Ilmenite flotation dispersing agent, preparation method thereof and ilmenite flotation method

Abstract

The invention provides an ilmenite flotation dispersing agent, a preparation method thereof and an ilmenite flotation method, and relates to the field of mineral flotation. The ilmenite flotation dispersant comprises the following raw materials: isopentenol polyoxyethylene ether, acrylic acid and a solvent, the mass ratio of the isopentenol polyoxyethylene ether to the solvent is 1: (2-5); the molar ratio of the isopentenol polyoxyethylene ether to the acrylic acid is 1: (1-5). Polymer molecules contain a large number of anion groups such as carboxylate radicals (-COO), the anion groups adsorb the surfaces of ilmenite and gangue minerals, mineral particles are negatively charged, electrostatic force enables the mineral particles to repel each other, meanwhile, the polymer molecules are of a comb-shaped structure, the structure can be adsorbed on the surfaces of the mineral particles, the mineral particles are dispersed through the steric hindrance effect, and therefore the mineral particles are dispersed. And agglomeration of mineral particles is reduced.

Description

Technical Field

[0001] The present application relates to the field of mineral flotation, and in particular to an ilmenite flotation dispersant and a preparation method thereof, and an ilmenite flotation method. Background Art

[0002] Titanium metal has irreplaceable industrial value in the fields of aerospace, chemical industry, and medical treatment due to its light weight, high strength, corrosion resistance, and biocompatibility. It is a key material in the high-end manufacturing industry. Ilmenite often coexists closely with magnetite, hematite, vanadium-titanium magnetite, rutile, sphene, and silicate gangue (such as pyroxene, amphibole, and chlorite). Gangue seriously interferes with the flotation of ilmenite during flotation.

[0003] Traditional processes are all based on strong acidic conditions and add a large amount of gangue inhibitors (such as water glass, sodium hexametaphosphate, carboxymethyl cellulose) to reduce the impact of gangue minerals on concentrates. Although this solution is widely used in industry, its shortcomings are becoming increasingly prominent. The strong acid flotation environment exacerbates equipment corrosion, and Fe 3+ 、Ti 4+ , Ca 2+ Mg 2+ A large amount of metal ions are dissolved, which interferes with the action of flotation reagents, reduces the selectivity of reagents and leads to a decrease in the quality of ilmenite concentrate. In order to obtain qualified ilmenite concentrate, the amount of flotation reagents needs to be further increased. In addition, a large amount of acidic wastewater is generated during the flotation process and a large amount of flotation reagents remain, which requires multi-stage neutralization-precipitation-filtration treatment, with a large amount of reagent consumption (such as an increase of 30%~50% in the amount of lime), and a large amount of heavy metal-containing sludge is generated, resulting in high disposal costs.

[0004] Therefore, it is becoming increasingly urgent to find flotation reagents with stable performance, suitable cost and environmental friendliness, optimize the current flotation reagent system, and carry out flotation operations under mild conditions as much as possible. Summary of the invention

[0005] The purpose of the present application is to provide an ilmenite flotation dispersant and a preparation method thereof and an ilmenite flotation method to solve the above problems.

[0006] To achieve the above objectives, the present application provides, in a first aspect, an ilmenite flotation dispersant, the raw materials of which include: Isoprenoyl polyoxyethylene ether, acrylic acid and solvent; The mass ratio of the isopentanol polyoxyethylene ether to the solvent is 1:2-5; The molar ratio of the isopentanol polyoxyethylene ether to the acrylic acid is 1:1-5.

[0007] Optionally, the ilmenite flotation dispersant meets at least one of the following conditions: A. the solvent comprises water; B. The pH of the ilmenite flotation dispersant is 6.0 - 7.0.

[0008] The second aspect of the present application provides a method for preparing the ilmenite flotation dispersant, comprising: Under an inert atmosphere, the isopentanol polyoxyethylene ether, the initiator, the acrylic acid, and the solvent are first mixed to react to obtain a reactant; The reactant and the pH regulator are mixed for a second time to obtain an ilmenite flotation dispersant; The initiator includes azobisisobutyronitrile, mercaptopropionic acid and ammonium persulfate.

[0009] Optionally, the preparation method of the ilmenite flotation dispersant meets at least one of the following conditions: A. The inert atmosphere comprises nitrogen; B. The reaction temperature is 50°C - 85°C and the reaction time is 1 h - 2.5 h; C. the mass ratio of the isopentanol polyoxyethylene ether, the azobisisobutyronitrile, the mercaptopropionic acid, and the ammonium persulfate is 1000:4 - 10:2 - 8:2 - 6; D. The pH adjuster includes sodium hydroxide.

