figure 3 This application provides a schematic diagram of a desulfurization method for high-sulfur bauxite. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0038] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range; for example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range such as 1, 2, 3, 4, 5, and 6, regardless of the range; in addition, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0039] In this document, terms including "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. "At least one" means one or more, and "more than one" means two or more; "at least one", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or plural items; for example, "at least one of a, b, or c", or "at least one of a, b, and c" can mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple. Unless otherwise specified, all raw materials, reagents, instruments, and equipment used in this application are commercially available or can be prepared by existing methods.

[0040] It should be noted that the defects of the activators such as sulfuric acid or copper sulfate used in the traditional flotation method in the background technology include: (1) Sulfuric acid is highly corrosive, highly polluting, and poses a great safety hazard. It is also harmful to the health of personnel. In addition, sulfuric acid is not conducive to industrial application in terms of transportation, storage, production management and pipeline corrosion. (2) Copper sulfate is expensive and has a certain degree of corrosivity. Long-term contact with it will cause great harm to the health of personnel. Furthermore, the discharge of wastewater after copper sulfate flotation treatment will have an adverse impact on the environment. (3) When encountering high-sulfur bauxite slurry with high mud content, since the sulfur in high-sulfur bauxite is concentrated in the pyrite component, these activators have low activation ability for pyrite, which will lead to poor activation performance of high-sulfur bauxite slurry, thereby affecting the indicators of bauxite concentrate after flotation treatment.

[0041] Figure 1 A schematic diagram of a flotation desulfurization activator provided in an embodiment of this application is shown as an example;

[0042] like Figure 1 As shown in the embodiment of this application, a flotation desulfurization activator is provided. The raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following conditions: copper hydroxide: 0-6 mol, ammonium carbonate: 0-6 mol; the flotation desulfurization activator satisfies the following conditions:

[0043] (2m+2n):q=12:1,

[0044] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide; and n is the amount of ammonium carbonate.

[0045] The amount of copper hydroxide can be 0 mol, 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, or 6 mol.

[0046] The amount of ammonium carbonate can be 0 mol, 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, or 6 mol.

[0047] In some optional embodiments, the amount of copper hydroxide is 1 mol to 6 mol, and the amount of ammonium carbonate is 1 mol to 6 mol.

[0048] In some optional embodiments, the molar mass fraction of copper hydroxide is 3 mol to 6 mol, and the molar mass fraction of ammonium carbonate is 1 mol to 3 mol.

[0049] In these embodiments, the amount of copper hydroxide can be 1 mol to 6 mol, the amount of ammonium carbonate can be 1 mol to 6 mol, or the amount of copper hydroxide can be 3 mol to 6 mol and the amount of ammonium carbonate can be 1 mol to 3 mol. This ensures that the flotation activator contains sufficient amounts of copper hydroxide and ammonium carbonate. The sufficient amounts of copper hydroxide and ammonium carbonate can promote the direct adsorption of copper ions onto the sulfur atoms of pyrite in the exposed fresh surface of high-sulfur bauxite, thereby preventing sulfur atoms on the surface of high-sulfur bauxite from occupying other active sites. This can improve the activity of the surface of high-sulfur bauxite, and thus improve the activation performance of the activator on high-sulfur bauxite.

[0050] The amount of copper hydroxide can be 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, or 6 mol.

[0051] The amount of ammonium carbonate can be 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, or 6 mol.

[0052] In some alternative embodiments, the flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0053]

[0054] In Formula 1, m is the amount of copper hydroxide; n is the amount of ammonium carbonate.

[0055] The amounts of copper hydroxide and ammonium carbonate satisfy the following: (2m+2n)=12;

[0056] In these embodiments, the flotation desulfurization activator can have a molecular structure as shown in Formula 1, and the amounts of copper hydroxide and ammonium carbonate can satisfy: (2m+2n)=12, which indicates that the reaction between phytic acid, copper hydroxide and ammonium carbonate in the flotation desulfurization activator is sufficient, thereby forming a stable flotation desulfurization activator.

