Phytate-based complex activator, and preparation method and application thereof

Abstract

The application relates to the technical field of recycling of ore resources, and particularly relates to a composite activator based on phytic acid and a preparation method and application thereof; raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator satisfies (3m+n):q=12:1, m:q=(0-4):1, and n:q=(0-12):1, wherein q is the amount of substance of the phytic acid; m is the amount of substance of the trivalent metal hydroxide; and n is the amount of substance of the ammonium bicarbonate; wherein the trivalent metal hydroxide includes aluminum hydroxide and / or iron hydroxide. The composite activator can increase the number of active sites on the surface of high-sulfur bauxite, so as to improve the activation performance of the activator on the high-sulfur bauxite; in addition, the composite activator has low corrosion of raw materials, can reduce the corrosion of the composite activator, and thus can improve the activation performance of the activator while reducing the corrosion of the activator.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of recycling of ore resources, and particularly relates to a composite activator based on phytic acid and a preparation method and application thereof. BACKGROUND

[0002] Domestic bauxite is mainly high-sulfur diaspore type bauxite, although most of the grade of this type of bauxite is high, but the sulfur content of this type of bauxite is also very high, so before the resource development and utilization of this type of bauxite, desulfurization treatment must be carried out first. At present, the most effective method of desulfurization treatment is mainly flotation method, and currently the traditional flotation method generally uses sulfuric acid or copper sulfate as an activator for activation.

[0003] However, sulfuric acid is a strong acid and has strong corrosivity, and copper sulfate also has certain corrosivity, and the activator with corrosion has strong corrosion to the flotation equipment, which easily affects the progress of flotation desulfurization, thereby affecting the index of bauxite concentrate after flotation treatment, and when high-sulfur bauxite slurry with high mud content is encountered, the high corrosivity of sulfuric acid or copper sulfate is difficult to activate this type of high-sulfur bauxite slurry, so that the activation performance of this type of activator is poor, thereby affecting the index of bauxite concentrate after flotation treatment. SUMMARY

[0004] The present application provides a composite activator based on phytic acid and a preparation method and application thereof, to solve the technical problem of how to reduce the corrosion of the activator while improving the activation performance of the activator.

[0005] In a first aspect, the present application provides a composite activator based on phytic acid, the raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator satisfies:

[0006] (3m+n):q=12:1,

[0007] m:q=(0~4):1, and

[0008] n:q=(0~12):1,

[0009] In the formula, q is the amount of substance of phytic acid;

[0010] m is the amount of substance of trivalent metal hydroxide;

[0011] n is the amount of substance of ammonium bicarbonate;

[0012] The trivalent metal hydroxide includes aluminum hydroxide and / or iron hydroxide.

[0013] Optionally, the composite activator also satisfies:

[0014] m:q=(1~4):1, and

[0015] n:q=(1~12):1,

[0016] q is the amount of substance of phytic acid;

[0017] m is the amount of substance of the trivalent metal hydroxide;

[0018] n is the amount of substance of ammonium bicarbonate.

[0019] Optionally, the composite activator further satisfies:

[0020] m:q=(1~3):1, and

[0021] n:q=(3~9):1,

[0022] q is the amount of substance of phytic acid;

[0023] m is the amount of substance of the trivalent metal hydroxide;

[0024] n is the amount of substance of ammonium bicarbonate.

[0025] Optionally, the composite activator has a molecular structure as shown in Formula 1.

[0026] ,

[0027] Formula 1,

[0028] In Formula 1, m is the amount of substance of the trivalent metal hydroxide, n is the amount of substance of ammonium bicarbonate, and M is a trivalent metal ion.

[0029] The amount of substance m of the trivalent metal hydroxide and the amount of substance n of the ammonium bicarbonate satisfy: (3m+n)=12.

[0030] In a second aspect, the application provides a method for preparing the composite activator of the first aspect, and the method comprises:

[0031] Mixing and heating phytic acid, trivalent metal hydroxide and ammonium bicarbonate to make the phytic acid, the trivalent metal hydroxide and the ammonium bicarbonate undergo a neutralization reaction to obtain a composite activator.

[0032] Optionally, the end temperature of the heating is 25℃-95℃, and the heating time is 0.5h-6h.

[0033] In a third aspect, the application provides an application of a composite activator, and the application comprises using the composite activator of the first aspect as a desulfurization reagent for desulfurization treatment of high-sulfur bauxite.

[0034] In a fourth aspect, the application provides a method for desulfurization of high-sulfur bauxite, the method comprising:

[0035] The high-sulfur bauxite is crushed and then ground to obtain high-sulfur bauxite powder;

[0036] A sodium silicate-based depressant is added to the high-sulfur bauxite powder for first pulp conditioning to obtain a first slurry;

[0037] The composite activator of the first aspect is added to the first slurry for second pulp conditioning to obtain a second slurry;

[0038] A xanthate-based desulfurization collector and a frother are added to the second slurry to obtain a flotation slurry;

[0039] An acid gas is introduced into the flotation slurry to avoid oxidation of the flotation slurry, and then the flotation slurry after introduction of the acid gas is subjected to flotation froth scraping to obtain a flotation mixture;

[0040] The flotation mixture is subjected to roughing, cleaning and scavenging to obtain an aluminum concentrate and a sulfur concentrate, respectively;

[0041] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥5×10 -5 :1;

[0042] The xanthate-based desulfurization collector comprises at least one of the following:

[0043] Ethyl xanthate, butyl xanthate, isobutyl xanthate, amyl xanthate and isoamyl xanthate.