[0010] Optionally, the first mixing includes: The isopentanol polyoxyethylene ether and part of the solvent are mixed for the third time to obtain a solution A; The acrylic acid, the mercaptopropionic acid and a portion of the solvent are mixed for the fourth time to obtain a solution B; The ammonium persulfate and the remaining solvents are mixed for a fifth time to obtain a solution C; The solution A, the solution B, the solution C and the azobisisobutyronitrile are mixed for the sixth time; Optionally, the preparation method of the ilmenite flotation dispersant meets at least one of the following conditions: A. the sixth mixing time is 1.5 h - 2 h; B. The mass concentration of the solution B is 10% - 30%; C. The mass concentration of the solution C is 1% - 5%.

[0011] The third aspect of the present application provides a flotation method for ilmenite, comprising: The ilmenite flotation dispersant is used for flotation.

[0012] Optionally, the flotation includes: grinding and pulping the ilmenite to obtain raw ore pulp; Desulfurizing the raw ore pulp to obtain desulfurized ore pulp; The desulfurized ore pulp, pH regulator, collector, inhibitor and ilmenite flotation dispersant are mixed, and roughing, scavenging and concentrating are performed respectively to obtain ilmenite concentrate.

[0013] Optionally, the flotation method of ilmenite satisfies at least one of the following conditions: A. The collector includes one or more of MOH and diesel; B. the pH adjusting agent includes sulfuric acid; C. The inhibitor includes one or more of water glass and sodium fluorosilicate.

[0014] Optionally, the flotation method of ilmenite satisfies at least one of the following conditions: A. The amount of the pH regulator used in the roughing, scavenging and concentrating is 500-1400 g / t of raw ore, 250-600 g / t of raw ore and 650-1000 g / t of raw ore respectively; B. The amount of the collector used in the roughing, scavenging and concentrating is 600-1200 g / t of raw ore, 300-600 g / t of raw ore and 100-800 g / t of raw ore respectively; C. The dosage of the dispersant in the roughing, scavenging and concentrating is 200-700 g / t of raw ore, 100-500 g / t of raw ore and 50-600 g / t of raw ore respectively; D. The dosage of the inhibitor in the roughing, scavenging and concentrating is 600-1400 g / t of raw ore, 200-1000 g / t of raw ore and 100-1200 g / t of raw ore respectively.

[0015] Compared with the prior art, the beneficial effects of this application include: The ilmenite flotation dispersant provided in this application contains a large amount of carboxylate (-COO - ) and other anionic groups, which adsorb on the surface of ilmenite and gangue minerals, making the mineral particles negatively charged. The electrostatic force makes the mineral particles repel each other and reduces the agglomeration of mineral particles. At the same time, the polymer molecules have a comb-like structure, which can be adsorbed on the surface of mineral particles, disperse the mineral particles through the steric hindrance effect and reduce the agglomeration of mineral particles. The molecules of ilmenite flotation dispersant have a long side chain structure, which forms a space barrier on the surface of mineral particles, preventing direct contact between mineral particles, thereby reducing the agglomeration and flocculation of particles.

[0016] The preparation method of the ilmenite flotation dispersant provided in the present application has a relatively simple preparation process, low requirements on reaction conditions, excellent synthesis effect and high efficiency, and significant cost-effectiveness; and the raw materials are commonly used in industry and can be stably supplied, and the pharmaceutical product is convenient for storage and transportation. It has the advantages of simple preparation, low cost, and environmental friendliness, and has good application prospects.

[0017] The flotation method of ilmenite provided in the present application has obvious agglomeration and flocculation phenomena between ilmenite and gangue minerals. Traditional ilmenite flotation usually requires the addition of a large amount of sulfuric acid in combination with traditional gangue mineral inhibitors (water glass, sodium fluorosilicate, carboxymethyl cellulose) to inhibit calcium magnesium silicate minerals in the flotation system. However, after adding the high-efficiency ilmenite flotation dispersant provided in the present application, the dispersion between ilmenite and gangue minerals is enhanced, the selectivity of the inhibitor on gangue minerals and the efficient collection of the collector on ilmenite are promoted, the dosage of reagents in the flotation process is further reduced, and efficient flotation separation of ilmenite is achieved under mild conditions, which solves the industry's demand for flotation reagents for complex and difficult-to-select ilmenite, and provides support for ilmenite beneficiation and efficient recovery of difficult-to-select resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0019] Figure 1 The schematic diagram of the chemical equation of the ilmenite flotation dispersant is shown; Figure 2 This is the infrared spectrum of the ilmenite flotation dispersant product prepared in Example 1; Figure 3 This is a schematic flow chart of the flotation method for ilmenite provided in Example 1. DETAILED DESCRIPTION

[0020] As used herein: "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0021] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0022] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0023] In these examples, parts and percentages are by mass unless otherwise indicated.

