Flotation desulfurization activating agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of recycling of ore soil resources, in particular to a flotation desulfurization activating agent and a preparation method and application thereof. The flotation desulfurization activating agent comprises the following raw materials in terms of 1 mol of phytic acid: 0-6 mol of copper hydroxide and 0-6 mol of ammonium carbonate; the flotation desulfurization activator satisfies the following formula: (2m + 2n): q = 12: 1, in the formula, 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 activating agent 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, copper ions of copper hydroxide can be promoted to be directly adsorbed on sulfur atoms of the pyrite in the high-sulfur bauxite with the exposed fresh surface through ammonium carbonate, so that the flotation desulfurization activating agent can be used for treating the pyrite in the high-sulfur bauxite. Therefore, the number of active sites on the surface of the high-sulfur bauxite can be increased, and the activation performance of the activator on the high-sulfur bauxite can be improved.

Description

Technical Field

[0001] The present application relates to the technical field of recycling and utilizing mineral resources, and in particular to a flotation desulfurization activator and a preparation method and application thereof. Background Art

[0002] Domestic bauxite is mainly diaspore-type high-sulfur bauxite. Although most of this type of bauxite has a high grade, the sulfur content of this type of bauxite is also very high. Therefore, desulfurization must be carried out before the development and utilization of this type of bauxite resources. At present, the most effective method for desulfurization is flotation. At present, traditional flotation methods generally use activators such as sulfuric acid or copper sulfate for activation.

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

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

[0005] In a first aspect, the present application provides a flotation desulfurization activator, wherein the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following conditions: copper hydroxide: 0 to 6 mol, ammonium carbonate: 0 to 6 mol; the flotation desulfurization activator meets 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 the copper hydroxide is 1 mol to 6 mol, and the amount of the ammonium carbonate is 1 mol to 6 mol.

[0009] Optionally, the amount of the copper hydroxide is 3 mol to 6 mol, and the amount of the 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 m of the copper hydroxide and the amount n of the ammonium carbonate satisfy: (2m+2n)=12.

[0014] In a second aspect, the present 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 make the phytic acid, copper hydroxide and ammonium carbonate undergo a neutralization reaction to obtain a flotation desulfurization activator.

[0016] Optionally, the terminal temperature of the heating is 25°C to 90°C, and the heating time is 0.5h to 6h.

[0017] In a third aspect, the present application provides an application of a flotation desulfurization activator, wherein the application includes using the flotation desulfurization activator described in the first aspect as a desulfurization reagent used in the desulfurization treatment of high-sulfur bauxite.

[0018] In a fourth aspect, the present application provides a method for desulfurization of high-sulfur bauxite, the method comprising:

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

[0020] Adding a sodium silicate inhibitor to the high-sulfur bauxite powder for a first slurry preparation to obtain a first slurry;

[0021] Adding the flotation desulfurization activator described in the first aspect to the first slurry for second slurry adjustment to obtain a second slurry;

[0022] Adding a xanthate desulfurization collector and a frother to the second slurry to obtain a flotation slurry;

[0023] Passing acidic gas into the flotation pulp to prevent the flotation pulp from being oxidized, and then flotation scraping the flotation pulp after the acidic gas is passed into the flotation pulp 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 relationship: m1:m2≥5×10 -5 :1;

[0026] The xanthate desulfurization collector comprises at least one of the following:

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

[0028] Optionally, the weight m3 of the fine-grained high-sulfur bauxite powder in the 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 scraping time is 13 minutes to 18 minutes.

[0030] The above technical solution provided by the embodiment of the present application has the following advantages compared with the prior art:

[0031] The embodiment of the present application provides a flotation desulfurization activator. The raw materials of the flotation desulfurization activator satisfy the following conditions based on 1 mol of phytic acid: 0 to 6 mol of copper hydroxide and 0 to 6 mol of ammonium carbonate; the flotation desulfurization activator satisfies the following conditions: (2m+2n):q=12:1, wherein 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 material of the flotation activator is generally 1 mol, which can promote the presence of sufficient phytic acid in the flotation activator. Sufficient phytic acid can increase the oxidation potential of the pyrite surface in the high-sulfur bauxite, and the hydrophilic substances in the pyrite in the high-sulfur bauxite with the increased surface oxidation potential are easily removed, thereby reducing the high-sulfur The content of hydrophilic substances coated on the surface of pyrite in bauxite is increased to expose the fresh surface of high-sulfur bauxite; in addition, the amount of copper hydroxide is generally 0-6 mol, and the amount of ammonium carbonate is generally 0-6 mol, and the flotation desulfurization activator can satisfy 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, and ammonium carbonate can be used to promote the copper ions of copper hydroxide to be directly adsorbed on the sulfur atoms of pyrite in the freshly exposed surface of high-sulfur bauxite 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 further improving the activation performance of the activator on high-sulfur bauxite. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0033] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

