Titanium ore physical and chemical coupling enhanced upgrading method

Abstract

The application relates to a titanium middling physical-chemical coupling reinforced upgrading method, and belongs to the technical field of titanium ore dressing. Manganese-containing minerals are mixed with titanium middlings for mixed grinding to obtain titanium middling slurry; a binary mixed collector is prepared: first, unsaturated fatty acid collectors and hydroxamic acid collectors are uniformly mixed according to a mass ratio of 10:1-20:1, and a water solution is added to prepare the binary mixed collector; desulfurization is carried out to obtain sulfur concentrate and desulfurization tailings; intensified flotation is carried out: the desulfurization tailings are coarsely selected to obtain coarse concentrate and coarse tailings; the coarse concentrate is subjected to 1-2 times of concentration to obtain titanium concentrate and middlings; the coarse tailings are subjected to 2-3 times of scavenging to obtain middlings and tailings; the middlings in the selection process are returned to the previous operation to form a closed-circuit flotation system. The method can effectively further prepare high-quality titanium concentrate from titanium middlings, and ensures a high recovery rate.

Description

TECHNICAL FIELD

[0001] The application relates to a physical and chemical coupling reinforced upgrading method for titanium ore, and belongs to the technical field of titanium ore beneficiation. BACKGROUND

[0002] Titanium metal has excellent properties such as silver-white metal luster, high strength and strong corrosion resistance, and is widely used in the fields of aviation, medical treatment, construction and the like. Titanium metal is mainly extracted from two minerals, i.e., rutile and ilmenite. Rutile contains relatively pure titanium dioxide, and is therefore widely used as the primary extraction object of titanium metal. However, the natural rutile resource is increasingly exhausted, and ilmenite has become the main source of extracting titanium. The ilmenite reserves in China are 200 million tons, accounting for 28% of the global reserves. According to the ore-forming process of ilmenite, the ilmenite is mainly divided into two types, i.e., rock ilmenite and placer ilmenite.

[0003] The rock ilmenite is a magmatic-hydrothermal type titanium deposit related to intrusive rocks, and mainly exists in the form of blocks. In the industrial separation process, the ilmenite is recovered by crushing and grinding to a certain particle size, then weak magnetic separation of iron, and finally strong magnetic separation-flotation of the tailings of the iron separation. In this separation process, although the +38 mu m particle size ilmenite has a certain recovery effect, due to the low grade of the rock ilmenite ore, the ore needs to be fully dissociated, and the recovery rate of the fine ilmenite is low, causing the waste of titanium resources. The placer ilmenite has a loose structure and exists in the form of particles. In the industrial separation process, the weak magnetic-strong magnetic-spiral chute separation process is adopted. In this separation process, although the ilmenite concentrate with high grade can be obtained, the recovery rate is low, and part of the ilmenite is lost in the tailings.

[0004] To recover ilmenite more effectively, patent CN.116116564A adds a collector hydroxamic acid to the spiral classification return sand product, and then enters the grinding machine for grinding operation. The titanium concentrate obtained by flotation of the grinding product has a titanium dioxide grade that is 0.08% to 0.5% higher than that of the titanium concentrate obtained by directly adding hydroxamic acid in the flotation operation, and the recovery rate is increased by 25.14% to 25.61%. However, a large amount of hydroxamic acid is used, which is high in cost and pollutes water bodies. Patent CN.111468286A adds lead nitrate as an activator for mixing and slurry preparation, and then performs conventional flotation of one roughing and three cleaning to obtain a titanium concentrate with a titanium dioxide grade of 47.06% to 47.31% and a recovery rate of 47.64% to 59.33%. However, the residual lead ions in the flotation wastewater can harm human health and the environment. Patent CN.110433965A uses an activator composed of lead nitrate, potassium permanganate and sodium hypochlorite in a specific ratio to enhance the adsorption of the collector on the surface of ilmenite through combined action of the activator. The titanium concentrate obtained has a titanium dioxide grade that is 4% to 7% higher than that of the titanium concentrate treated with lead nitrate alone, and the recovery rate is increased by 6% to 8%. However, the complex types of flotation reagents result in a complex chemical environment in water bodies, which has great potential harm and high cost for post-treatment.

