Methods for the efficient recovery of zirconium, hafnium, and titanium from paleoriver-lacustrine zirconium-hafnium placer deposits

Abstract

This disclosure relates to the field of mineral processing technology and provides a method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zircon-hafnium placer deposits. The method includes: pre-treating the paleoriver-lacustrine zircon-hafnium placer ore, performing gravity separation pre-enrichment, grinding, desulfurization flotation, weak magnetic separation, and strong magnetic separation to obtain strong magnetic separation concentrate and strong magnetic separation tailings; performing gravity separation on the strong magnetic separation tailings to obtain zirconium-hafnium concentrate and gravity-separated zirconium-hafnium tailings; classifying the strong magnetic separation concentrate to obtain coarse-grained concentrate and fine-grained concentrate; performing coarse-grained gravity separation on the coarse-grained concentrate to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings; performing fine-grained strong magnetic separation on the fine-grained concentrate to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings; and combining the gravity-separated titanium pre-enriched concentrate and the magnetically separated titanium pre-enriched concentrate for titanium flotation to obtain ilmenite concentrate and titanium flotation tailings. The method disclosed herein enables the synergistic enrichment and efficient recovery of zirconium, hafnium, and titanium in novel paleofluvial lacustrine zircon-hafnium placer deposits.

Description

Technical Field

[0001] This disclosure relates to the field of mineral processing technology, for example to a method for the efficient recovery of zirconium, hafnium, and titanium from paleofluvial lacustrine zirconium-hafnium placer deposits. Background Technology

[0002] Zirconium, hafnium, and titanium are widely used in core fields such as nuclear energy and aerospace. Zirconium is widely used in various industries including modern ceramics, specialty glass, nuclear energy, chemicals, precision casting, and medicine; among them, nuclear-grade sponge zirconium is a key basic material in nuclear reactors and is known in the nuclear industry as the "number one metal of the atomic age." Hafnium is a strategic mineral related to national defense security, used in the control rods and protection devices of nuclear reactors in the nuclear energy industry, and is irreplaceable in the nuclear energy industry. Titanium is an important raw material for the military and aerospace fields. Most ilmenite is mainly used to produce titanium dioxide, and its end products are used in traditional industries such as chemicals, power, and metallurgy, while a small portion of ilmenite is used to produce titanium materials.

[0005] China has a diverse range of zircon deposits, which have been identified as two main categories: endogenic and exogenic. Endogenic deposits mainly include alkaline rock type, alkaline granite type, pegmatite type, and granulite type; exogenic deposits are mainly coastal sedimentary type, fluvial alluvial type, and weathering crust type.

[0006] Furthermore, in their article "The Discovery of Paleofluvial-Lumpal Zircon Sand Deposits on the Northern Edge of the Kubai Basin in Xinjiang Achieves a Breakthrough in Zircon Exploration in my country," Liu Bing et al. pointed out that the Yuhai Zircon Sand Deposit, a Paleofluvial-Lumpal Zircon Sand Deposit with super-large-scale potential, was discovered in the Cenozoic strata on the northern edge of the Kubai Basin. This discovery significantly increases China's zircon reserves and plays a positive role in alleviating dependence on foreign zircon resources. More importantly, the successful identification of this deposit provides new strategic ideas and exploration directions for zircon resource exploration in China and even globally. However, the Paleofluvial-Lumpal Zircon Sand Deposit discovered by Liu Bing et al. is a newly discovered type of deposit. Research on the efficient enrichment of zircon of this type is only in the exploratory stage. Moreover, the combined process of "grinding-gravity separation-roughing-cleaning-re-selection-two-stage magnetic separation" mentioned in the article only provides a preliminary exploration of zircon in the ore. It cannot comprehensively recover titanium, nor can it achieve the synergistic enrichment and efficient recovery of zircon, hafnium, and titanium in the ore.