[0024] "Mass parts" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass parts of component A are a parts and the mass parts of component B are b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass parts of all components is not limited to 100 parts.

[0025] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0026] The first aspect of the present application provides an ilmenite flotation dispersant, the raw materials of which include: Isoprenol polyoxyethylene ether, acrylic acid, solvent; The mass ratio of the isopentanol polyoxyethylene ether to the solvent is 1:2-5; Optionally, the mass ratio of isopentanol polyoxyethylene ether to the solvent may be 1:2, 1:3, 1:4, 1:5 or any value between 1:2 and 5; The molar ratio of the isopentanol polyoxyethylene ether to the acrylic acid is 1:1-5.

[0027] Optionally, the molar ratio of isopentanol polyoxyethylene ether to acrylic acid can be 1:1, 1:2, 1:3, 1:4, 1:5 or any value between 1:1 and 5.

[0028] In some embodiments, the ilmenite flotation dispersant satisfies at least one of the following conditions: A. the solvent comprises water; B. The pH value of the ilmenite flotation dispersant is 6.0 - 7.0.

[0029] Optionally, the pH value of the ilmenite flotation dispersant may be 6.0, 6.2, 6.4, 6.6, 6.8, 7 or any value between 6.0 and 7.0.

[0030] It should be noted that under pH 6.0 - 7.0, the oxidative side reactions caused by residual free radicals can be reduced, and a small amount of -COOH groups may be retained under weak acidic conditions, enhancing the Ca 2+ Mg 2+ The chelating ability further improves the dispersion performance.

[0031] The second aspect of the present application provides a method for preparing the ilmenite flotation dispersant, comprising: Under an inert atmosphere, first mixing the isopentanol polyoxyethylene ether, the initiator, the acrylic acid and the solvent to obtain a reactant; The reactant and the pH regulator are mixed for a second time to obtain an ilmenite flotation dispersant; The initiator includes azobisisobutyronitrile, mercaptopropionic acid, and ammonium persulfate; It should be noted that azobisisobutyronitrile is an oil-soluble free radical initiator, which can promote the dispersion of various reactants. Its decomposition produces two free radicals that will attack the double bonds of isopentanol polyoxyethylene ether and acrylic acid, starting the chain growth reaction. In addition, the decomposition temperature of azobisisobutyronitrile is close to the reaction temperature. Using azobisisobutyronitrile as an initiator can avoid side reactions caused by high temperature. In some embodiments, the chemical equation of the reaction is as follows Figure 1 As shown, Figure 1 where a is 5 - 15, b is 1 -5, n is 5 - 15, and m is 10 - 80.

[0032] It should be noted that the initiator azobisisobutyronitrile decomposes to produce free radicals that attack isopentanol polyoxyethylene ether and acrylic acid. Acrylic acid polymerizes to form a main chain rich in carboxylic acid groups. The addition of mercaptopropionic acid and ammonium persulfate will continue to decompose the free radicals, promote the grafting of isopentanol polyoxyethylene ether with the main chain to form a comb-like structure with alternating side chains, and terminate the long chain through hydrogen bond transfer to control the molecular weight of the product. Nitrogen mainly plays the role of isolating oxygen in the entire reaction process to avoid the reaction of free radicals and oxygen to generate oxides to block the reaction. Sodium hydroxide is added at the end of the reaction to make the product present a neutral or weakly acidic environment, thereby reducing oxidative side reactions caused by residual free radicals.

[0033] In some embodiments, the method for preparing the ilmenite flotation dispersant satisfies at least one of the following conditions: A. The inert atmosphere comprises nitrogen; B. The reaction temperature is 50°C - 85°C and the reaction time is 1 h - 2.5 h; Optionally, the reaction temperature may be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or any value between 50°C and 85°C, and the reaction time may be 1 h, 1.5 h, 2 h, 2.5 h or any value between 1 h and 2.5 h; It should be noted that at this reaction temperature, the multi-dimensional requirements of initiator decomposition, monomer reactivity and chain transfer efficiency can be balanced. The appropriate temperature can generate a stable free radical flow, ensure the copolymerization rate, and accurately control the molecular weight to obtain a product that meets the requirements. C. the mass ratio of the isopentanol polyoxyethylene ether, the azobisisobutyronitrile, the mercaptopropionic acid, and the ammonium persulfate is 1000:4 - 10:2 - 8:2 - 6; Optionally, the mass ratio of isopentanol polyoxyethylene ether, azobisisobutyronitrile, mercaptopropionic acid, and ammonium persulfate can be 1000:4:2:2, 1000:10:2:2, 1000:4:8:2, 1000:4:2:6, 1000:10:8:6, or any value between 1000:4 - 10:2 -8:2 - 6; D. The pH adjuster includes sodium hydroxide.