[0057] Figure 2 An exemplary schematic diagram of a method for preparing the flotation desulfurization activator provided in an embodiment of this application is shown;

[0058] Based on a general inventive concept, such as Figure 2 As shown in the embodiments of this application, a method for preparing the flotation desulfurization activator is provided, the method comprising:

[0059] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide and ammonium carbonate to obtain a flotation desulfurization activator.

[0060] This method is for preparing the flotation desulfurization activator mentioned above. The specific composition of the flotation desulfurization activator can be referred to the above embodiments. Since this preparation method adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0061] It should be noted that the mixing and heating can be carried out simultaneously to ensure that phytic acid, copper hydroxide and ammonium carbonate are mixed evenly, so as to facilitate the subsequent neutralization reaction to proceed fully.

[0062] In some optional embodiments, the final temperature of the heating is 25°C to 90°C, and the heating time is 0.5h to 6h.

[0063] In these embodiments, the final heating temperature can be 25°C to 90°C, and the heating time can be 0.5h to 6h, which can promote the full neutralization reaction between phytic acid, copper hydroxide and ammonium carbonate to obtain a sufficient amount of flotation desulfurization activator.

[0064] The final temperature of the heating can be 25°C, 50°C, 70°C, or 90°C.

[0065] The heating time can be 0.5h, 2h, 4h or 6h.

[0066] Based on a general inventive concept, embodiments of this application provide an application of a flotation desulfurization activator, the application including using the flotation desulfurization activator as a desulfurization reagent in the desulfurization treatment of high-sulfur bauxite.

[0067] This application is based on the flotation desulfurization activator described above. The specific composition of the flotation desulfurization activator can be referred to in the above embodiments. Since this application adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0068] Figure 3 An exemplary schematic diagram of a desulfurization method for high-sulfur bauxite provided in an embodiment of this application is shown;

[0069] Based on a general inventive concept, such as Figure 3 As shown, this application provides a desulfurization method for high-sulfur bauxite, the method comprising:

[0070] S1. The high-sulfur bauxite is crushed and then ground to obtain high-sulfur bauxite powder;

[0071] S2. Add sodium silicate inhibitors to the high-sulfur bauxite powder for the first slurry preparation to obtain the first slurry;

[0072] S3. The flotation desulfurization activator is added to the first slurry for a second slurry preparation to obtain a second slurry;

[0073] S4. Add xanthate-based desulfurization collector and frother to the second slurry to obtain flotation slurry;

[0074] S5. Acidic gas is introduced into the flotation pulp to prevent the flotation pulp from being oxidized, and then the flotation pulp after the acidic gas is introduced is subjected to flotation skimming to obtain a flotation mixture;

[0075] S6. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain aluminum concentrate and sulfur concentrate respectively;

[0076] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥5×10 -5 :1;

[0077] The xanthate-based desulfurizing collector includes at least one of the following:

[0078] Ethyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate and isopentyl xanthate.

[0079] This method is based on the above-mentioned flotation desulfurization activator. The specific composition of the flotation desulfurization activator can be referred to the above embodiments. Since this method adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0080] It should be noted that this sodium silicate inhibitor can effectively inhibit the flotation of aluminosilicate minerals in high-sulfur bauxite powder. In addition, the sodium silicate inhibitor can disperse the high-sulfur bauxite mud in the first slurry.