[0005] Therefore, it is a technical problem for those skilled in the art to provide a green and efficient method for strengthening ilmenite flotation. SUMMARY

[0006] In view of the problems and deficiencies of the prior art, the present application provides a physical and chemical coupling method for strengthening and upgrading titanium middlings. The method can effectively prepare high-quality titanium concentrate from titanium middlings and ensure a high recovery rate.

[0007] The present application is achieved by the following technical solutions:

[0008] A physical and chemical coupling method for strengthening and upgrading titanium middlings, comprising the following steps:

[0009] (1) Co-grinding: Manganese-containing minerals are added to the titanium middlings for mixed grinding to obtain a titanium middlings slurry with a-74um content of 85% to 95%;

[0010] (2) Preparation of binary mixed collector: First, unsaturated fatty acid collector and hydroxamic acid collector are uniformly mixed in a mass ratio of 10:1 to 20:1, water is added, and the mixture is allowed to react at a temperature of 25 to 80°C for 2 to 5 hours to prepare a binary mixed collector with a concentration of 20wt.% to 40wt.%;

[0011] (3) Desulfurization: Sulfuric acid, butyl xanthate and 2 #Oil, each role 2~5min after the flotation operation, get sulfur concentrate and desulfurization tailings;

[0012] (4) Intensified flotation: the desulfurization tailings obtained in step (3) are subjected to roughing to obtain rough concentrate and rough tailings, wherein 250g / t~600g / t gangue mineral inhibitor, 300g / t~900g / t new type of binary collector, and 30g / t~60g / t foaming agent are added in the roughing process, and each reagent is added for 3~5min; the rough concentrate is subjected to 1~2 times of cleaning to obtain titanium concentrate and middlings; the rough tailings are subjected to 2~3 times of scavenging to obtain middlings and tailings; the middlings in the beneficiation process are returned to the previous operation to form the entire closed-circuit flotation system.

[0013] The manganese-containing mineral is a certain proportion of one or more of rhodochrosite, manganite and pyrolusite.

[0014] The average grade of titanium dioxide in the titanium middlings is 15~22wt.%, and the mass ratio of manganese-containing mineral to titanium middlings is 1:100~1:25.

[0015] The mixed grinding mode adopts rod grinding or ball grinding.

[0016] The concentration of the titanium middlings grinding ore slurry is 40~60wt.%.

[0017] The unsaturated fatty acid collector has 12~20 carbon atoms; the hydroxamic acid collector is a hydroxamic acid compound containing a carbonyl group or both a carbonyl group and an oxime group. The new type of binary mixed collector has excellent selective collecting capacity for ilmenite and can also flocculate fine ilmenite to a certain extent. The new type of binary mixed collector has strong surface activity, good foaming performance, and also affects the gas-liquid interface surface activity and the flotation foam characteristics, and has excellent collecting performance.

[0018] The gangue mineral inhibitor is acidified water glass or carboxymethyl starch. The acidified water glass is prepared by mixing water glass and oxalic acid at a mass ratio of 3:1.

[0019] The reagent dosage of the cleaning and scavenging operations is reduced by 1 / 8~1 / 2 compared with the previous operation.

[0020] When the sulfur content in the titanium middlings is less than 0.1wt.%, desulfurization treatment is not needed, and the co-ground product directly enters the intensified flotation process.

[0021] The titanium concentrate obtained above has a titanium dioxide grade of 42wt.%~49wt.% and a recovery rate of 70%~85%.

[0022] The specific technical principle of the present application is as follows:

[0023] The application provides a physical-chemical coupling reinforced upgrading method for titanium ore, which mainly comprises a physical grinding process and a flotation surface chemical regulation process. Figure 1

[0024]

[0025] Under the action of the above mechanism, the physical-chemical coupling reinforced upgrading method can effectively improve the flotation recovery effect of ilmenite.