[0044] Optionally, the weight m3 of fine 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= (0.75-0.85):1, and the particle size of the fine high-sulfur bauxite powder is ≤0.074 mm.

[0045] Optionally, the time for the flotation froth scraping is 12-20 min.

[0046] The above technical solution provided by the embodiments of the application has the following advantages compared with the prior art:

[0047] The application provides a composite activator based on phytic acid, raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, the composite activator satisfies (3m+n):q=12:1, m:q=(0-4):1 and n:q=(0-12):1, wherein q is the amount of substance of phytic acid, m is the amount of substance of trivalent metal hydroxide, and n is the amount of substance of ammonium bicarbonate; wherein the trivalent metal hydroxide includes aluminum hydroxide and / or iron hydroxide. The raw materials of the composite activator can include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator can satisfy (3m+n):q=12:1, which can promote sufficient phytic acid in the composite activator, the sufficient phytic acid can improve the oxidation potential of the pyrite surface in the high-sulfur bauxite, the hydrophilic substance of the pyrite in the high-sulfur bauxite with the improved surface oxidation potential is easy to be removed, so that the content of the hydrophilic substance wrapped on the surface of the pyrite in the high-sulfur bauxite can be reduced, and the fresh surface of the high-sulfur bauxite is exposed; in addition, the composite activator can also satisfy m:q=(0-4):1 and n:q=(0-12):1, and the composite activator can satisfy that the ratio of the sum of the amount of substance m of the trivalent metal hydroxide and the amount of substance n of the ammonium bicarbonate to the amount of substance of the phytic acid is 12:1, the metal ion of the aluminum hydroxide or the iron hydroxide can be directly adsorbed on the sulfur atom of the pyrite in the high-sulfur bauxite with the fresh surface through the ammonium bicarbonate, so that the sulfur atom on the surface of the high-sulfur bauxite can be prevented from occupying other active sites, 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; in addition, the corrosion of the phytic acid, the trivalent metal hydroxide and the ammonium bicarbonate is low, the corrosion of the composite activator can be reduced, and the activation performance of the activator can be improved while the corrosion of the activator is reduced. BRIEF DESCRIPTION OF DRAWINGS

[0048] The accompanying drawings, which are incorporated herein and constitute part of the specification, illustrate embodiments consistent with the application and, together with the description, serve to explain the principles of the application.

[0049] In order to more clearly illustrate the technical solutions in the embodiments of the application or in the prior art, the accompanying drawings needed to be used in the embodiments or the prior art description will be briefly introduced as follows. Obviously, for those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

[0050] Figure 1 A microcosmic schematic view of the composite activator based on phytic acid provided by the embodiments of the application;

[0051] Figure 2 A macroscopic schematic view of the composite activator based on phytic acid provided by the embodiments of the application;

[0052] Figure 3 A process flow diagram for preparing the composite activator provided in the embodiments of the present application is shown in the following.

[0053] Figure 4 A process flow diagram for a desulfurization method of high-sulfur bauxite provided in the embodiments of the present application is shown in the following. DETAILED DESCRIPTION

[0054] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of protection of the present application.

[0055] Various embodiments of the present application can exist in the form of a range; it should be understood that the description in the form of a range is merely for the convenience and brevity, and should not be understood as a hard limit on the scope of the present application; therefore, it should be considered that the described range has specifically disclosed all possible sub-ranges and single values in 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 in the range, such as 1, 2, 3, 4, 5 and 6, which applies to any range; in addition, whenever a numerical range is indicated in this document, it refers to any cited number (fraction or integer) in the indicated range.

[0056] In this document, the terms "comprises", "comprising", "includes", "including" or "contains", "containing" means "including, but not limited to". The terms "first", "second", "third", etc. are used only to distinguish one entity or operation from another, and do not necessarily require or imply any actual relationship or order between or among such entities or operations. The term "and / or" describes the association relationship of the associated objects, which means that there can be three relationships, for example, A and / or B can represent: A exists alone, A and B exist together, B exists alone; Where A and B can be singular or plural. "At least one" means one or more, "multiple" means two or more; "At least one", "at least one of the following" or the like means any combination of the items, including single item (s) or multiple items (s) ; For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased or prepared by existing methods.

[0057] Figure 1 An exemplary micrograph of a phytic acid-based composite activator provided by the embodiments of the present application is shown;

[0058] Figure 2 An exemplary macrograph of a phytic acid-based composite activator provided by the embodiments of the present application is shown;

[0059] As Figure 1 and Figure 2 shown, the embodiments of the present application provide a phytic acid-based composite activator, the raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, the composite activator satisfies:

[0060] (3m+n):q=12:1,

[0061] m:q=(0~4):1, and

[0062] n:q=(0~12):1,

[0063] In the formula, q is the amount of substance of phytic acid;

[0064] m is the amount of substance of trivalent metal hydroxide;

[0065] n is the amount of substance of ammonium bicarbonate;

[0066] Wherein, the trivalent metal hydroxide includes aluminum hydroxide and / or iron hydroxide.