[0081] It should be noted that the addition of this flotation desulfurization activator can promote the direct adsorption of copper ions from copper hydroxide onto the sulfur atoms of pyrite in high-sulfur bauxite exposed on its fresh surface. This prevents sulfur atoms on the surface of high-sulfur bauxite from occupying other active sites, thereby increasing the number of active sites on the surface of high-sulfur bauxite. A sufficient number of active sites can significantly affect the interaction between pyrite and xanthate-based desulfurization collectors in high-sulfur bauxite. When the concentration of xanthate-based desulfurization collectors is high, some copper-xanthate compounds will form on the surface of pyrite in high-sulfur bauxite, and a hydrophobic double xanthate layer will be formed. These copper-xanthate compounds and the double xanthate extract... The xanthate-based desulfurization collector improves the collectability of pyrite in high-sulfur bauxite. Furthermore, ammonium ions in the flotation desulfurization activator promote electrochemical reactions on the surface of pyrite in high-sulfur bauxite, generating a hydrophobic double xanthate layer, thus enhancing the collectability of the xanthate-based desulfurization collector for pyrite in high-sulfur bauxite. Additionally, ammonium ions in the flotation desulfurization activator bind water molecules to form hydrated ammonia molecules. These hydrated ammonia molecules reduce the stability of the hydration layer at the solid-liquid interface between the flotation tailings and the xanthate-based desulfurization collector, thereby dispersing the slime of high-sulfur bauxite covered by hydrophilic substances on the surface of pyrite in high-sulfur bauxite.

[0082] It should be noted that the acidic gas can be a mixture of carbon dioxide and nitrogen, and the volume fraction of carbon dioxide in the acidic gas can be 0% to 50%, while the volume fraction of nitrogen in the acidic gas can be 50% to 100%.

[0083] It should be noted that the addition of this acidic gas can prevent the oxidation of the pyrite surface in high-sulfur bauxite by oxygen. Additionally, the carbon dioxide gas in the acidic gas will form H₂CO₃ and HCO₃⁻ in the flotation pulp. - CO3 2- Plasma can further promote the electrochemical reaction of xanthate collectors on the surface of pyrite in high-sulfur bauxite and generate a hydrophobic double xanthate layer. In addition, these ions can also increase the ability of pyrite in high-sulfur bauxite to adsorb xanthate collectors.

[0084] It should be noted that the first and second slurry preparations are only set up to distinguish the operations, and not to indicate the order of operations; the first and second slurry preparations can be carried out by stirring to ensure that the materials are fully mixed.

[0085] In some optional embodiments, the weight m3 of the fine-grained high-sulfur bauxite powder and the weight m4 of the high-sulfur bauxite powder satisfy the relationship: m3:m4=(0.75:1)~(0.85:1), and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0086] In these embodiments, the weights m3 and m4 of fine-grained high-sulfur bauxite powder in the high-sulfur bauxite powder can satisfy the relationship: m3:m4 = (0.75:1) ~ (0.85:1), and the particle size of the fine-grained high-sulfur bauxite powder is generally ≤0.074mm. This can promote the effective combination of sodium silicate inhibitors, flotation desulfurization activators, xanthate desulfurization collectors, and frothers with the high-sulfur bauxite powder, thereby obtaining sufficient aluminum concentrate and sulfur concentrate.

[0087] The weights m3 and m4 of the fine-grained high-sulfur bauxite powder in this high-sulfur bauxite powder can satisfy the following relationship: m3:m4 = 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84 or 0.85.

[0088] In some optional embodiments, the flotation skimming time is 13 min to 18 min;

[0089] In these embodiments, the flotation skimming time can be 13 min to 18 min, which can promote sufficient flotation skimming to remove impurities floating in the flotation pulp after acidic gas by flotation skimming.

[0090] The flotation time for skimming bubbles can be 13 min, 14 min, 15 min, 16 min, 17 min, or 18 min.

[0091] The present application is further illustrated below with reference to specific embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to industry standards; if no corresponding industry standard exists, they are performed according to general international standards, conventional conditions, or conditions recommended by the manufacturer.

[0092] Example 1

[0093] like Figure 1 As shown, a flotation desulfurization activator is provided. The raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following conditions: copper hydroxide: 6 mol, ammonium carbonate: 0 mol; the flotation desulfurization activator satisfies the following conditions:

[0094] (2m+2n):q=12:1,

[0095] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide, which is 6; and n is the amount of ammonium carbonate, which is 0.

[0096] The flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0097]

[0098] In Formula 1, m is the amount of copper hydroxide, which is 6; n is the amount of ammonium carbonate, which is 0.

[0099] The amounts of copper hydroxide and ammonium carbonate satisfy the following equation: (2m+2n)=12.