[0026] Compared with the traditional flotation reagent system and the existing process flow, the method has the following advantages:

[0027] 1. The manganese-containing mineral is co-ground with the ilmenite ore, and in the co-grinding process, the ion intensity of the slurry is increased due to the existence of free manganese ions and hydroxyl manganese ions, the mutual restraint effect between ions is enhanced, the metal ions such as Fe 2+ , Ti 4+ and OH- in the slurry are surrounded and separated by free ions, the combination to form Fe(OH)2 and Ti(OH)4 is reduced, the original dissolution equilibrium is destroyed, and only the dissolution of the mineral surface can reach a new balance, so that the ilmenite surface appears redissolution phenomenon. The exposed fresh ilmenite surface increases the number of Ti-O-Ti / Fe active sites on the ilmenite surface, thereby increasing the adsorption of the collector on the ilmenite surface and enhancing the floatability of the ilmenite.

[0028] 2. A small amount of manganese-containing mineral is co-ground with the ilmenite ore, and in the co-grinding process, part of the manganese atoms in the manganese-containing mineral are converted into free manganese ions in the mechanical grinding process, and the part of the manganese ions selectively adsorb on the surface of the ilmenite and act as a new active site on the surface of the ilmenite, thereby increasing the adsorption of the collector on the surface of the ilmenite and improving the flotation performance of the ilmenite.​

[0029] 3. The titanium, iron, and manganese ions present in the co-ground slurry can be combined with the free titanium, iron, and manganese ions in the slurry to form stable complex collectors, which have stronger adsorption stability on the surface of ilmenite, greatly improving the flotation efficiency of ilmenite.

[0030] 4. The novel binary collector used has excellent foaming properties and low foam viscosity, reducing gangue minerals entrained in the foam product and making it more conducive to subsequent processing such as filtration and dehydration. Furthermore, it also possesses excellent stability and strong collecting ability. Attached Figure Description

[0031] Figure 1 This is a schematic diagram illustrating the principle of the present invention;

[0032] Figure 2 This is a schematic diagram of the process of this invention. Detailed Implementation

[0033] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0034] Example 1

[0035] like Figure 2 As shown, an experimental study was conducted on a weathered ilmenite pre-enriched concentrate. Analysis revealed that the TiO2 grade of the concentrate was 15.66 wt.%, the S content (an impurity element) was 0.06 wt.%, and the main gangue minerals were kaolinite, feldspar, and pyroxene. The specific implementation method is as follows:

[0036] (1) Co-grinding: Manganese-containing minerals and titanium middlings are mixed and ground. The manganese-containing minerals are composed of pyrolusite and rhodochrosite in a mass ratio of 1:1. The mass ratio of manganese-containing minerals to titanium middlings is 1.2:100, and a slurry with a mineral particle size of -74um accounting for 90% is obtained.

[0037] (2) Preparation of binary mixed collector: Sodium oleate and benzoic acid were mixed uniformly at a mass ratio of 10:1, and an aqueous solution was added. The mixture was reacted at 30°C for 2.5 h to prepare a binary mixed collector with a concentration of 30 wt.%.

[0038] (3) Enhanced flotation: The titanium middlings slurry obtained in step (1) is subjected to roughing to obtain rough concentrate and rough tailings. During the roughing process, 450 g / t gangue mineral inhibitor carboxymethyl starch, 500 g / t novel binary collector, and 40 g / t frother are added sequentially. #Oil, sequentially for 3 min, 4 min and 1 min, and then rough selection; then, fine selection I, II, and scavenging I, II, the amount of reagent of scavenging I is reduced by 1 / 2 than that of rough selection, the amount of reagent of scavenging II is reduced by 1 / 4 than that of scavenging I, the amount of reagent of fine selection I is reduced by 1 / 4 than that of rough selection, the amount of reagent of fine selection II is reduced by 1 / 8 than that of fine selection I, the middlings are returned to the previous selection according to the order to form a closed-circuit flotation, and the flotation concentrate and tailings are obtained; the middlings in the selection process are returned to the previous operation to form a closed-circuit flotation system.

[0039] In the embodiment, the flotation concentrate has a titanium dioxide grade of 41.57% and a recovery rate of 75.12%.