[0034] It should be noted that the final product of the reaction contains a large number of carboxylic acid groups (-COOH). -COOH will be in a protonated state under acidic conditions. The unionized -COOH is highly hydrophobic and has poor solubility in subsequent use. The acidic environment will cause the product to be unstable and trigger side reactions, resulting in side chain breakage or main chain degradation. The addition of sodium hydroxide can not only adjust the pH value, but also convert the carboxylic acid group into sodium carboxylate to reduce side reactions, thereby greatly improving the water solubility and stability of the product.

[0035] In some embodiments, the first mixing comprises: The isopentanol polyoxyethylene ether and part of the solvent are mixed for the third time to obtain a solution A; The acrylic acid, the mercaptopropionic acid and a portion of the solvent are mixed for the fourth time to obtain a solution B; The ammonium persulfate and the remaining solvents are mixed for a fifth time to obtain a solution C; The solution A, the solution B, the solution C and the azobisisobutyronitrile are mixed for the sixth time; It should be noted that the core purpose of step-by-step mixing and step-by-step addition of reactants is to optimize the molecular structure and avoid side reactions by accurately controlling the reaction process. Partial addition helps control the temperature during the reaction; adjust the reactivity of the monomers and build an ideal dispersant structure; inhibit the generation of side reactions and ensure the controllability and safety of the operation; In some embodiments, the method for preparing the ilmenite flotation dispersant satisfies at least one of the following conditions: A. the sixth mixing time is 1.5 h - 2 h; Optionally, the sixth mixing time may be 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, 2 h or any value between 1.5 h and 2 h; B. The mass concentration of the solution B is 10% - 30%; Optionally, the mass concentration of solution B may be 10%, 20%, 30%, or any value between 10% and 30%; C. The mass concentration of the solution C is 1% - 5%.

[0036] Optionally, the mass concentration of solution C can be 1%, 2%, 3%, 4%, 5% or any value between 1% and 5%.

[0037] The third aspect of the present application provides a flotation method for ilmenite, comprising: The ilmenite flotation dispersant is used for flotation.

[0038] In some embodiments, the flotation comprises: grinding and pulping the ilmenite to obtain raw ore pulp; Desulfurizing the raw ore pulp to obtain desulfurized ore pulp; The desulfurized ore pulp, pH regulator, collector, inhibitor and ilmenite flotation dispersant are mixed, and roughing, scavenging and concentrating are performed respectively to obtain ilmenite concentrate.

[0039] In some embodiments, the flotation method of ilmenite satisfies at least one of the following conditions: A. The collector includes one or more of MOH, U-T, and MOS diesel; It should be noted that the collector mainly plays the role of collecting ilmenite in flotation, and the addition of dispersant can improve the selectivity of the collector.

[0040] B. the pH adjusting agent includes sulfuric acid; C. The inhibitor includes one or more of water glass, sodium fluorosilicate and carboxymethyl cellulose (CMC).

[0041] It should be noted that the inhibitor mainly plays the role of inhibiting gangue minerals in the flotation process. The addition of dispersant helps to disperse the sludge and enhance the inhibitor effect.