[0100] The raw ore from a high-sulfur bauxite mine in Chongqing was selected, with a sulfur content of 3.85%.

[0101] like Figure 2 As shown, a method for preparing a flotation desulfurization activator includes:

[0102] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide and ammonium carbonate to obtain a flotation desulfurization activator.

[0103] The final heating temperature was 90℃, and the heating time was 6 hours.

[0104] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite includes:

[0105] S1. The high-sulfur bauxite is crushed to 3mm and then ground to obtain high-sulfur bauxite powder.

[0106] S2. Add sodium silicate inhibitors to high-sulfur bauxite powder at a mass ratio of 1500 g / t and stir for 3 minutes to prepare the first slurry.

[0107] S3. Add the flotation desulfurization activator to the first slurry at a mass ratio of 100g / t and stir for 3 minutes to prepare the second slurry.

[0108] S4. Add xanthate-based desulfurization collector at a mass ratio of 700 g / t and frother at a mass ratio of 300 g / t to the second slurry and stir for 6 minutes to obtain flotation slurry;

[0109] S5. A mixture of CO2 and N2 acidic gas is introduced into the flotation pulp to prevent the flotation pulp from being oxidized. Then, the flotation pulp after the acidic gas is introduced is subjected to flotation skimming to obtain a flotation mixture.

[0110] S6. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain aluminum concentrate and sulfur concentrate respectively;

[0111] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥10×10 -5 :1;

[0112] The xanthate-based desulfurization collector is pentyl xanthate.

[0113] The mass ratio of fine-grained high-sulfur bauxite powder to high-sulfur bauxite powder in high-sulfur bauxite powder meets the following requirements: fine-grained high-sulfur bauxite powder : high-sulfur bauxite powder = 0.80, and the particle size of fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0114] The flotation time for skimming bubbles is 14 minutes.

[0115] Example 2

[0116] A flotation desulfurization activator, wherein the raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate, and based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following: copper hydroxide: 0 mol, ammonium carbonate: 6 mol; the flotation desulfurization activator satisfies the following:

[0117] (2m+2n):q=12:1,

[0118] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide, which is 0; and n is the amount of ammonium carbonate, which is 6.

[0119] The flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0120]

[0121] In Formula 1, m is the amount of copper hydroxide, which is 0; n is the amount of ammonium carbonate, which is 6.

[0122] The amounts of copper hydroxide and ammonium carbonate satisfy the following equation: (2m+2n)=12.

[0123] The raw ore from a high-sulfur bauxite mine in Henan Province was selected, with a sulfur content of 2.36%.

[0124] like Figure 2 As shown, a method for preparing a flotation desulfurization activator includes:

[0125] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide and ammonium carbonate to obtain a flotation desulfurization activator.

[0126] The final heating temperature was 25℃, and the heating time was 0.5h.

[0127] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite includes:

[0128] S1. The high-sulfur bauxite is crushed to 3mm and then ground to obtain high-sulfur bauxite powder.

[0129] S2. Add sodium silicate inhibitors to high-sulfur bauxite powder at a mass ratio of 2000 g / t and stir for 3 minutes to prepare the first slurry.

[0130] S3. Add the flotation desulfurization activator to the first slurry at a mass ratio of 80g / t and stir for 3 minutes to perform a second slurry conditioning to obtain the second slurry;

[0131] S4. Add xanthate-based desulfurization collector at a mass ratio of 600 g / t and frother at a mass ratio of 200 g / t to the second slurry and stir for 6 minutes to obtain flotation slurry;

[0132] S5. A mixture of CO2 and N2 acidic gas is introduced into the flotation pulp to prevent the flotation pulp from being oxidized. Then, the flotation pulp after the acidic gas is introduced is subjected to flotation skimming to obtain a flotation mixture.

[0133] S6. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain aluminum concentrate and sulfur concentrate respectively;

[0134] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥8×10 -5 :1;

[0135] The xanthate-based desulfurization collector is pentyl xanthate.