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

[0035] Figure 2 A schematic flow chart of a method for preparing the flotation desulfurization activator provided in an embodiment of the present application;

[0036] Figure 3 A schematic flow chart of a method for desulfurization of high-sulfur bauxite is provided in an embodiment of the present application. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0038] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be understood as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within the 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., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range; in addition, whenever a numerical range is indicated in this document, it is meant to include any cited numbers (fractions or integers) within the indicated range.

[0039] In this article, the terms including "including" and the like mean "including but not limited to". Relational terms such as "first" and "second" are used only 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 "plurality" 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 items or plural items; for example, "at least one of a, b, or c", or "at least one of a, b, and c" can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in this application can be purchased on the market or prepared by existing methods.

[0040] It should be noted that the activators such as sulfuric acid or copper sulfate used in the traditional flotation method in the background technology have the following defects: (1) sulfuric acid is highly corrosive, highly polluting, has great safety hazards, and is 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 certain corrosiveness. Long-term contact with it is harmful to the human body, and the wastewater discharged after copper sulfate flotation treatment will have adverse effects on the environment; (3) when encountering high-sulfur bauxite slurry with a large mud content, since the sulfur in the high-sulfur bauxite is concentrated in the pyrite component, these activators have low activation ability for pyrite, which will result in poor activation performance of the high-sulfur bauxite slurry, thereby affecting the indicators of the bauxite concentrate after flotation treatment.

[0041] Figure 1 A schematic diagram of a flotation desulfurization activator provided in an embodiment of the present application is shown exemplarily;

[0042] like Figure 1 As shown, the embodiment of the present application provides a flotation desulfurization activator, the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following conditions: copper hydroxide: 0-6 mol, ammonium carbonate: 0-6 mol; the flotation desulfurization activator meets 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 the copper hydroxide substance may be 0 mol, 1 mol, 2 mol, 3 mol, 4 mol, 5 mol or 6 mol.

[0046] The amount of substance of the 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 the copper hydroxide is 3 mol to 6 mol, and the molar mass fraction of the 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, 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, which can promote the presence of sufficient copper hydroxide and sufficient ammonium carbonate in the flotation activator. Sufficient copper hydroxide and sufficient ammonium carbonate can promote copper ions to be directly adsorbed on the sulfur atoms of pyrite in the high-sulfur bauxite with a fresh surface exposed, so as to avoid the sulfur atoms on the surface of the high-sulfur bauxite occupying other active sites, thereby improving the activity of the surface of the high-sulfur bauxite, and further improving the activation performance of the activator on the high-sulfur bauxite.

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

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

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

[0053]

[0054]

[0055] In formula 1, m is the amount of copper hydroxide; n is the amount of ammonium carbonate;

[0056] The amount of the copper hydroxide and the amount of the ammonium carbonate satisfy: (2m+2n)=12;

[0057] In these embodiments, the flotation desulfurization activator may have a molecular structure as shown in Formula 1, and the amount of copper hydroxide and the amount of ammonium carbonate may satisfy: (2m+2n)=12, which indicates that the phytic acid, copper hydroxide and ammonium carbonate in the flotation desulfurization activator react sufficiently to form a stable flotation desulfurization activator.

[0058] Figure 2 A schematic flow chart of a method for preparing the flotation desulfurization activator provided in an embodiment of the present application is shown exemplarily;

[0059] Based on a general inventive concept, such as Figure 2 As shown, the embodiment of the present application provides a method for preparing the flotation desulfurization activator, the method comprising:

[0060] S1. Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to allow the phytic acid, copper hydroxide and ammonium carbonate to undergo a neutralization reaction to obtain a flotation desulfurization activator.

[0061] This method is a method for preparing the above-mentioned flotation desulfurization activator. The specific composition of the flotation desulfurization activator can refer to the above-mentioned embodiment. Since the preparation method adopts part or all of the technical solutions of the above-mentioned embodiment, it at least has all the beneficial effects brought by the technical solutions of the above-mentioned embodiment, which will not be repeated here one by one.