[0042] In some embodiments, the flotation method of ilmenite satisfies at least one of the following conditions: A. The amount of the pH regulator used in the roughing, scavenging and concentrating is 500-1400 g / t of raw ore, 250-600 g / t of raw ore and 650-1000 g / t of raw ore respectively; Optionally, the amount of the pH regulator used in the roughing process can be 500 g / t of raw ore, 1000 g / t of raw ore, 1400 g / t of raw ore, or any value between 500 and 1400 g / t of raw ore; the amount of the pH regulator used in the scavenging process can be 250 g / t of raw ore, 300 g / t of raw ore, 500 g / t of raw ore, 600 g / t of raw ore, or any value between 250 and 600 g / t of raw ore; the amount of the pH regulator used in the concentrating process can be 650 g / t of raw ore, 800 g / t of raw ore, 1000 g / t of raw ore, or any value between 650 and 1000 g / t of raw ore; B. The amount of the collector used in the roughing, scavenging and concentrating is 600-1200 g / t of raw ore, 300-600 g / t of raw ore and 100-800 g / t of raw ore respectively; Optionally, the amount of the collector used in the roughing process can be 600 g / t of raw ore, 1000 g / t of raw ore, 1200 g / t of raw ore, or any value between 600 and 1200 g / t of raw ore; the amount of the collector used in the scavenging process can be 300 g / t of raw ore, 400 g / t of raw ore, 500 g / t of raw ore, 600 g / t of raw ore, or any value between 300 and 600 g / t of raw ore; the amount of the collector used in the concentrating process can be 100 g / t of raw ore, 300 g / t of raw ore, 400 g / t of raw ore, 500 g / t of raw ore, 600 g / t of raw ore, 800 g / t of raw ore, or any value between 100 and 800 g / t of raw ore; C. The dosage of the dispersant in the roughing, scavenging and concentrating is 200-700 g / t of raw ore, 100-500 g / t of raw ore and 50-600 g / t of raw ore respectively; Optionally, the amount of the dispersant used in the roughing process can be 200 g / t of raw ore, 500 g / t of raw ore, 600 g / t of raw ore, 700 g / t of raw ore, or any value between 200 and 700 g / t of raw ore; the amount of the dispersant used in the scavenging process can be 100 g / t of raw ore, 200 g / t of raw ore, 300 g / t of raw ore, 500 g / t of raw ore, or any value between 100 and 500 g / t of raw ore; the amount of the dispersant used in the concentrating process can be 50 g / t of raw ore, 200 g / t of raw ore, 300 g / t of raw ore, 600 g / t of raw ore, or any value between 50 and 600 g / t of raw ore; D. The dosage of the inhibitor in the roughing, scavenging and concentrating is 600-1400 g / t of raw ore, 200-1000 g / t of raw ore and 100-1200 g / t of raw ore respectively.

[0043] Optionally, the amount of the inhibitor used in roughing can be 600 g / t of raw ore, 1000 g / t of raw ore, 1200 g / t of raw ore, 1400 g / t of raw ore or any value between 600 - 1400 g / t of raw ore; the amount of the inhibitor used in scavenging can be 200 g / t of raw ore, 400 g / t of raw ore, 600 g / t of raw ore, 1000 g / t of raw ore or any value between 200 - 1000 g / t of raw ore; the amount of the inhibitor used in concentrating can be 100 g / t of raw ore, 400 g / t of raw ore, 800 g / t of raw ore, 1200 g / t of raw ore or any value between 100 - 1200 g / t of raw ore.

[0044] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0045] The ilmenite flotation in the examples and comparative examples of the present application contains trace pyrite, and is accompanied by silicate minerals such as titanium pyroxene, hornblende, biotite, etc. The total iron TFe grade in the ilmenite raw material is 15.59%, TiO 2 The grade is 18.77%, and the complex composition of the gangue greatly increases the difficulty of flotation.

[0046] Example 1 In a first aspect, the present embodiment provides an ilmenite flotation dispersant, the raw materials of which include isopentanol polyoxyethylene ether, acrylic acid, and a solvent; Wherein, the molar ratio of isopentanol polyoxyethylene ether to acrylic acid is 1:1; The solvent is water.

[0047] The second aspect of this embodiment provides a method for preparing an ilmenite flotation dispersant, and the specific steps are as follows: S1: adding isopentanol polyoxyethylene ether and deionized water in a four-necked flask at a mass ratio of 1:2, introducing nitrogen gas and heating to 70° C. to dissolve, thereby obtaining an isopentanol polyoxyethylene ether solution, also referred to as solution A; S2: Weighing acrylic acid in a molar ratio of 1:1 between isopentanol polyoxyethylene ether and acrylic acid, and weighing mercaptopropionic acid in a mass ratio of 1000:4 between isopentanol polyoxyethylene ether and mercaptopropionic acid, mixing the weighed acrylic acid and mercaptopropionic acid, adding them to deionized water to dissolve and obtaining a solution B with a mass concentration of 20%; S3: Weigh ammonium persulfate according to the mass ratio of isopentanol polyoxyethylene ether and ammonium persulfate of 1000:2, and dissolve the weighed ammonium persulfate in deionized water to obtain a solution C with a mass concentration of 2%; S4: adding solution B and solution C into solution A by a peristaltic pump, and during the pumping process, adding azobisisobutyronitrile in batches into solution A, wherein the mass ratio of isopentanol polyoxyethylene ether to initiator azobisisobutyronitrile is 1000:8, and the whole pumping process takes 2 h; S5: After the pumping is completed, continue stirring and heating to 80°C, keep warm for 2 hours, and then cool down to room temperature; S6: adding the reactant obtained in step S5 to a 40% by mass NaOH solution, adjusting the pH value to 7.0, and obtaining an ilmenite flotation dispersant (HEID).