[0136] The mass ratio of fine-grained high-sulfur bauxite powder to high-sulfur bauxite powder in high-sulfur bauxite powder meets the following requirements: fine-grained high-sulfur bauxite powder : high-sulfur bauxite powder = 0.80, and the particle size of fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0137] The flotation time for skimming bubbles is 13 minutes.

[0138] Example 3

[0139] A flotation desulfurization activator, wherein the raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate, and based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following: copper hydroxide: 3 mol, ammonium carbonate: 3 mol; the flotation desulfurization activator satisfies the following:

[0140] (2m+2n):q=12:1,

[0141] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide, which is 3; and n is the amount of ammonium carbonate, which is 3.

[0142] The flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0143]

[0144] In Formula 1, m is the amount of copper hydroxide, which is 3; n is the amount of ammonium carbonate, which is 3.

[0145] The amounts of copper hydroxide and ammonium carbonate satisfy the following equation: (2m+2n)=12.

[0146] The raw ore from a high-sulfur bauxite mine in Guizhou Province was selected, with a sulfur content of 4.97%.

[0147] like Figure 2 As shown, a method for preparing a flotation desulfurization activator includes:

[0148] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide and ammonium carbonate to obtain a flotation desulfurization activator.

[0149] The final heating temperature was 50℃, and the heating time was 3 hours.

[0150] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite includes:

[0151] S1. The high-sulfur bauxite is crushed to 3mm and then ground to obtain high-sulfur bauxite powder.

[0152] S2. Add sodium silicate inhibitors to high-sulfur bauxite powder at a mass ratio of 2000 g / t and stir for 3 minutes to prepare the first slurry.

[0153] S3. Add the flotation desulfurization activator to the first slurry at a mass ratio of 100g / t and stir for 3 minutes to prepare the second slurry.

[0154] S4. Add xanthate-based desulfurization collector at a mass ratio of 900 g / t and frother at a mass ratio of 400 g / t to the second slurry and stir for 6 minutes to obtain flotation slurry;

[0155] S5. A mixture of CO2 and N2 acidic gas is introduced into the flotation pulp to prevent the flotation pulp from being oxidized. Then, the flotation pulp after the acidic gas is introduced is subjected to flotation skimming to obtain a flotation mixture.

[0156] S6. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain aluminum concentrate and sulfur concentrate respectively;

[0157] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥10×10 -5 :1;

[0158] The xanthate-based desulfurization collector is pentyl xanthate.

[0159] The mass ratio of fine-grained high-sulfur bauxite powder to high-sulfur bauxite powder in high-sulfur bauxite powder meets the following requirements: fine-grained high-sulfur bauxite powder : high-sulfur bauxite powder = 0.85, and the particle size of fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0160] The flotation time for skimming bubbles is 15.0 min.

[0161] Example 4

[0162] A flotation desulfurization activator, wherein the raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate, and based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following: copper hydroxide: 4 mol, ammonium carbonate: 2 mol; the flotation desulfurization activator satisfies the following:

[0163] (2m+2n):q=12:1,

[0164] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide, which is 4; and n is the amount of ammonium carbonate, which is 2.

[0165] The flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0166]

[0167] In Formula 1, m is the amount of copper hydroxide, which is 4; n is the amount of ammonium carbonate, which is 2.

[0168] The amounts of copper hydroxide and ammonium carbonate satisfy the following condition: (2m+2n)≥12.

[0169] like Figure 2 As shown, a method for preparing a flotation desulfurization activator includes:

[0170] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide and ammonium carbonate to obtain a flotation desulfurization activator.

[0171] The final heating temperature was 75℃, and the heating time was 4 hours.

[0172] A decarbonized bauxite slurry was selected, with a sulfur content of 4.54%.