[0067] The complex activator can satisfy m:q=0:1, 1:1, 2:1, 3:1 or 4:1.

[0068] The complex activator can satisfy: n:q=0:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1 or 12:1.

[0069] In some alternative embodiments, the complex activator further satisfies:

[0070] m:q=(1-4):1, and

[0071] n:q=(1-12):1,

[0072] In the formula, q is the amount of substance of phytic acid;

[0073] m is the amount of substance of the trivalent metal hydroxide;

[0074] n is the amount of substance of ammonium bicarbonate;

[0075] In some alternative embodiments, the complex activator further satisfies:

[0076] m:q=(1-3):1, and

[0077] n:q=(3-9):1,

[0078] In the formula, q is the amount of substance of phytic acid;

[0079] m is the amount of substance of the trivalent metal hydroxide;

[0080] n is the amount of substance of ammonium bicarbonate;

[0081] In these embodiments, the complex activator can further satisfy m:q=(1-4):1 and n:q=(1-12):1, and the complex activator can further satisfy m:q=(1-3):1 and n:q=(3-9):1, which can cause there to be sufficient trivalent metal hydroxide and sufficient ammonium bicarbonate in the complex activator, and the sufficient trivalent metal hydroxide and the sufficient ammonium bicarbonate can cause the trivalent metal ions to directly adsorb on the sulfur atoms of the pyrite exposed on the fresh surface of the high-sulfur bauxite, so as to avoid the sulfur atoms on the surface of the high-sulfur bauxite from occupying other active sites, thereby increasing the activity of the surface of the high-sulfur bauxite, and further improving the activation performance of the activator on the high-sulfur bauxite.

[0082] In some alternative embodiments, the complex activator has a molecular structure as shown in Formula 1.

[0083] ,

[0084] Formula 1,

[0085] In Formula 1, m is the amount of substance of the trivalent metal hydroxide, n is the amount of substance of the ammonium bicarbonate, and M is a trivalent metal ion;

[0086] The amount of substance m of the trivalent metal hydroxide and the amount of substance n of the ammonium bicarbonate satisfy: (3m+n)=12;

[0087] In these embodiments, the composite activator can have a molecular structure as shown in Formula 1, and the amount of substance of the trivalent metal hydroxide and the amount of substance of the ammonium bicarbonate can satisfy: (3m+n)=12; it can be explained that the reaction among phytic acid, trivalent metal hydroxide and ammonium bicarbonate in the composite activator is sufficient, so that a stable composite activator can be formed.

[0088] Figure 3 An exemplary flowchart of a method for preparing the composite activator provided by the embodiments of the present application is shown;

[0089] Based on a general application, as Figure 3 shown, the embodiments of the present application provide a method for preparing the composite activator, which comprises:

[0090] S1. mixing and heating phytic acid, trivalent metal hydroxide and ammonium bicarbonate to make the phytic acid, the trivalent metal hydroxide and the ammonium bicarbonate undergo a neutralization reaction to obtain a composite activator.

[0091] The method is a preparation method for the composite activator described above, and the specific composition of the composite activator can refer to the above embodiments. Since the preparation method adopts part or all of the technical solutions of the above embodiments, it at least has all the beneficial effects brought by the technical solutions of the above embodiments, which will not be repeated here.

[0092] In some optional embodiments, the end point temperature of the heating is 25℃-95℃, and the heating time is 0.5h-6h.

[0093] In these embodiments, the end point temperature of the heating can be 25℃-95℃, and the heating time can be 0.5h-6h, which can promote the neutralization reaction among phytic acid, copper hydroxide and ammonium bicarbonate to be sufficient to obtain sufficient composite activator.

[0094] The end point temperature of the heating can be 25℃, 35℃, 45℃, 55℃, 65℃, 75℃, 85℃ or 95℃.

[0095] The heating time can be 0.5 h, 1.0 h, 1.5 h, 2.0 h, 2.5 h, 3.0 h, 3.5 h, 4.0 h, 4.5 h, 5.0 h, 5.5 h, or 6.0 h.

[0096] Based on one general inventive concept, the application provides an application of a composite activator, which comprises using the composite activator as a desulfurization reagent for desulfurization treatment of high-sulfur bauxite.

[0097] The application is achieved based on the above-mentioned composite activator, and the specific composition of the composite activator can refer to the above-mentioned embodiments. Since the application adopts part or all of the technical solutions of the above-mentioned embodiments, it at least has all the beneficial effects brought by the technical solutions of the above-mentioned embodiments, which will not be repeated here.