[0048] The infrared spectrum of the ilmenite flotation dispersant is as follows Figure 2 As shown, 1343 cm -1 and 962 cm -1 The vibration peak at 1100 cm is the bending vibration peak of -OH and -COOH in the symmetric plane. -1 The adsorption at 1281 cm -1 The peak at is the absorption peak of unsaturated polyester (C-COOR).

[0049] The third aspect of this embodiment provides a flotation method for ilmenite, and the specific steps are as follows: The ilmenite is ground and stirred for slurry preparation. The slurry undergoes desulfurization, a roughing operation, a scavenging operation and four concentration processes to obtain ilmenite concentrate.

[0050] Among them, the reagents and dosage used in the desulfurization operation are: sulfuric acid 300g / t raw ore, butyl xanthate 50 g / t raw ore, No. 2 oil 10 g / t raw ore; The reagents and dosages used in titanium roughing are: sulfuric acid 500 g / t raw ore, dispersant 200 g / t raw ore, water glass inhibitor 400 g / t raw ore, MOH collector 800 g / t raw ore, diesel 80 g / t raw ore; The dosage of titanium scavenging agent is half of that of titanium roughing agent; The rougher concentrate obtained from the titanium roughing and the scavenger concentrate obtained from the titanium scavenging were combined for four times of concentration to obtain ilmenite concentrate, wherein the amounts of sulfuric acid used in the four concentrations were 300 g / t of raw ore, 200 g / t of raw ore, 100 g / t of raw ore, and 50 g / t of raw ore, respectively; the amounts of dispersant used in the four concentrations were 150 g / t of raw ore, 100 g / t of raw ore, 50 g / t of raw ore, and 25 g / t of raw ore, respectively; the amounts of MOH collector used in the four concentrations were 400 g / t of raw ore, 300 g / t of raw ore, 200 g / t of raw ore, and 100 g / t of raw ore, respectively; the amounts of diesel used in the four concentrations were 40 g / t of raw ore, 30 g / t of raw ore, 20 g / t of raw ore, and 10 g / t of raw ore, respectively; the amounts of water glass inhibitor used in the four concentrations were 200 g / t of raw ore, 100 g / t of raw ore, 50 g / t of raw ore, and 25 g / t of raw ore, respectively g / t raw ore, 50 g / t raw ore.

[0051] Closed-circuit test was carried out on ilmenite. The whole closed-circuit process was as follows: Figure 3 As shown, the relevant properties of the sulfide obtained from the desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained from the titanium scavenging and the ilmenite feed were tested, and the specific data are shown in Table 1.

[0052] Table 1 Test results

[0053] It can be seen from Table 1 that by adding the ilmenite flotation dispersant of Example 1, the ilmenite concentrate TiO 2 The grade is 48.16%, and TiO 2 The operation recovery rate is 82.23%. Compared with the conventional process reagent system, the addition of the dispersant of Example 1 can significantly reduce the dosage of other reagents and obtain qualified ilmenite concentrate.

[0054] Example 2 The difference from Example 1 is that in the ilmenite flotation dispersant and preparation method thereof, the mass ratio of isopentanol polyoxyethylene ether to azobisisobutyronitrile is 1000:6, the mass ratio of isopentanol polyoxyethylene ether to ammonium persulfate is 1000:3, the molar ratio of isopentanol polyoxyethylene ether to acrylic acid is 1:3, the mass ratio of isopentanol polyoxyethylene ether to mercaptopropionic acid is 1000:3, and NaOH solution is used to adjust the pH value to 7.2.

[0055] The ilmenite flotation dispersant prepared in this example was used for flotation. The flotation method was the same as that in Example 1. The sulfide obtained by desulfurization during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 2.

[0056] Table 2 Test results

[0057] It can be seen from Table 2 that the addition of the ilmenite flotation dispersant of Example 2 increases the ilmenite concentrate TiO 2 The grade is 47.87%, and TiO 2 The operation recovery rate is 82.87%. Compared with the conventional process reagent system, the addition of the dispersant in Example 2 can significantly reduce the dosage of other reagents, and a qualified ilmenite concentrate can be obtained.

[0058] Example 3 The difference from Example 1 is that in the ilmenite flotation dispersant and preparation method thereof, the mass ratio of isopentanol polyoxyethylene ether to initiator azobisisobutyronitrile is 1000:5, the mass ratio of isopentanol polyoxyethylene ether to ammonium persulfate is 1000:4, the molar ratio of isopentanol polyoxyethylene ether to acrylic acid is 1:4, the mass ratio of isopentanol polyoxyethylene ether to mercaptopropionic acid is 1000:7, and NaOH solution is used to adjust the pH value to 6.9.