[0062] It should be noted that the mixing and heating can be carried out simultaneously to promote uniform mixing of phytic acid, copper hydroxide and ammonium carbonate, so as to facilitate the subsequent neutralization reaction to proceed fully.

[0063] In some optional embodiments, the end temperature of the heating is 25°C to 90°C, and the heating time is 0.5h to 6h;

[0064] In these embodiments, the terminal temperature of heating can be 25° C. to 90° C., and the heating time can be 0.5 h to 6 h, which can promote the neutralization reaction between phytic acid, copper hydroxide and ammonium carbonate to obtain a sufficient amount of flotation desulfurization activator.

[0065] The end point temperature of the heating may be 25°C, 50°C, 70°C or 90°C.

[0066] The heating time can be 0.5 h, 2 h, 4 h or 6 h.

[0067] Based on a general inventive concept, an embodiment of the present application provides an application of a flotation desulfurization activator, wherein the application includes using the flotation desulfurization activator as a desulfurization reagent for desulfurization treatment of high-sulfur bauxite.

[0068] This application is realized based on the above-mentioned flotation desulfurization activator. The specific composition of the flotation desulfurization activator can refer to the above-mentioned embodiment. Since this application adopts part or all of the technical solutions of the above-mentioned embodiment, it has at least all the beneficial effects brought by the technical solutions of the above-mentioned embodiment, which will not be repeated here one by one.

[0069] Figure 3 A schematic diagram of a desulfurization method for high-sulfur bauxite provided in an embodiment of the present application is shown as an example;

[0070] Based on a general inventive concept, such as Figure 3 As shown, the present application provides a desulfurization method for high-sulfur bauxite, the method comprising:

[0071] S1. crushing the high-sulfur bauxite and then grinding it to obtain high-sulfur bauxite powder;

[0072] S2. adding a sodium silicate inhibitor to the high-sulfur bauxite powder for a first slurry adjustment to obtain a first slurry;

[0073] S3. adding the flotation desulfurization activator to the first slurry for a second slurry adjustment to obtain a second slurry;

[0074] S4. adding a xanthate desulfurization collector and a frother to the second slurry to obtain a flotation slurry;

[0075] S5. introducing acidic gas into the flotation pulp to prevent the flotation pulp from being oxidized, and then flotation scraping the flotation pulp after introducing acidic gas to obtain a flotation mixture;

[0076] S6. roughing, concentrating and scavenging the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0077] The weight m1 of the flotation desulfurization activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥5×10 -5 :1;

[0078] The xanthate desulfurization collector comprises at least one of the following:

[0079] Ethyl xanthate, butyl xanthate, isobutyl xanthate, amyl xanthate and isopentyl xanthate.

[0080] The method is implemented based on the above-mentioned flotation desulfurization activator. The specific composition of the flotation desulfurization activator can refer to the above-mentioned embodiment. Since the method adopts part or all of the technical solutions of the above-mentioned embodiment, it has at least all the beneficial effects brought by the technical solutions of the above-mentioned embodiment, which will not be repeated here.

[0081] It should be noted that the sodium silicate inhibitor can effectively inhibit the floating of aluminosilicate minerals in the high-sulfur bauxite powder. In addition, the sodium silicate inhibitor can disperse the high-sulfur bauxite mud in the first slurry.

[0082] It should be noted that the addition of the flotation desulfurization activator can promote the copper ions of copper hydroxide to be directly adsorbed on the sulfur atoms of pyrite in the high-sulfur bauxite with fresh surface exposed, so as to avoid the sulfur atoms on the surface of the high-sulfur bauxite occupying other active sites, thereby increasing the number of active sites on the surface of the high-sulfur bauxite. A sufficient number of active sites can significantly affect the effect of pyrite in the high-sulfur bauxite and the xanthate desulfurization collector. When the concentration of the xanthate desulfurization collector is high, some copper-xanthate compounds and a hydrophobic dixanthate layer will be generated on the surface of pyrite in the high-sulfur bauxite. These copper-xanthate compounds and dixanthate extract The capture of pyrite in high-sulfur bauxite by xanthate desulfurization collectors is improved; in addition, the ammonium ions in the flotation desulfurization activator can promote the electrochemical reaction of the xanthate collectors on the surface of pyrite in high-sulfur bauxite and generate a hydrophobic double xanthate layer, which can improve the capture of pyrite in high-sulfur bauxite by the xanthate desulfurization collectors; in addition, the ammonium ions in the flotation desulfurization activator will also combine with water molecules to obtain hydrated molecules of ammonia, which will reduce the stability of the solid-liquid interface hydration layer of the flotation tailings and the xanthate desulfurization collectors, thereby dispersing the high-sulfur bauxite sludge whose surface of pyrite in high-sulfur bauxite is covered by hydrophilic substances.