[0098] Figure 4 An exemplary flowchart of a high-sulfur bauxite desulfurization method provided by the application is shown;

[0099] Based on one general inventive concept, as Figure 4 shown, the application provides a high-sulfur bauxite desulfurization method, which comprises:

[0100] S1. crushing high-sulfur bauxite and then grinding to obtain high-sulfur bauxite powder;

[0101] S2. adding a sodium silicate-based depressant to the high-sulfur bauxite powder for first slurry preparation to obtain a first slurry;

[0102] S3. adding the composite activator to the first slurry for second slurry preparation to obtain a second slurry;

[0103] S4. adding a xanthate-based desulfurization collector and a frother to the second slurry to obtain a flotation slurry;

[0104] S5. passing an acid gas into the flotation slurry to avoid oxidation of the flotation slurry, and then performing flotation froth scraping on the flotation slurry after the acid gas is passed in to obtain a flotation mixture;

[0105] performing roughing, cleaning, and scavenging on the flotation mixture to obtain an aluminum concentrate and a sulfur concentrate, respectively;

[0106] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥5×10 -5 :1;

[0107] The xanthate-based desulfurization collector comprises at least one of:

[0108] Ethyl xanthate, butyl xanthate, isobutyl xanthate, pentyl xanthate and isopentyl xanthate.

[0109] This method is based on the above-mentioned composite activator. The specific composition of the composite 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.

[0110] 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.

[0111] It should be noted that the addition of this composite activator can promote the direct adsorption of copper ions from copper hydroxide onto the sulfur atoms of pyrite in high-sulfur bauxite exposed on fresh surfaces, thus preventing sulfur atoms on the surface of high-sulfur bauxite from occupying other active sites. This increases 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 and hydrophobic bixanthate layers will form on the surface of pyrite in high-sulfur bauxite. The composite activator improves the collectability of xanthate-based desulfurization collectors for pyrite in high-sulfur bauxite. Furthermore, the ammonium ions in the composite activator promote electrochemical reactions on the surface of pyrite in high-sulfur bauxite by the xanthate collectors, generating a hydrophobic double xanthate layer, which further enhances the collectability of xanthate-based desulfurization collectors for pyrite in high-sulfur bauxite. Additionally, the ammonium ions in the composite 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.

[0112] 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%.

[0113] 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.

[0114] It should be noted that the first and second slurries are only set for distinguishing the operations, and not for indicating the operation sequence; the first and second slurries can be stirred to facilitate the mixing of the materials.

[0115] In some alternative 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= (0.75-0.85):1, and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074 mm.

[0116] In these 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 can satisfy the relationship: m3:m4= (0.75-0.85):1, and the particle size of the fine-grained high-sulfur bauxite powder is generally ≤0.074 mm, which can facilitate the effective combination of the sodium silicate inhibitor, the composite activator, the xanthate desulfurization collector, and the foaming agent with the high-sulfur bauxite powder, so that sufficient aluminum concentrate and sulfur concentrate can be obtained.

[0117] 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 can 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.

[0118] In some alternative embodiments, the time for the flotation scraping is 13-18 min.

[0119] In these embodiments, the time for the flotation scraping can be 13-18 min, which can facilitate the sufficient flotation scraping to remove the impurities floated in the flotation slurry after the acid gas by the flotation scraping.

[0120] The time for the flotation scraping can be 13 min, 14 min, 15 min, 16 min, 17 min, or 18 min.

[0121] The present application will be further described below in conjunction with specific examples. In the following examples, the experimental methods not specified in the specific conditions are generally determined according to the industry standards; if there is no corresponding industry standard, the general international standards, conventional conditions, or the conditions suggested by the manufacturers are used.

[0122] Example 1

[0123] A composite activator, the raw materials of the composite activator include phytic acid, trivalent metal hydroxide, and ammonium bicarbonate, and the composite activator satisfies:

[0124] (3m+n):q=12:1,

[0125] m:q=4:1, and

[0126] n:q=0:1,

[0127] wherein q is the amount of substance of phytic acid, 1 mol;

[0128] m is the amount of substance of the trivalent metal hydroxide, 4 mol;

[0129] n is the amount of substance of ammonium bicarbonate, 0 mol;

[0130] wherein the trivalent metal hydroxide is aluminum hydroxide.

[0131] The composite activator has a molecular structure as shown in Formula 1,

[0132] ,

[0133] Formula 1,

[0134] In Formula 1, m is the amount of substance of the trivalent metal hydroxide, and has a value of 4; n is the amount of substance of ammonium bicarbonate, and has a value of 0, and M is a trivalent metal ion Al 3+ ;

[0135] A high-sulfur bauxite ore with a sulfur content of 2.41% was selected from a certain bauxite mine in Henan.

[0136] As shown in Figure 3 , a method for preparing a composite activator comprises:

[0137] S1. mixing and heating phytic acid, trivalent metal hydroxide and ammonium bicarbonate to make phytic acid, trivalent metal hydroxide and ammonium bicarbonate undergo a neutralization reaction to obtain a composite activator.

[0138] The end point temperature of heating is 25°C, and the heating time is 0.5 h.