[0059] The ilmenite flotation dispersant prepared in this example was used for flotation. The flotation method was the same as that in Example 1. The sulfide obtained by desulfurization during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 3.

[0060] Table 3 Test results

[0061] It can be seen from Table 3 that the addition of the ilmenite flotation dispersant of Example 3 increases the ilmenite concentrate TiO 2 The grade is 48.22%, and TiO 2 The operation recovery rate is 79.16%. Compared with the conventional process reagent system, the addition of the dispersant of Example 3 can significantly reduce the dosage of other reagents, and a qualified ilmenite concentrate can be obtained.

[0062] Comparative Example 1 The difference from Example 1 is that no acrylic acid is added.

[0063] The ilmenite flotation dispersant prepared in this comparative example was subjected to flotation. The flotation method was consistent with that in Example 1. The sulfide obtained by desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 4.

[0064] Table 4 Test results

[0065] It can be seen from Table 4 that the addition of the ilmenite flotation dispersant of Comparative Example 1 increases the concentration of TiO 2 The grade is only 38.95%, and TiO 2 The operating recovery rate is 83.40%. Compared with the addition of the dispersant in Example 1, the addition of the dispersant in Comparative Example 1 cannot obtain a qualified ilmenite concentrate. Comparative Example 2 The difference from Example 1 is that mercaptopropionic acid is not added.

[0066] The ilmenite flotation dispersant prepared in this comparative example was subjected to flotation. The flotation method was consistent with that in Example 1. The sulfide obtained by desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 5.

[0067] Table 5 Test results

[0068] It can be seen from Table 5 that the addition of the ilmenite flotation dispersant of Comparative Example 2 increases the concentration of TiO 2 The grade is only 40.09%, and TiO 2 The operating recovery rate is 58.37%. Compared with the addition of the dispersant in Example 1, the addition of the dispersant in Comparative Example 2 cannot obtain a qualified ilmenite concentrate.

[0069] Comparative Example 3 The difference from Example 1 is that no ammonium persulfate is added.

[0070] The ilmenite flotation dispersant prepared in this comparative example was subjected to flotation. The flotation method was consistent with that in Example 1. The sulfide obtained by desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 6.

[0071] Table 6 Test results

[0072] It can be seen from Table 6 that the addition of the ilmenite flotation dispersant of Comparative Example 3 increases the ilmenite concentrate TiO 2 The grade is only 42.13%, and TiO 2 The operating recovery rate is 81.54%. Compared with the addition of the dispersant in Example 1, the addition of the dispersant in Comparative Example 3 cannot obtain high-quality ilmenite concentrate.

[0073] Comparative Example 4 The difference from Example 1 is that no pH adjuster is added.

[0074] The ilmenite flotation dispersant prepared in this comparative example was subjected to flotation. The flotation method was consistent with that in Example 1. The sulfide obtained by desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 7.

[0075] Table 7 Test results

[0076] It can be seen from Table 7 that the addition of the ilmenite flotation dispersant of Comparative Example 4 increases the ilmenite concentrate TiO 2 The grade is only 37.98%, and TiO 2 The operating recovery rate is 54.35%. Compared with the addition of the dispersant in Example 1, the addition of the dispersant in Comparative Example 4 cannot obtain a qualified ilmenite concentrate.

[0077] Comparative Example 5 The difference from Example 1 is that azobisisobutyronitrile is replaced by V-50 (azobisisobutyramidine).

[0078] The ilmenite flotation dispersant prepared in this comparative example was subjected to flotation. The flotation method was consistent with that in Example 1. The sulfide obtained by desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 8.

[0079] Table 8 Test results

[0080] It can be seen from Table 8 that the addition of the ilmenite flotation dispersant of Comparative Example 5 increases the ilmenite concentrate TiO 2 The grade is only 41.16%, and TiO 2 The operating recovery rate is 57.72%. Compared with the addition of the dispersant in Example 1, the addition of the dispersant in Comparative Example 5 cannot obtain high-quality ilmenite concentrate.

[0081] Comparative Example 6 The difference from Example 1 is that prenol polyoxyethylene ether is replaced by polyethylene glycol methacrylate (MPEG).

[0082] The ilmenite flotation dispersant prepared in this comparative example was subjected to flotation. The flotation method was consistent with that in Example 1. The sulfide obtained by desulfurization operation during the flotation process, the ilmenite concentrate obtained after four concentrations, the tailings obtained by titanium scavenging, and the relevant properties of the ilmenite feed were tested. The specific data are shown in Table 9.