[0040] In addition, under the same conditions, the manganese-containing mineral is not used for co-milling with the raw ore, a comparative experiment is performed, and a flotation concentrate with a TiO2 grade of 38.28% and an operation recovery rate of 71.33% is obtained. It is found through comparison of the two methods that after the manganese-containing mineral is used for co-milling with the raw ore, the TiO2 grade and the recovery rate of the ilmenite concentrate obtained through flotation are increased by 3.29% and 3.79%, respectively.

[0041] Table 1: Flotation test results of weathered ilmenite pre-concentration concentrate

[0042]

[0043] Comparative Example 1

[0044] The binary mixed collector is replaced by the same amount of sodium oleate, and the beneficiation experiment is performed under the same conditions as in Example 1, and the flotation concentrate grade and recovery rate obtained are shown in Table 2.

[0045] Comparative Example 2

[0046] The binary mixed collector is replaced by the same amount of benzohydroxamic acid, and the beneficiation experiment is performed under the same conditions as in Example 1, and the flotation concentrate grade and recovery rate obtained are shown in Table 2.

[0047] Table 2: Flotation test results of different collector systems under co-milling conditions

[0048]

[0049]

[0050] As can be seen from Table 2, the binary collector is used and the manganese-containing mineral is co-milled, the flotation concentrate has a higher titanium dioxide grade and a better recovery rate.

[0051] Example 2

[0052] As Figure 2As shown, an experimental study was conducted on a pre-enriched ilmenite concentrate from olivine pyroxene. Analysis revealed that the TiO2 grade of this concentrate was 17.78 wt.%, and the sulfur content was 0.61 wt.%. The main gangue minerals in this ore are pyroxene, chlorite, and serpentine. The specific implementation method is as follows:

[0053] (1) Co-grinding: Manganese-containing minerals and titanium middlings are mixed and ground. The manganese-containing minerals are composed of pyrolusite and rhodochrosite in a mass ratio of 1:2. The mass ratio of manganese-containing minerals to titanium middlings is 1.5:100, and a slurry with a mineral particle size of -74um accounting for 86wt.% is obtained.

[0054] (2) Preparation of binary mixed collector: Sodium oleate and salicylic acid were mixed uniformly at a mass ratio of 12:1, and an aqueous solution was added. The mixture was reacted at a temperature of 25℃ for 3 hours to prepare a binary mixed collector with a concentration of 30wt.%.

[0055] (3) Desulfurization:

[0056] In step (1), sulfuric acid (75 wt.% sulfuric acid solution concentration, 10 g / t), 400 g / t butyl xanthate, and 30 g / t 2 g / t butyl xanthate were added sequentially to the titanium middlings ore slurry. # The oil was treated with sulfuric acid (75 wt.%) to adjust the pH to 4.0. After each treatment for 1 min, 3 min, and 1 min, flotation desulfurization was started to obtain sulfur concentrate and desulfurized tailings. The titanium dioxide grade in the desulfurized tailings was 18.02 wt.%.

[0057] (4) Enhanced flotation: The desulfurized tailings obtained in step (3) are subjected to roughing to obtain rough concentrate and rough tailings. During the roughing process, 500g / t gangue mineral inhibitor acidified water glass, 600g / t novel binary collector, and 50g / t frother are added sequentially. # Oil is applied sequentially for 3 minutes, 4 minutes, and 1 minute for roughing; then cleaning operations I and II and scavenging operations I and II are performed. The reagent dosage for scavenging operation I is reduced by 1 / 4 compared to roughing, the reagent dosage for scavenging operation II is reduced by 1 / 8 compared to scavenging operation I, the reagent dosage for cleaning operation I is reduced by 1 / 4 compared to roughing, and the reagent dosage for cleaning operation II is reduced by 1 / 8 compared to cleaning operation I. The middlings are returned to the previous stage of the beneficiation operation in sequence to form a closed-circuit flotation system, obtaining flotation concentrate and tailings. The middlings in the beneficiation process are returned to the previous stage of the operation to form a closed-circuit flotation system.

[0058] In this embodiment, the titanium dioxide grade of the flotation concentrate is 42.83%, and the recovery rate is 74.03%.