[0139] As shown in Figure 4 , a method for desulfurizing a high-sulfur bauxite ore comprises:

[0140] S1. crushing the high-sulfur bauxite ore to 3 mm, and then grinding to obtain a high-sulfur bauxite ore powder;

[0141] S2. adding a sodium silicate-based depressant to the high-sulfur bauxite ore powder at a mass ratio of 1500 g / t and stirring for 3 min for first slurry preparation to obtain a first slurry;

[0142] S3. The composite activator is added to the first slurry in a mass ratio of 80 g / t and stirred for 3 min for second sizing to obtain a second slurry;

[0143] S4. The xanthate desulfurization collector is added to the second slurry in a mass ratio of 700 g / t and the frother is added in a mass ratio of 300 g / t and stirred for 6 min to obtain a flotation slurry;

[0144] S5. The mixed gas of CO2 and N2 is introduced into the flotation slurry to avoid oxidation of the flotation slurry, and then the flotation slurry after the introduction of the acid gas is scraped for flotation to obtain a flotation mixture;

[0145] S6. The flotation mixture is roughed, cleaned and scavenged to obtain an aluminum concentrate and a sulfur concentrate, respectively;

[0146] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥8×10 -5 :1;

[0147] The xanthate desulfurization collector is pentyl xanthate.

[0148] 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=0.80:1, and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074 mm.

[0149] The time of the flotation scraping is 13 min.

[0150] Example 2

[0151] A composite activator, the raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator satisfies:

[0152] (3m+n):q=12:1,

[0153] m:q=1:1, and

[0154] n:q=9:1,

[0155] In the formula, q is the amount of substance of phytic acid, 1 mol;

[0156] m is the amount of substance of trivalent metal hydroxide, 1 mol;

[0157] n is the amount of substance of ammonium bicarbonate, 9 mol;

[0158] The trivalent metal hydroxide is aluminum hydroxide.

[0159] The composite activator has a molecular structure as shown in Formula 1,

[0160] ,

[0161] Formula 1,

[0162] In formula 1, m is the amount of substance of aluminum hydroxide or iron hydroxide, and is 1; n is the amount of substance of ammonium bicarbonate, and is 9, and M is a trivalent metal ion Al 3+ ;

[0163] A certain magnetic separation aluminum concentrate slurry is selected, and the sulfur content thereof is 5.74%.

[0164] As shown in Figure 3 , a method for preparing a composite activator comprises the following steps:

[0165] S1. Mixing and heating phytic acid, trivalent metal hydroxide and ammonium bicarbonate to make phytic acid, trivalent metal hydroxide and ammonium bicarbonate undergo a neutralization reaction to obtain a composite activator.

[0166] The end point temperature of heating is 50 DEG C, and the heating time is 2h.

[0167] As shown in Figure 4 , a method for desulfurizing high-sulfur bauxite comprises the following steps:

[0168] S1. A magnetic separation aluminum concentrate slurry with a mass concentration of 28% is added to a flotation machine at 1.5L and stirred for 3min to perform first slurry preparation to obtain a first slurry;

[0169] S2. The composite activator is added to the first slurry according to a mass ratio of 150g / t and stirred for 3min to perform second slurry preparation to obtain a second slurry;

[0170] S3. The xanthate desulfurization collector is added to the second slurry according to a mass ratio of 900g / t, and the foaming agent is added to the second slurry according to a mass ratio of 450g / t, and the mixture is stirred for 6min to obtain a flotation slurry;

[0171] S4. The mixed gas of CO2 and N2 is introduced into the flotation slurry to avoid oxidation of the flotation slurry, and then the flotation slurry after the introduction of the acid gas is subjected to flotation scraping to obtain a flotation mixture;

[0172] S5. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain an aluminum concentrate and a sulfur concentrate, respectively;

[0173] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥15x10 -5 :1;

[0174] The xanthate desulfurization collector is butyl xanthate.

[0175] The weight m3 of the fine high-sulfur bauxite powder and the weight m4 of the high-sulfur bauxite powder satisfy the relationship m3:m4=0.75:1, and the fine high-sulfur bauxite powder has a particle size of ≤0.074 mm.

[0176] The time for the flotation to scrape the froth is 17.0 min.

[0177] Example 3

[0178] A composite activator, raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator satisfies, in terms of 1 mol of the phytic acid:

[0179] (3m+n):q=12:1,

[0180] m:q=2:1, and

[0181] n:q=6:1,

[0182] In the formula, q is the amount of substance of the phytic acid, 1 mol;

[0183] m is the amount of substance of the trivalent metal hydroxide, 2 mol;

[0184] n is the amount of substance of the ammonium bicarbonate, 6 mol;

[0185] The trivalent metal hydroxide is aluminum hydroxide.

[0186] The composite activator has a molecular structure as shown in Formula 1,

[0187] ,

[0188] Formula 1,

[0189] In Formula 1, m is the amount of substance of the aluminum hydroxide or the iron hydroxide, and has a value of 2; n is the amount of substance of the ammonium bicarbonate, and has a value of 6, and M is the trivalent metal ion Al 3+ ;

[0190] The raw ore of a high-sulfur bauxite in Guizhou is selected, and the sulfur content of the raw ore is 5.05%.