[0173] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite includes:

[0174] S1. Add 1.5L of decarburized bauxite slurry with a mass concentration of 27% to the flotation machine and stir for 3 minutes to perform the first slurry conditioning to obtain the first slurry;

[0175] S2. Add the flotation desulfurization activator to the first slurry at a mass ratio of 100g / t and stir for 3 minutes to perform a second slurry conditioning to obtain the second slurry;

[0176] S3. Add xanthate-based desulfurization collector at a mass ratio of 800 g / t and frother at a mass ratio of 400 g / t to the second slurry and stir for 6 minutes to obtain flotation slurry;

[0177] S5. A mixture of CO2 and N2 acidic gas is introduced into the flotation pulp to prevent the flotation pulp from being oxidized. Then, the flotation pulp after the acidic gas is introduced is subjected to flotation skimming to obtain a flotation mixture.

[0178] S6. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain aluminum concentrate and sulfur concentrate respectively;

[0179] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥10×10 -5 :1;

[0180] The xanthate-based desulfurization collector is butyl xanthate.

[0181] The flotation time for skimming bubbles is 17 minutes.

[0182] Example 5

[0183] A flotation desulfurization activator, wherein the raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate, and based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following: copper hydroxide: 2 mol, ammonium carbonate: 4 mol; the flotation desulfurization activator satisfies the following:

[0184] (2m+2n):q=12:1,

[0185] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide, which is 2; and n is the amount of ammonium carbonate, which is 4.

[0186] The flotation desulfurization activator has a molecular structure as shown in Formula 1.

[0187]

[0188] In Formula 1, m is the amount of copper hydroxide, which is 2; n is the amount of ammonium carbonate, which is 4.

[0189] The amounts of copper hydroxide and ammonium carbonate satisfy the following equation: (2m+2n)=12.

[0190] like Figure 2 As shown, a method for preparing a flotation desulfurization activator includes:

[0191] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide and ammonium carbonate to obtain a flotation desulfurization activator.

[0192] The final heating temperature was 50℃, and the heating time was 2 hours.

[0193] A magnetically separated aluminum concentrate slurry was selected, with a sulfur content of 5.22%.

[0194] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite includes:

[0195] S1. Add 1.5L of magnetic aluminum concentrate slurry with a mass concentration of 28% to the flotation machine and stir for 3 minutes to perform the first slurry conditioning to obtain the first slurry;

[0196] S2. Add the flotation desulfurization activator to the first slurry at a mass ratio of 150g / t and stir for 3 minutes to prepare the second slurry.

[0197] S3. Add xanthate-based desulfurization collector at a mass ratio of 900 g / t and frother at a mass ratio of 450 g / t to the second slurry and stir for 6 minutes to obtain flotation slurry;

[0198] S4. A mixture of CO2 and N2 acidic gas is introduced into the flotation pulp to prevent the flotation pulp from being oxidized. Then, the flotation pulp after the acidic gas is introduced is subjected to flotation skimming to obtain a flotation mixture.

[0199] S5. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain aluminum concentrate and sulfur concentrate respectively;

[0200] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥15×10 -5 :1;

[0201] The xanthate-based desulfurization collector is butyl xanthate.

[0202] The flotation time for skimming bubbles is 18 minutes.

[0203] Comparative Example 1

[0204] Comparative Example 1 and Example 1 will be compared. The difference between Comparative Example 1 and Example 1 is as follows:

[0205] Copper sulfate was used as a flotation desulfurization activator.

[0206] Comparative Example 2

[0207] Comparative Example 2 and Example 2 will be compared. The difference between Comparative Example 1 and Example 2 is as follows:

[0208] Oxalic acid was used as an activator for flotation desulfurization.

[0209] Comparative Example 3

[0210] Comparative Example 3 and Example 3 will be compared. The difference between Comparative Example 1 and Example 3 is as follows:

[0211] Sulfuric acid was used as the flotation desulfurization activator.

[0212] Comparative Example 4

[0213] Comparative Example 4 and Example 4 will be compared. The difference between Comparative Example 1 and Example 4 is as follows:

[0214] Copper sulfate was used as a flotation desulfurization activator.

[0215] Comparative Example 5

[0216] Comparative Example 5 and Example 5 will be compared. The difference between Comparative Example 1 and Example 5 is as follows:

[0217] Sulfuric acid was used as the flotation desulfurization activator.