[0083] It should be noted that the acid gas may be a mixed gas of carbon dioxide gas and nitrogen gas, the volume fraction of carbon dioxide gas in the acid gas may be 0% to 50%, and the volume fraction of nitrogen gas in the acid gas may be 50% to 100%.

[0084] It should be noted that the addition of the acidic gas can prevent oxygen from oxidizing the surface of pyrite in high-sulfur bauxite. In addition, the carbon dioxide in the acidic gas will also form H2CO3 and HCO3 in the flotation pulp. - 、CO3 2- Plasma, these ions 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.

[0085] It should be noted that the first slurry mixing and the second slurry mixing are only set to distinguish operations, rather than to mark the order of operations; the first slurry mixing and the second slurry mixing can be performed by stirring to promote sufficient mixing of the various materials.

[0086] In some optional embodiments, the weight m3 of the fine-grained high-sulfur bauxite powder in the 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.

[0087] In these embodiments, the weight m3 of the fine-grained high-sulfur bauxite powder and the weight m4 of the 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, which 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 a sufficient amount of aluminum concentrate and sulfur concentrate.

[0088] The weight m3 of the fine-grained high-sulfur bauxite powder and the weight m4 of the high-sulfur bauxite powder in the high-sulfur bauxite powder may satisfy the 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.

[0089] In some optional embodiments, the flotation scraping time is 13min to 18min;

[0090] In these embodiments, the flotation scraping time may be 13 minutes to 18 minutes, which can promote the flotation scraping to be fully carried out, so that the impurities floating in the flotation pulp after the acid gas are removed by the flotation scraping method.

[0091] The flotation scraping time can be 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes or 18 minutes.

[0092] The present application is further described below in conjunction with specific examples. The experimental methods in the following examples that do not specify specific conditions are usually measured according to industry standards; if there are no corresponding industry standards, they are carried out according to common international standards, conventional conditions, or conditions recommended by the manufacturer.

[0093] Example 1

[0094] like Figure 1 As shown, a flotation desulfurization activator, the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following requirements: copper hydroxide: 6 mol, ammonium carbonate: 0 mol; the flotation desulfurization activator meets the following requirements:

[0095] (2m+2n):q=12:1,

[0096] 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.

[0097] The flotation desulfurization activator has a molecular structure as shown in Formula 1,

[0098]

[0099] In formula 1, m is the amount of copper hydroxide, which is 6; n is the amount of ammonium carbonate, which is 0;

[0100] The amount of copper hydroxide and the amount of ammonium carbonate satisfy: (2m+2n)=12.

[0101] The raw ore of a high-sulfur bauxite mine in Chongqing was selected, and its sulfur content was 3.85%.

[0102] like Figure 2 As shown, a method for preparing a flotation desulfurization activator comprises:

[0103] 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.

[0104] The final temperature of heating was 90°C and the heating time was 6 h.

[0105] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite comprises:

[0106] S1. crushing the high-sulfur bauxite to 3 mm and then grinding it to obtain high-sulfur bauxite powder;

[0107] S2. adding a sodium silicate inhibitor to the high-sulfur bauxite powder at a mass ratio of 1500 g / t and stirring for 3 min to perform a first slurry to obtain a first slurry;

[0108] S3. The flotation desulfurization activator is added to the first slurry at a mass ratio of 100 g / t and stirred for 3 min for a second slurry adjustment to obtain a second slurry;

[0109] S4. The xanthate desulfurization collector was added to the second slurry at a mass ratio of 700 g / t and the frother at a mass ratio of 300 g / t and stirred for 6 min to obtain a flotation slurry;

[0110] S5. A mixture of CO2 and N2 is passed into the flotation pulp to prevent the flotation pulp from being oxidized, and then the flotation pulp after the acid gas is passed is flotated and scraped to obtain a flotation mixture;

[0111] S6. roughing, concentrating and scavenging the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0112] Among them, the weight of the flotation desulfurization activator m1 and the weight of the first slurry m2 satisfy the relationship: m1:m2≥10×10 -5 :1;

[0113] The xanthate desulfurization collector is amyl xanthate.