[0191] As Figure 3 shown, a method for preparing a composite activator includes:

[0192] As Figure 3 shown, a method for preparing a composite activator includes:

[0193] S1. The phytic acid, the trivalent metal hydroxide and the ammonium bicarbonate are mixed and heated to make the phytic acid, the trivalent metal hydroxide and the ammonium bicarbonate perform a neutralization reaction, so as to obtain the composite activator.

[0194] The end point temperature of heating is 50℃, and the time of heating is 3h.

[0195] As shown in Figure 4 A desulfurization method of high-sulfur bauxite, comprising:

[0196] S1. crushing the high-sulfur bauxite to 3mm, and then grinding to obtain high-sulfur bauxite powder;

[0197] S2. adding a sodium silicate type depressant to the high-sulfur bauxite powder at a mass ratio of 2000g / t and stirring for 3min to perform first slurry preparation to obtain a first slurry;

[0198] S3. adding a composite activator to the first slurry at a mass ratio of 100g / t and stirring for 3min to perform second slurry preparation to obtain a second slurry;

[0199] S4. adding a xanthate type desulfurization collector at a mass ratio of 900g / t and a frother at a mass ratio of 400g / t to the second slurry and stirring for 6min to obtain a flotation slurry;

[0200] S5. passing a mixed gas of CO2 and N2 into the flotation slurry to avoid oxidation of the flotation slurry, and then performing flotation scraping of the flotation slurry after passing the acid gas to obtain a flotation mixture;

[0201] S6. performing roughing, cleaning and scavenging on the flotation mixture to obtain an aluminum concentrate and a sulfur concentrate, respectively;

[0202] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥10×10 -5 :1;

[0203] The xanthate type desulfurization collector is pentyl xanthate.

[0204] The weight m3 of the fine 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=0.85:1, the particle size of the fine high-sulfur bauxite powder is ≤0.074mm, and the particle size of the fine high-sulfur bauxite powder is ≤0.074mm.

[0205] The time of flotation scraping is 20.0min.

[0206] Example 4

[0207] A composite activator, the raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator satisfies:

[0208] (3m+n):q=12:1,

[0209] m:q=3:1, and

[0210] n:q=3:1,

[0211] In the formula, q is the amount of substance of phytic acid, 1 mol;

[0212] m is the amount of substance of the trivalent metal hydroxide, 3 mol;

[0213] n is the amount of substance of ammonium bicarbonate, 3 mol;

[0214] The trivalent metal hydroxide is aluminum hydroxide.

[0215] The composite activator has a molecular structure as shown in Formula 1,

[0216] ,

[0217] Formula 1,

[0218] In Formula 1, m is the amount of substance of aluminum hydroxide or iron hydroxide, and has a value of 3; n is the amount of substance of ammonium bicarbonate, and has a value of 3.

[0219] As shown in Figure 3 , a method for preparing a composite activator comprises:

[0220] S1. Mixing and heating phytic acid, trivalent metal hydroxide, and ammonium bicarbonate to make phytic acid, trivalent metal hydroxide, and ammonium bicarbonate undergo a neutralization reaction to obtain a composite activator.

[0221] The end point temperature of heating is 75°C, and the heating time is 4h.

[0222] A certain decarburized bauxite slurry is selected, and the sulfur content thereof is 4.41%.

[0223] As shown in Figure 4 , a method for desulfurizing high-sulfur bauxite comprises:

[0224] S1. A 1.5L decarburized bauxite slurry with a mass concentration of 27% is added to a flotation machine and stirred for 3min for first slurry preparation to obtain a first slurry;

[0225] S2. The composite activator is added to the first slurry according to a mass ratio of 100g / t and stirred for 3min for second slurry preparation to obtain a second slurry;

[0226] S3. The xanthate desulfurization collector is added to the second slurry according to a mass ratio of 800g / t, and the foaming agent is added according to a mass ratio of 400g / t, and the mixture is stirred for 6min to obtain a flotation slurry;

[0227] S5. The mixed gas of CO2 and N2 is introduced into the flotation slurry to avoid the oxidation of the flotation slurry, and then the flotation slurry after the introduction of the acid gas is subjected to flotation scraping to obtain a flotation mixture;

[0228] S6. The flotation mixture is subjected to roughing, cleaning and scavenging to obtain an aluminum concentrate and a sulfur concentrate, respectively.

[0229] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥10×10 -5 ;

[0230] The weight m3 of the fine 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=0.85:1, and the particle size of the fine high-sulfur bauxite powder is ≤0.074mm.

[0231] The xanthate desulfurization collector is butyl xanthate.

[0232] The time of the flotation scraping is 16.0min.

[0233] Example 5

[0234] A composite activator, the raw materials of the composite activator include phytic acid, trivalent metal hydroxide and ammonium bicarbonate, and the composite activator satisfies:

[0235] (3m+n):q=12:1,

[0236] m:q=4:1, and

[0237] n:q=0:1,

[0238] In the formula, q is the amount of substance of phytic acid, 1mol;

[0239] m is the amount of substance of trivalent metal hydroxide, 4mol;

[0240] n is the amount of substance of ammonium bicarbonate, 0mol;

[0241] The trivalent metal hydroxide is iron hydroxide.