[0218] Relevant experimental and effect data:

[0219] The performance parameters of the aluminum concentrate and sulfur concentrate obtained from each embodiment and comparative example are shown in Table 1.

[0220]

[0221]

[0222] As shown in Table 1, the sulfur content of the aluminum concentrate obtained in Example 1 can be reduced to 0.44%, and the sulfur content of the sulfur concentrate can reach 336.56%. The sulfur recovery rate of Example 1 through the sulfur concentrate is 92.68%. In contrast, the sulfur content of the aluminum concentrate obtained in Comparative Example 1 can be reduced to 0.49%, and the sulfur content of the sulfur concentrate can reach 33.79%. The sulfur recovery rate of Comparative Example 1 through the sulfur concentrate is only 88.55%.

[0223] The sulfur content of the aluminum concentrate obtained in Example 2 can be reduced to 0.29%, and the sulfur content of the sulfur concentrate can reach 30.71%. The sulfur recovery rate of Example 2 through the sulfur concentrate is 88.52%. In contrast, the sulfur content of the aluminum concentrate obtained in Comparative Example 2 can be reduced to 0.37%, and the sulfur content of the sulfur concentrate can reach 23.28%. The sulfur recovery rate of Comparative Example 2 through the sulfur concentrate is only 85.66%.

[0224] The sulfur content of the aluminum concentrate obtained in Example 3 can be reduced to 0.53%, and the sulfur content of the sulfur concentrate can reach 38.51%. The sulfur recovery rate of Example 3 through the sulfur concentrate is 90.57%. In contrast, the sulfur content of the aluminum concentrate obtained in Comparative Example 3 can be reduced to 0.69%, and the sulfur content of the sulfur concentrate can reach 32.28%. The sulfur recovery rate of Comparative Example 3 through the sulfur concentrate is only 88.00%.

[0225] The sulfur content of the aluminum concentrate obtained in Example 4 can be reduced to 0.31%, and the sulfur content of the sulfur concentrate can reach 33.51%. The sulfur recovery rate of Example 4 through the sulfur concentrate is 94.05%. In contrast, the sulfur content of the aluminum concentrate obtained in Comparative Example 4 can be reduced to 0.38%, and the sulfur content of the sulfur concentrate can reach 31.07%. The sulfur recovery rate of Comparative Example 4 through the sulfur concentrate is only 92.77%.

[0226] The sulfur content of the aluminum concentrate obtained in Example 5 can be reduced to 0.44%, and the sulfur content of the sulfur concentrate can reach 36.56%. The sulfur recovery rate of Example 5 through the sulfur concentrate is 92.68%. In contrast, the sulfur content of the aluminum concentrate obtained in Comparative Example 5 can be reduced to 0.56%, and the sulfur content of the sulfur concentrate can reach 32.51%. The sulfur recovery rate of Comparative Example 5 through the sulfur concentrate is only 90.83%.

[0227] In summary, the flotation desulfurization activator provided in this application can reduce the content of hydrophilic substances coating the surface of pyrite in high-sulfur bauxite, thereby exposing the fresh surface of the high-sulfur bauxite. In addition, ammonium carbonate can promote the direct adsorption of copper ions of copper hydroxide onto the sulfur atoms of pyrite in the exposed fresh surface of the high-sulfur bauxite, thereby increasing the number of active sites on the surface of the high-sulfur bauxite and thus improving the activation performance of the activator on the high-sulfur bauxite.

[0228] In addition, the flotation desulfurization activator provided in this application embodiment uses only phytic acid, copper hydroxide and ammonium carbonate as raw materials. Therefore, the flotation desulfurization activator has good environmental compatibility. Furthermore, the flotation desulfurization activator does not require the use of highly toxic chemicals such as lead nitrate, nor does it use highly corrosive liquid strong acids such as sulfuric acid. Therefore, the flotation desulfurization activator provided in this application embodiment is also green, environmentally friendly and safe to use.