[0114] The mass ratio of fine-grained high-sulfur bauxite powder and high-sulfur bauxite powder in the high-sulfur bauxite powder satisfies: fine-grained high-sulfur bauxite powder: high-sulfur bauxite powder = 0.80, and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0115] The flotation scraping time is 14 minutes.

[0116] Example 2

[0117] A flotation desulfurization activator, the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following requirements: copper hydroxide: 0 mol, ammonium carbonate: 6 mol; the flotation desulfurization activator meets the following requirements:

[0118] (2m+2n):q=12:1,

[0119] 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.

[0120] The flotation desulfurization activator has a molecular structure as shown in Formula 1,

[0121]

[0122]

[0123] In formula 1, m is the amount of copper hydroxide, which is 0; n is the amount of ammonium carbonate, which is 6;

[0124] The amount of copper hydroxide and the amount of ammonium carbonate satisfy: (2m+2n)=12.

[0125] The raw ore of a high-sulfur bauxite mine in Henan was selected, and its sulfur content was 2.36%.

[0126] like Figure 2 As shown, a method for preparing a flotation desulfurization activator comprises:

[0127] 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.

[0128] The end point temperature of heating was 25°C and the heating time was 0.5 h.

[0129] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite comprises:

[0130] S1. crushing the high-sulfur bauxite to 3 mm and then grinding it to obtain high-sulfur bauxite powder;

[0131] S2. adding a sodium silicate inhibitor to the high-sulfur bauxite powder at a mass ratio of 2000 g / t and stirring for 3 min to perform a first slurry to obtain a first slurry;

[0132] S3. The flotation desulfurization activator is added to the first slurry at a mass ratio of 80 g / t and stirred for 3 min for a second slurry adjustment to obtain a second slurry;

[0133] S4. The xanthate desulfurization collector was added to the second slurry at a mass ratio of 600 g / t and the frother at a mass ratio of 200 g / t and stirred for 6 min to obtain a flotation slurry;

[0134] S5. A mixture of CO2 and N2 is passed into the flotation pulp to prevent the flotation pulp from being oxidized, and then the flotation pulp after the acid gas is passed is flotated and scraped to obtain a flotation mixture;

[0135] S6. roughing, concentrating and scavenging the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0136] Among them, the weight of the flotation desulfurization activator m1 and the weight of the first slurry m2 satisfy the relationship: m1:m2≥8×10 -5 :1;

[0137] The xanthate desulfurization collector is amyl xanthate.

[0138] The mass ratio of fine-grained high-sulfur bauxite powder and high-sulfur bauxite powder in the high-sulfur bauxite powder satisfies: fine-grained high-sulfur bauxite powder: high-sulfur bauxite powder = 0.80, and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0139] The flotation scraping time is 13 minutes.

[0140] Example 3

[0141] A flotation desulfurization activator, the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following requirements: copper hydroxide: 3 mol, ammonium carbonate: 3 mol; the flotation desulfurization activator meets the following requirements:

[0142] (2m+2n):q=12:1,

[0143] In the formula, q is the amount of phytic acid; m is the amount of copper hydroxide, which is 3; n is the amount of ammonium carbonate, which is 3.

[0144] The flotation desulfurization activator has a molecular structure as shown in Formula 1,

[0145]

[0146] In formula 1, m is the amount of copper hydroxide, which is 3; n is the amount of ammonium carbonate, which is 3;

[0147] The amount of copper hydroxide and the amount of ammonium carbonate satisfy: (2m+2n)=12.

[0148] The raw ore of a high-sulfur bauxite mine in Guizhou was selected, and its sulfur content was 4.97%.

[0149] like Figure 2 As shown, a method for preparing a flotation desulfurization activator comprises:

[0150] 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.

[0151] The final temperature of heating was 50°C and the heating time was 3 h.

[0152] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite comprises:

[0153] S1. crushing the high-sulfur bauxite to 3 mm and then grinding it to obtain high-sulfur bauxite powder;

[0154] S2. adding a sodium silicate inhibitor to the high-sulfur bauxite powder at a mass ratio of 2000 g / t and stirring for 3 min to perform a first slurry to obtain a first slurry;

[0155] S3. The flotation desulfurization activator is added to the first slurry at a mass ratio of 100 g / t and stirred for 3 min for a second slurry adjustment to obtain a second slurry;

[0156] S4. The xanthate desulfurization collector was added to the second slurry at a mass ratio of 900 g / t and the frother at a mass ratio of 400 g / t and stirred for 6 min to obtain a flotation slurry;

[0157] S5. A mixture of CO2 and N2 is passed into the flotation pulp to prevent the flotation pulp from being oxidized, and then the flotation pulp after the acid gas is passed is flotated and scraped to obtain a flotation mixture;

[0158] S6. roughing, concentrating and scavenging the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0159] Among them, the weight of the flotation desulfurization activator m1 and the weight of the first slurry m2 satisfy the relationship: m1:m2≥10×10 -5 :1;

[0160] The xanthate desulfurization collector is amyl xanthate.