[0059] In addition, under the same conditions, without using manganese-containing minerals for co-milling with the raw ore, a comparative experiment was conducted to obtain a flotation concentrate with a Ti02 grade of 39.29% and an operation recovery rate of 70.64%. Comparison of the two methods found that after using manganese-containing minerals for co-milling with the raw ore, the Ti02 grade and recovery rate of the ilmenite concentrate obtained by flotation were increased by 3.54% and 3.39%, respectively.

[0060] Table 3 Experimental results of flotation of pre-concentration concentrate of garnet rock ilmenite

[0061]

[0062] Comparative Example 3

[0063] The binary mixed collector was replaced with an equivalent amount of sodium oleate, and the beneficiation experiment was conducted under the same conditions as Example 2, and the Ti02 grade and recovery rate of the flotation concentrate obtained are shown in Table 4.

[0064] Comparative Example 4

[0065] The binary mixed collector was replaced with an equivalent amount of salicylhydroxamic acid, and the beneficiation experiment was conducted under the same conditions as Example 2, and the Ti02 grade and recovery rate of the flotation concentrate obtained are shown in Table 4.

[0066] Table 4 Experimental results of flotation under co-milling conditions with different collector systems

[0067]

[0068] As can be seen from Table 4, using a binary collector and simultaneously adding manganese-containing minerals for co-milling, the Ti02 grade of the flotation concentrate is higher, and the recovery rate is better.

[0069] Example 3

[0070] As shown in Table 3, an experimental study was conducted on the pre-concentration concentrate of semi-weathered ilmenite, and the test analysis showed that the Ti02 grade of the concentrate was 18.35wt.%, the content of impurity element S was 0.04wt.%, and the main gangue minerals were kaolinite and feldspar. The specific implementation method is as follows: Figure 2

[0071] (1) Co-milling: The manganese-containing minerals were mixed with the titanium concentrate for grinding, the manganese-containing minerals were composed of romanechite and rhodochrosite with a mass ratio of 2:1, and the mass ratio of manganese-containing minerals to titanium concentrate was 1:100, and a slurry with a mineral particle size of-74um accounting for 88% was obtained;

[0072] (2) Preparation of binary mixed collector: sodium oleate and benzylhydroxamic acid were uniformly mixed according to a mass ratio of 12:1, and water was added, and under the condition of a temperature of 30℃, the action lasted for 3h, and a binary mixed collector with a concentration of 35wt.% was prepared; ​

[0073] (3) Intensified flotation: roughing of the titanium middling slurry obtained in step (1) to obtain a rough concentrate and a rough tailing, wherein 400 g / t of gangue mineral depressant acidified water glass, 600 g / t of a new type of binary collector, and 30 g / t of a frother 2 are sequentially added in the roughing process # oil, sequentially acting for 3 min, 4 min, and 1 min, and then roughing; and then cleaning I and II operations and scavenging I and II operations, the reagent dosage of scavenging I being reduced by 1 / 2 compared with that of the roughing, the reagent dosage of scavenging II being reduced by 1 / 2 compared with that of the scavenging I, the reagent dosage of cleaning I being reduced by 1 / 6 compared with that of the roughing, the reagent dosage of cleaning II being reduced by 1 / 8 compared with that of the cleaning I, the middling being returned to the previous operation in sequence to form a closed-circuit flotation, and a flotation concentrate and a tailing being obtained; the middling in the operation is returned to the previous operation to form a closed-circuit flotation system.

[0074] In this embodiment, the flotation concentrate has a titanium dioxide grade of 43.88 wt.%, and a recovery rate of 72.44%.

[0075] In addition, under the same conditions, no manganese-containing minerals are used for co-milling with the raw ore, a comparative experiment is performed, a flotation concentrate with a TiO2 grade of 40.66% and an operation recovery rate of 69.71% is obtained. It is found by comparing the two methods that after using manganese-containing minerals for co-milling with the raw ore, the TiO2 grade and the recovery rate of the ilmenite concentrate recovered by flotation are increased by 3.22% and 2.73%, respectively.

[0076] Table 5: Flotation test results of semi-weathered ilmenite pre-concentration concentrate

[0077]

[0078] Comparative Example 5

[0079] The binary mixed collector is replaced with the same amount of sodium oleate, and the beneficiation experiment is performed under the same conditions as in Example 3, and the flotation concentrate grade and recovery rate obtained are shown in Table 6.