[0229] Furthermore, the application of a flotation desulfurization activator provided in this application embodiment can be used as a desulfurization reagent in the desulfurization treatment of high-sulfur bauxite, which can reduce the sulfur content in the obtained bauxite concentrate to below 0.60% and increase the sulfur recovery rate in the sulfur concentrate to 88.00%.

[0230] Furthermore, the desulfurization method for high-sulfur bauxite provided in this application uses a flotation desulfurization activator that is inexpensive and highly adaptable, and can be widely used to remove sulfur and other impurities from high-sulfur bauxite or low-sulfur bauxite with a sulfur content of less than 6%. In addition, when this flotation desulfurization activator is applied to the flotation desulfurization process of bauxite, after one roughing, two cleaning, and three scavenging processes, or one roughing, three cleaning, and three scavenging processes, most of the sulfur impurities in the sulfur-containing bauxite can be floated out. The aluminum concentrate obtained after cleaning can meet the raw material requirements for alumina production, and the sulfur concentrate after scavenging meets the requirements for sulfuric acid raw materials.

[0231] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed in this application.

Claims

1. A flotation desulfurization activator, characterized in that, The raw materials for the flotation desulfurization activator include phytic acid, copper hydroxide, and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials for the flotation desulfurization activator satisfy the following conditions: copper hydroxide: 0–6 mol, ammonium carbonate: 0–6 mol; the flotation desulfurization activator satisfies the following conditions: (2m+2n):q=12:1, In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide; and n is the amount of ammonium carbonate. The flotation desulfurization activator has the molecular structure shown in Formula 1. Equation 1 In Formula 1, m is the amount of copper hydroxide; n is the amount of ammonium carbonate.

2. The flotation desulfurization activator according to claim 1, characterized in that, The amount of copper hydroxide is 1 mol to 6 mol, and the amount of ammonium carbonate is 1 mol to 6 mol.

3. The flotation desulfurization activator according to claim 1, characterized in that, The amount of copper hydroxide is 3 mol to 6 mol, and the amount of ammonium carbonate is 1 mol to 3 mol.

4. A method for preparing the flotation desulfurization activator as described in any one of claims 1 to 3, characterized in that, The method includes: Phytic acid, copper hydroxide, and ammonium carbonate are mixed and heated to neutralize the phytic acid, copper hydroxide, and ammonium carbonate, thereby obtaining a flotation desulfurization activator.

5. The method according to claim 4, characterized in that, The final temperature of the heating is 25℃ to 90℃, and the heating time is 0.5h to 6h.

6. An application of a flotation desulfurization activator, characterized in that, The application includes using the flotation desulfurization activator as described in any one of claims 1 to 3 as a desulfurization reagent for the desulfurization treatment of high-sulfur bauxite.

7. A desulfurization method for high-sulfur bauxite, characterized in that, The method includes: The high-sulfur bauxite is crushed and then ground to obtain high-sulfur bauxite powder. Sodium silicate inhibitors are added to the high-sulfur bauxite powder for the first slurry preparation to obtain the first slurry. The flotation desulfurization activator as described in any one of claims 1 to 3 is added to the first slurry for a second slurry preparation to obtain a second slurry; Xanthate-based desulfurization collectors and frothers are added to the second slurry to obtain flotation slurry; Acidic gas is introduced into the flotation pulp to prevent it from being oxidized. The flotation pulp after the acidic gas is introduced is then subjected to flotation skimming to obtain a flotation mixture. The flotation mixture is subjected to roughing, cleaning, and scavenging to obtain aluminum concentrate and sulfur concentrate, respectively. The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the following relationship: m1:m2≥5×10 -5 :1; The xanthate-based desulfurizing collector includes at least one of the following: Ethyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate and isopentyl xanthate.

8. The desulfurization method according to claim 7, characterized in that, The weights m3 and m4 of the fine-grained high-sulfur bauxite powder satisfy the following relationship: m3:m4 = (0.75:1) ~ (0.85:1), and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

9. The desulfurization method according to claim 7, characterized in that, The flotation skimming time is 13 to 18 minutes.

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