[0161] The mass ratio of fine-grained high-sulfur bauxite powder and high-sulfur bauxite powder in the high-sulfur bauxite powder satisfies: fine-grained high-sulfur bauxite powder: high-sulfur bauxite powder = 0.85, and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0162] The flotation scraping time is 15.0min.

[0163] Example 4

[0164] A flotation desulfurization activator, the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following requirements: copper hydroxide: 4 mol, ammonium carbonate: 2 mol; the flotation desulfurization activator meets the following requirements:

[0165] (2m+2n):q=12:1,

[0166] 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.

[0167] The flotation desulfurization activator has a molecular structure as shown in Formula 1,

[0168]

[0169] In formula 1, m is the amount of copper hydroxide, which is 4; n is the amount of ammonium carbonate, which is 2;

[0170] The amount of substance of copper hydroxide and the amount of substance of ammonium carbonate satisfy: (2m+2n)≥12.

[0171] like Figure 2 As shown, a method for preparing a flotation desulfurization activator comprises:

[0172] 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.

[0173] The final temperature of heating was 75°C and the heating time was 4 h.

[0174] A decarbonized bauxite slurry was selected, and its sulfur content was 4.54%.

[0175] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite comprises:

[0176] S1. 1.5 L of decarbonized bauxite slurry having a mass concentration of 27% was added to a flotation machine and stirred for 3 min for a first slurry adjustment to obtain a first slurry;

[0177] S2. adding the flotation desulfurization activator to the first slurry at a mass ratio of 100 g / t and stirring for 3 min for a second slurry adjustment to obtain a second slurry;

[0178] S3. The xanthate desulfurization collector was added to the second slurry at a mass ratio of 800 g / t and the frother at a mass ratio of 400 g / t and stirred for 6 min to obtain a flotation slurry;

[0179] S5. A mixture of CO2 and N2 is passed into the flotation pulp to prevent the flotation pulp from being oxidized, and then the flotation pulp after the acid gas is passed is flotated and scraped to obtain a flotation mixture;

[0180] S6. roughing, concentrating and scavenging the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0181] Among them, the weight of the flotation desulfurization activator m1 and the weight of the first slurry m2 satisfy the relationship: m1:m2≥10×10 -5 :1;

[0182] The xanthate desulfurization collector is butyl xanthate.

[0183] The flotation scraping time is 17 minutes.

[0184] Example 5

[0185] A flotation desulfurization activator, the raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following requirements: copper hydroxide: 2 mol, ammonium carbonate: 4 mol; the flotation desulfurization activator meets the following requirements:

[0186] (2m+2n):q=12:1,

[0187] 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.

[0188] The flotation desulfurization activator has a molecular structure as shown in Formula 1,

[0189]

[0190] In formula 1, m is the amount of copper hydroxide, which is 2; n is the amount of ammonium carbonate, which is 4;

[0191] The amount of copper hydroxide and the amount of ammonium carbonate satisfy: (2m+2n)=12.

[0192] like Figure 2 As shown, a method for preparing a flotation desulfurization activator comprises:

[0193] 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.

[0194] The final temperature of heating was 50°C and the heating time was 2 h.

[0195] A magnetic aluminum concentrate slurry was selected, and its sulfur content was 5.22%.

[0196] like Figure 3 As shown, a desulfurization method for high-sulfur bauxite comprises:

[0197] S1. Add 1.5 L of magnetic aluminum concentrate slurry with a mass concentration of 28% to a flotation machine and stir for 3 min for the first slurry adjustment to obtain a first slurry;

[0198] S2. adding the flotation desulfurization activator to the first slurry at a mass ratio of 150 g / t and stirring for 3 min to perform a second slurry adjustment to obtain a second slurry;

[0199] S3. The xanthate desulfurization collector was added to the second slurry at a mass ratio of 900 g / t and the frother at a mass ratio of 450 g / t and stirred for 6 min to obtain a flotation slurry;

[0200] S4. A mixture of CO2 and N2 is passed into the flotation pulp to prevent the flotation pulp from being oxidized, and then the flotation pulp after the acid gas is passed is flotated and scraped to obtain a flotation mixture;

[0201] S5. roughing, concentrating and scavenging the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0202] Among them, the weight of the flotation desulfurization activator m1 and the weight of the first slurry m2 satisfy the following relationship: m1:m2≥15×10 -5 :1;

[0203] The xanthate desulfurization collector is butyl xanthate.