[0083] Table 9 Test results

[0084] It can be seen from Table 9 that the addition of the ilmenite flotation dispersant of Comparative Example 6 increases the ilmenite concentrate TiO 2 The grade is only 43.11%, and TiO 2 The operating recovery rate is 66.93%. Compared with the addition of the dispersant in Example 1, the addition of the dispersant in Comparative Example 6 cannot obtain high-quality ilmenite concentrate.

[0085] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

[0086] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A dispersant for ilmenite flotation, characterized in that: Its raw materials include: Isoprenoyl polyoxyethylene ether, acrylic acid and solvent; The mass ratio of the isopentanol polyoxyethylene ether to the solvent is 1:2-5; The molar ratio of the isopentanol polyoxyethylene ether to the acrylic acid is 1:1-5.

2. The ilmenite flotation dispersant according to claim 1, characterized in that: At least one of the following conditions is met: A. the solvent comprises water; B. The pH value of the ilmenite flotation dispersant is 6.0 - 7.

0.

3. A method for preparing an ilmenite flotation dispersant according to claim 1 or 2, characterized in that: include: Under an inert atmosphere, the isopentanol polyoxyethylene ether, the initiator, the acrylic acid and the solvent are first mixed to react to obtain a reactant; The reactant and the pH regulator are mixed for a second time to obtain an ilmenite flotation dispersant; The initiator includes azobisisobutyronitrile, mercaptopropionic acid and ammonium persulfate.

4. The method for preparing an ilmenite flotation dispersant according to claim 3, characterized in that: At least one of the following conditions is met: A. The inert atmosphere comprises nitrogen; B. The reaction temperature is 50°C - 85°C and the reaction time is 1 h - 2.5 h; C. the mass ratio of the isopentanol polyoxyethylene ether, the azobisisobutyronitrile, the mercaptopropionic acid, and the ammonium persulfate is 1000:4 - 10:2 - 8:2 - 6; D. The pH adjuster includes sodium hydroxide.

5. The method for preparing an ilmenite flotation dispersant according to claim 3, characterized in that: The first mixing comprises: The isopentanol polyoxyethylene ether and part of the solvent are mixed for the third time to obtain a solution A; The acrylic acid, the mercaptopropionic acid and a portion of the solvent are mixed for the fourth time to obtain a solution B; The ammonium persulfate and the remaining solvents are mixed for a fifth time to obtain a solution C; The solution A, the solution B, the solution C, and the azobisisobutyronitrile are mixed for the sixth time.

6. The method for preparing an ilmenite flotation dispersant according to claim 5, characterized in that: At least one of the following conditions is met: A. the sixth mixing time is 1.5 h - 2 h; B. The mass concentration of the solution B is 10% - 30%; C. The mass concentration of the solution C is 1% - 5%.

7. A flotation method for ilmenite, characterized in that: include: Flotation is carried out using the ilmenite flotation dispersant described in claim 1 or 2.

8. The flotation method of ilmenite according to claim 7, characterized in that: The flotation comprises: grinding and pulping the ilmenite to obtain raw ore pulp; Desulfurizing the raw ore pulp to obtain desulfurized ore pulp; The desulfurized ore pulp, pH regulator, collector, inhibitor and ilmenite flotation dispersant are mixed, and roughing, scavenging and concentrating are performed respectively to obtain ilmenite concentrate.

9. The flotation method of ilmenite according to claim 8, characterized in that: At least one of the following conditions is met: A. The collector includes one or more of MOH, U-Ti, MOS, and diesel; B. the pH adjusting agent includes sulfuric acid; C. The inhibitor includes one or more of water glass, sodium fluorosilicate, and carboxymethyl cellulose.

10. The flotation method of ilmenite according to claim 9, characterized in that: At least one of the following conditions is met: A. The amount of the pH regulator used in the roughing, scavenging and concentrating is 500-1400 g / t of raw ore, 250-600 g / t of raw ore and 650-1000 g / t of raw ore respectively; B. The amount of the collector used in the roughing, scavenging and concentrating is 600-1200 g / t of raw ore, 300-600 g / t of raw ore and 100-800 g / t of raw ore respectively; C. The amount of the dispersant used in the roughing, scavenging and concentrating is 200-700 g / t of raw ore, 100-500 g / t of raw ore and 50-600 g / t of raw ore respectively; D. The dosage of the depressant in the roughing, scavenging and concentrating is 600-1400 g / t of raw ore, 200-1000 g / t of raw ore and 100-1200 g / t of raw ore respectively.

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