[0080] Comparative Example 6

[0081] The binary mixed collector is replaced with the same amount of benzohydroxamic acid, and the beneficiation experiment is performed under the same conditions as in Example 3, and the flotation concentrate grade and recovery rate obtained are shown in Table 6.

[0082] Table 6: Flotation test results of different collector systems under co-milling conditions

[0083]

[0084] As can be seen from Table 6, using a binary collector and simultaneously adding manganese-containing mineral slurry for co-milling, the flotation concentrate has a higher titanium dioxide grade and a better recovery rate.

[0085] The above detailed description of the application has been given with reference to specific embodiments thereof, but it is not intended to limit the application to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the application.

Claims

1. A physical-chemical coupling strengthening and upgrading method for titanium middlings, characterized in that The steps include the following: (1) Co-grinding: the manganese-containing mineral is added to the titanium middlings for mixing and grinding to obtain a titanium middlings slurry with a-74um content of 85% to 95%; The mass ratio of the manganese-containing mineral to the titanium middlings is 1:100 to 1:25; (2) Preparation of a binary mixed collector: first, an unsaturated fatty acid collector and a hydroxamic acid collector are uniformly mixed at a mass ratio of 10:1 to 20:1, and then a water solution is added, and the mixture is reacted at a temperature of 25 to 80℃ for 2 to 5 hours to prepare a binary mixed collector with a concentration of 20wt.% to 40wt.%; (3) Desulfurization: sulfuric acid, butyl xanthate and 2 # oil are added into the titanium middlings slurry obtained in step (1) in turn, and after each of them acts for 2-5 min, a flotation operation is performed to obtain a sulfur concentrate and a desulfurized tailing; (4) Intensified flotation: the desulfurization tailings obtained in step (3) are subjected to roughing to obtain a rough concentrate and a rough tailings, wherein 250g / t to 600g / t of a gangue mineral depressant, 300g / t to 900g / t of a new binary collector, and 30g / t to 60g / t of a frother are sequentially added in the roughing process, and the various reagents are allowed to act for 3 to 5 minutes after being added; the rough concentrate is subjected to 1 to 2 times of cleaning to obtain a titanium concentrate and a middlings; the rough tailings are subjected to 2 to 3 times of scavenging to obtain a middlings and a tailings; the middlings in the beneficiation process are returned to the previous operation to form a closed-circuit flotation system.

2. The physical-chemical coupling enhanced upgrading method of titanium middlings according to claim 1, characterized in that: The manganese-containing mineral is one or a mixture of any ratio of rhodochrosite, manganite and pyrolusite.

3. The physical-chemical coupling enhanced upgrading method of titanium middlings according to claim 1, characterized in that: The average grade of titanium dioxide in the titanium middlings is 15 to 22wt.%.

4. The physical-chemical coupling enhanced upgrading method of titanium middlings according to claim 1, characterized in that: The co-grinding method is rod milling or ball milling.

5. The physical-chemical coupling enhanced upgrading method of titanium middlings according to claim 1, characterized in that: The concentration of the titanium middlings grinding slurry is 40 to 60wt.%.

6. The physical-chemical coupling enhanced upgrading method of titanium middlings according to claim 1, characterized in that: The unsaturated fatty acid collector has 12 to 20 carbon atoms; the hydroxamic acid collector is a hydroxamic acid compound containing a carbonyl group or both a carbonyl group and a hydroxyl group.

7. The physical-chemical coupling intensified upgrading method of titanium middlings according to claim 1, characterized in that: The gangue mineral depressant is acidified water glass or carboxymethyl starch.

8. The physical-chemical coupling intensified upgrading method of titanium middlings according to claim 1, characterized in that: The reagent dosage for the cleaning and scavenging operations is reduced by 1 / 8 to 1 / 2 compared with the previous operation.

9. The physical-chemical coupling intensified upgrading method of titanium middlings according to claim 1, characterized in that: When the sulfur content in the titanium middlings is less than 0.1wt.%, desulfurization treatment is not required, and the co-ground product directly enters the intensified flotation process.

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