[0204] The flotation scraping time is 18 minutes.

[0205] Comparative Example 1

[0206] Comparative Example 1 and Example 1 are compared. The difference between Comparative Example 1 and Example 1 is:

[0207] Copper sulfate is used as flotation desulfurization activator.

[0208] Comparative Example 2

[0209] Comparing Comparative Example 2 with Example 2, the difference between Comparative Example 1 and Example 2 is:

[0210] Oxalic acid is used as a flotation desulfurization activator.

[0211] Comparative Example 3

[0212] Comparing Comparative Example 3 with Example 3, the difference between Comparative Example 1 and Example 3 is:

[0213] Sulfuric acid is used as the activator for flotation desulfurization.

[0214] Comparative Example 4

[0215] Comparing Comparative Example 4 with Example 4, the difference between Comparative Example 1 and Example 4 is:

[0216] Copper sulfate is used as flotation desulfurization activator.

[0217] Comparative Example 5

[0218] Comparing Comparative Example 5 with Example 5, the difference between Comparative Example 1 and Example 5 is:

[0219] Sulfuric acid is used as the activator for flotation desulfurization.

[0220] Related experiments and effect data:

[0221] The performance parameters of the aluminum concentrate and sulfur concentrate obtained in each embodiment and comparative example are shown in Table 1.

[0222]

[0223]

[0224] It can be seen from Table 1 that the sulfur content of the aluminum concentrate obtained in Example 1 can be reduced to 0.44%, the sulfur content of the sulfur concentrate can reach 336.56%, and the recovery rate of sulfur recovered by the sulfur concentrate in Example 1 is 92.68%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 1 can be reduced to 0.49%, the sulfur content of the sulfur concentrate can reach 33.79%, and the recovery rate of sulfur recovered by the sulfur concentrate in Comparative Example 1 is only 88.55%.

[0225] The sulfur content of the aluminum concentrate obtained in Example 2 can be reduced to 0.29%, the sulfur content of the sulfur concentrate can reach 30.71%, and the recovery rate of sulfur recovered through the sulfur concentrate in Example 2 is 88.52%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 2 can be reduced to 0.37%, the sulfur content of the sulfur concentrate can reach 23.28%, and the recovery rate of sulfur recovered through the sulfur concentrate in Comparative Example 2 is only 85.66%.

[0226] The sulfur content of the aluminum concentrate obtained in Example 3 can be reduced to 0.53%, the sulfur content of the sulfur concentrate can reach 38.51%, and the recovery rate of sulfur recovered through the sulfur concentrate in Example 3 is 90.57%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 3 can be reduced to 0.69%, the sulfur content of the sulfur concentrate can reach 32.28%, and the recovery rate of sulfur recovered through the sulfur concentrate in Comparative Example 3 is only 88.00%.

[0227] The sulfur content of the aluminum concentrate obtained in Example 4 can be reduced to 0.31%, the sulfur content of the sulfur concentrate can reach 33.51%, and the recovery rate of sulfur recovered through the sulfur concentrate in Example 4 is 94.05%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 4 can be reduced to 0.38%, the sulfur content of the sulfur concentrate can reach 31.07%, and the recovery rate of sulfur recovered through the sulfur concentrate in Comparative Example 4 is only 92.77%.

[0228] The sulfur content of the aluminum concentrate obtained in Example 5 can be reduced to 0.44%, the sulfur content of the sulfur concentrate can reach 36.56%, and the recovery rate of sulfur recovered through the sulfur concentrate in Example 5 is 92.68%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 5 can be reduced to 0.56%, the sulfur content of the sulfur concentrate can reach 32.51%, and the recovery rate of sulfur recovered through the sulfur concentrate in Comparative Example 5 is only 90.83%.

[0229] In summary, the flotation desulfurization activator provided in the embodiments of the present application can reduce the content of hydrophilic substances coated on the surface of pyrite in high-sulfur bauxite to expose the fresh surface of the high-sulfur bauxite. In addition, ammonium carbonate can be used to promote the copper ions of copper hydroxide to be directly adsorbed on the sulfur atoms of pyrite in the high-sulfur bauxite with the fresh surface exposed, thereby increasing the number of active sites on the surface of the high-sulfur bauxite, and further improving the activation performance of the activator on the high-sulfur bauxite.