[0242] The composite activator has a molecular structure as shown in Formula 1,

[0243] ,

[0244] Formula 1,

[0245] In Formula 1, m is the amount of substance of aluminum hydroxide or iron hydroxide, and the value is 4; n is the amount of substance of ammonium bicarbonate, and the value is 0, and M is the trivalent metal ion Fe 3+ ;

[0246] As shown in Figure 3 A method for preparing a composite activator comprises:

[0247] S1. mixing and heating phytic acid, trivalent metal hydroxide and ammonium bicarbonate to make phytic acid, trivalent metal hydroxide and ammonium bicarbonate undergo a neutralization reaction to obtain a composite activator.

[0248] The end point temperature of heating is 95℃, and the time of heating is 6h.

[0249] Select a high-sulfur bauxite ore from Chongqing, and the sulfur content of the ore is 4.08%.

[0250] As shown in Figure 4 A desulfurization method for high-sulfur bauxite comprises:

[0251] S1. crushing the high-sulfur bauxite to 3mm, and then grinding to obtain high-sulfur bauxite powder;

[0252] S2. adding a sodium silicate-based depressant to the high-sulfur bauxite powder at a mass ratio of 1500g / t and stirring for 3min to perform first slurry preparation to obtain a first slurry;

[0253] S3. adding a composite activator to the first slurry at a mass ratio of 100g / t and stirring for 3min to perform second slurry preparation to obtain a second slurry;

[0254] S4. adding a xanthate-based desulfurization collector at a mass ratio of 700g / t and a frother at a mass ratio of 300g / t to the second slurry and stirring for 6min to obtain a flotation slurry;

[0255] S5. passing a mixed gas of CO2 and N2 into the flotation slurry to avoid oxidation of the flotation slurry, and then performing flotation scraping on the flotation slurry after the acid gas is passed to obtain a flotation mixture;

[0256] S6. performing roughing, cleaning and scavenging on the flotation mixture to obtain aluminum concentrate and sulfur concentrate, respectively;

[0257] The weight m1 of the composite activator and the weight m2 of the first slurry satisfy the relationship: m1:m2≥10×10 -5 ;

[0258] The xanthate-based desulfurization collector is pentyl xanthate.

[0259] 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=0.80:1, and the particle size of the fine-grained high-sulfur bauxite powder is ≤0.074mm.

[0260] The time for flotation and froth scraping was 15 min.

[0261] Comparative Example 1

[0262] Comparative Example 1 and Example 1 were compared, and the difference between Comparative Example 1 and Example 1 was that:

[0263] Only oxalic acid was used as a complex activator.

[0264] Comparative Example 2

[0265] Comparative Example 2 and Example 2 were compared, and the difference between Comparative Example 1 and Example 2 was that:

[0266] Only sulfuric acid was used as a complex activator.

[0267] Comparative Example 3

[0268] Comparative Example 3 and Example 3 were compared, and the difference between Comparative Example 1 and Example 3 was that:

[0269] Only sulfuric acid was used as a complex activator.

[0270] Comparative Example 4

[0271] Comparative Example 4 and Example 4 were compared, and the difference between Comparative Example 1 and Example 4 was that:

[0272] Only copper sulfate was used as a complex activator.

[0273] Comparative Example 5

[0274] Comparative Example 5 and Example 5 were compared, and the difference between Comparative Example 1 and Example 5 was that:

[0275] Only copper sulfate was used as a complex activator.

[0276] Related experiments and effect data:

[0277] The performance parameters of the aluminum concentrate and the sulfur concentrate obtained in each example and comparative example were respectively determined, and the results are shown in Table 1.

[0278] Table 1

[0279]

[0280] As can be seen from Table 1, the sulfur content of the aluminum concentrate obtained in Example 1 can be reduced to 0.29%, the sulfur content of the sulfur concentrate can reach 29.98%, and the recovery rate of sulfur recovered by the sulfur concentrate in Example 1 is 88.81%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 1 can be reduced to 0.36%, the sulfur content of the sulfur concentrate can reach 24.29%, and the recovery rate of sulfur recovered by the sulfur concentrate in Comparative Example 1 is only 86.35%.

[0281] The sulfur content of the aluminum concentrate obtained in Example 2 can be reduced to 0.46%, the sulfur content of the sulfur concentrate can reach 37.28%, and the recovery rate of sulfur recovered by the sulfur concentrate in Example 2 is 93.13%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 2 can be reduced to 0.58%, the sulfur content of the sulfur concentrate can reach 34.39%, and the recovery rate of sulfur recovered by the sulfur concentrate in Comparative Example 2 is only 91.44%.

[0282] The sulfur content of the aluminum concentrate obtained in Example 3 can be reduced to 0.51%, the sulfur content of the sulfur concentrate can reach 38.22%, and the recovery rate of sulfur recovered by 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 0.68%, the sulfur content of the sulfur concentrate can reach 32.74%, and the recovery rate of sulfur recovered by the sulfur concentrate in Comparative Example 3 is only 88.37%.