[0230] In addition, the flotation desulfurization activator provided in the embodiment of the present application uses only phytic acid, copper hydroxide and ammonium carbonate as raw materials, so the flotation desulfurization activator has good environmental compatibility. In addition, the flotation desulfurization activator does not need to use 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 the embodiment of the present application is also green, environmentally friendly and safe to use.

[0231] In addition, the application of a flotation desulfurization activator provided in an embodiment of the present application can be used as a desulfurization reagent used in the desulfurization treatment of high-sulfur bauxite, which can reduce the sulfur content in the obtained aluminum concentrate to below 0.60%, and can also increase the sulfur recovery rate in the sulfur concentrate to 88.00%.

[0232] In addition, a desulfurization method for high-sulfur bauxite provided in an embodiment of the present application uses a flotation desulfurization activator which is low-cost and highly adaptable, and can be widely used to remove impurities such as sulfur from high-sulfur bauxite or low-sulfur bauxite with a sulfur content of less than 6%; in addition, the flotation desulfurization activator is applied to the flotation desulfurization process of bauxite, and then after one roughing selection, two fine selections, three scavenging selections or one roughing selection, three fine selections, three scavenging selections, most of the sulfur impurities in the sulfur-containing bauxite can be floated out, and the aluminum concentrate obtained after fine selection can meet the requirements of the raw material indicators required for alumina production, and the sulfur concentrate after scavenging meets the requirements of sulfuric acid raw materials.

[0233] The above is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. It will be apparent to those skilled in the art that various modifications to these embodiments are possible, and the general principles defined in the present application can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown in the present application, but will conform to the widest scope consistent with the principles and novel features applied for by the present application.

Claims

1. A flotation desulfurization activator, It is characterized in that The raw materials of the flotation desulfurization activator include phytic acid, copper hydroxide and ammonium carbonate. Based on 1 mol of phytic acid, the raw materials of the flotation desulfurization activator meet the following requirements: copper hydroxide: 0-6 mol, ammonium carbonate: 0-6 mol; the flotation desulfurization activator meets the following requirements: (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.

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

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

4. The flotation desulfurization activator according to claim 1, It is characterized in that The flotation desulfurization activator has a molecular structure as shown in Formula 1, In formula 1, m is the amount of copper hydroxide; n is the amount of ammonium carbonate; The amount m of the copper hydroxide and the amount n of the ammonium carbonate satisfy: (2m+2n)=12.

5. A method for preparing the flotation desulfurization activator according to any one of claims 1 to 4, It is characterized in that The method comprises: Phytic acid, copper hydroxide and ammonium carbonate are mixed and heated to make the phytic acid, copper hydroxide and ammonium carbonate undergo a neutralization reaction to obtain a flotation desulfurization activator.

6. The method according to claim 5, It is characterized in that The terminal temperature of the heating is 25° C. to 90° C., and the heating time is 0.5 h to 6 h.

7. Application of a flotation desulfurization activator, It is characterized in that The application includes using the flotation desulfurization activator as described in any one of claims 1 to 4 as a desulfurization reagent used in the desulfurization treatment of high-sulfur bauxite.

8. A method for desulfurization of high-sulfur bauxite, It is characterized in that The method comprises: The high-sulfur bauxite is crushed and then ground to obtain high-sulfur bauxite powder; Adding a sodium silicate inhibitor to the high-sulfur bauxite powder for a first slurry preparation to obtain a first slurry; adding the flotation desulfurization activator according to any one of claims 1 to 4 to the first slurry for second slurry adjustment to obtain a second slurry; Adding a xanthate desulfurization collector and a frother to the second slurry to obtain a flotation slurry; Passing acidic gas into the flotation pulp to prevent the flotation pulp from being oxidized, and then flotation scraping the flotation pulp after the acidic gas is passed into the flotation pulp 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 relationship: m1:m2≥5×10 -5 :1; The xanthate desulfurization collector comprises at least one of the following: Ethyl xanthate, butyl xanthate, isobutyl xanthate, amyl xanthate and isopentyl xanthate.

9. The desulfurization method according to claim 8, It is characterized in that The weight m3 of the fine-grained high-sulfur bauxite powder in the 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.

10. The desulfurization method according to claim 8, It is characterized in that The flotation scraping time is 13 minutes to 18 minutes.

Images