[0283] The sulfur content of the aluminum concentrate obtained in Example 4 can be reduced to 0.33%, the sulfur content of the sulfur concentrate can reach 33.84%, and the recovery rate of sulfur recovered by the sulfur concentrate in Example 4 is 93.42%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 4 can be reduced to 0.40%, the sulfur content of the sulfur concentrate can reach 30.57%, and the recovery rate of sulfur recovered by the sulfur concentrate in Comparative Example 4 is only 92.13%.

[0284] The sulfur content of the aluminum concentrate obtained in Example 5 can be reduced to 0.41%, the sulfur content of the sulfur concentrate can reach 36.09%, and the recovery rate of sulfur recovered by the sulfur concentrate in Example 5 is 90.98%; while the sulfur content of the aluminum concentrate obtained in Comparative Example 5 can be reduced to 0.51%, 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 5 is only 88.84%.

[0285] In summary, the composite activator provided in the embodiments of the present application 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. In addition, the ammonium bicarbonate can promote the direct adsorption of aluminum hydroxide or iron hydroxide and other trivalent metal ions on the sulfur atoms of the pyrite in the high-sulfur bauxite with the fresh surface exposed, so as to increase the number of active sites on the surface of the high-sulfur bauxite, and further improve the activation performance of the activator on the high-sulfur bauxite. In addition, the corrosion of phytic acid, trivalent metal hydroxide and ammonium bicarbonate is relatively low, which can reduce the corrosion of the composite activator, so as to improve the activation performance of the activator while reducing the corrosion of the activator.

[0286] In addition, the composite activator provided by the embodiment of the present application uses only phytic acid, trivalent metal hydroxide and ammonium bicarbonate as raw materials, and therefore has good environmental compatibility. In addition, the composite activator does not need to use toxic chemicals such as lead nitrate, and also does not need to use liquid strong acids such as sulfuric acid with strong corrosivity, and therefore the composite activator provided by the embodiment of the present application is also green, environmentally friendly and safe to use.

[0287] In addition, the application of the composite activator provided by the embodiment of the present application can reduce the sulfur content in the obtained aluminum concentrate to less than or equal to 0.60%, and can also improve the sulfur recovery rate in the sulfur concentrate to 88.00%.

[0288] In addition, the desulfurization method for high-sulfur bauxite provided by the embodiment of the present application uses the composite activator with low cost and strong adaptability, and can be widely applied to remove sulfur and other impurities in high-sulfur bauxite or low-sulfur bauxite with a sulfur content of less than 6%. In addition, the composite activator can be applied to the flotation desulfurization process of bauxite, and most of the sulfur impurities in the sulfur-containing bauxite can be floated out through one roughing, two cleaning, three scavenging or one roughing, three cleaning, three scavenging, etc. The aluminum concentrate obtained after cleaning can meet the requirements of the raw material indexes for the production of aluminum oxide, and the sulfur concentrate obtained after scavenging can meet the requirements of sulfuric acid raw materials.

[0289] The above only describes specific embodiments of the present application, so that those skilled in the art can understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, 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 of the present application.

Claims

1. A phytate-based complex activator, characterized by, The raw materials of the composite activator include phytic acid, trivalent metal hydroxide, and ammonium bicarbonate, and the composite activator satisfies the following: (3m+n):q=12:1, m:q=(0~4):1, and n:q=(0~12):1, In the formula, q is the amount of phytic acid. m is the amount of substance of the trivalent metal hydroxide; n is the amount of ammonium bicarbonate; The trivalent metal hydroxide includes aluminum hydroxide and / or iron hydroxide; The composite activator has a molecular structure as shown in Formula 1; ， Formula 1, In Formula 1, m is the amount of substance of the trivalent metal hydroxide, n is the amount of substance of ammonium bicarbonate, and M is the trivalent metal ion.

2. The complexing activator of claim 1, wherein The composite activator also satisfies: m:q=(1~4):1, and n:q=(1~12):1, In the formula, q is the amount of phytic acid. m is the amount of substance of the trivalent metal hydroxide; n is the amount of ammonium bicarbonate.

3. The complexing activator of claim 1, wherein The composite activator also satisfies: m:q=(1~3):1, and n:q=(3~9):1, In the formula, q is the amount of phytic acid. m is the amount of substance of the trivalent metal hydroxide; n is the amount of ammonium bicarbonate.

4. A process for the preparation of a complex activator as claimed in any one of claims 1 to 3, characterized in that, The method includes: Phytic acid, trivalent metal hydroxide, and ammonium bicarbonate are mixed and heated to neutralize the phytic acid, trivalent metal hydroxide, and ammonium bicarbonate, thereby obtaining a composite activator.

5. The method of claim 4, wherein, The final temperature of the heating is 25℃ to 95℃, and the heating time is 0.5h to 6h.

6. Use of a complex activator, characterized in that The application includes using the composite activator as described in any one of claims 1 to 3 as a desulfurization reagent in 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 composite 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 composite activator and the weight m2 of the first slurry satisfy the 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 weight m3 of the fine-grained high-sulfur bauxite powder and the weight m4 of the high-sulfur bauxite powder satisfy the following relationship: m3:m4=(0.75~0.85):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 12 min to 20 min.

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