[0007] In conclusion, developing methods for the synergistic enrichment and efficient recovery of zirconium, hafnium, and titanium in newly discovered paleofluvial lacustrine zirconium-hafnium placer deposits is of great significance for supporting the comprehensive development and evaluation of this type of mine. Summary of the Invention

[0008] The purpose of this disclosure is to overcome the shortcomings of the prior art and provide a method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zirconium-hafnium placer deposits. This method aims to at least achieve the efficient and synergistic enrichment of zirconium, hafnium, and titanium from new types of paleoriver-lacustrine zirconium-hafnium placer deposits, and to obtain high-grade and high-recovery zirconium-hafnium concentrate and ilmenite concentrate, thereby significantly improving the utilization rate of zirconium, hafnium, and titanium in the ore.

[0009] The purpose of this disclosure is achieved through the following technical solution: On the one hand, a method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zircon-hafnium placer deposits is provided. The method includes: pre-treating the paleoriver-lacustrine zircon-hafnium placer ore to liberate it, obtaining pre-treated minerals; subjecting the pre-treated minerals to gravity separation pre-enrichment, obtaining gravity separation pre-enrichment concentrate and gravity separation pre-enrichment tailings; grinding the gravity separation pre-enrichment concentrate to obtain grinding products; subjecting the grinding products to desulfurization flotation to obtain sulfide mineral concentrate and desulfurization tailings; subjecting the desulfurization tailings to weak magnetic separation to obtain weak magnetic separation concentrate and weak magnetic separation tailings; subjecting the weak magnetic separation tailings to strong magnetic separation to obtain strong magnetic separation concentrate and strong magnetic separation tailings; and further processing the strong magnetic separation tailings... The process involves gravity separation to obtain zirconium-hafnium concentrate and gravity-separated zirconium-hafnium tailings; classification of the high-intensity magnetic separation concentrate to obtain coarse-grained concentrate and fine-grained concentrate; coarse-grained concentrate undergoing coarse-grained gravity separation to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings; fine-grained concentrate undergoing fine-grained high-intensity magnetic separation to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings; merging the gravity-separated titanium pre-enriched concentrate and the magnetically separated titanium pre-enriched concentrate to obtain titanium pre-enriched concentrate; and titanium pre-enriched concentrate undergoing titanium flotation to obtain ilmenite concentrate and titanium flotation tailings.

[0010] In some examples, the method further includes: merging the gravity separation pre-enriched tailings, the sulfide mineral concentrate, the weak magnetic separation concentrate, the gravity separation titanium pre-enriched tailings, the magnetic separation titanium pre-enriched tailings, and the titanium flotation tailings into a final tailings.

[0011] In some embodiments, in the paleofluvial lacustrine zirconium-hafnium placer ore, the grade of ZrO2 is not less than 0.15%, the grade of HfO2 is not less than 25ppm, and the grade of TiO2 is not less than 0.3%.

[0012] It should be noted that the paleofluvial-lacustrine zircon-hafnium placer ore (i.e., the paleofluvial-lacustrine zircon-hafnium placer ore) is hosted in Cenozoic strata and distributed in Tertiary sedimentary strata. It is generally developed into various sedimentary facies such as piedmont alluvial-diluvial, fan delta, delta, and lacustrine. The ore is semi-consolidated sandstone and conglomerate, and the main rock assemblage is fine sandstone and conglomerate. The contents of zirconium, hafnium, and titanium in the fine sandstone and conglomerate are not significantly different. Compared with other types of deposits, the mineral composition of the paleofluvial-lacustrine zircon-hafnium placer ore is relatively simple and the grain size composition is relatively uniform. However, the grain size distribution of this type of deposit is uneven, with contents of each grain size. Moreover, the intercalation characteristics of zirconium, hafnium, titanium, and gangue minerals in each grain size of ore are complex, making separation and purification difficult.

[0013] The main mineral composition and physical properties of the paleofluvial lacustrine zirconium-hafnium placer deposits are as follows: Zircon is non-magnetic, with a hardness of 7.5-8, is brittle, and a specific gravity of 4.4-4.8 (3.6-4.0 for isotropic forms); Ilmenite is weakly magnetic, brittle, with a hardness of 5-5.5 and a density of 4.4-5 g / cm³. 3 Specific gravity 4.70~4.78; magnetite, strongly magnetic, Mohs hardness 5.5~6, density 5.16~5.18 g / cm³ 3 Specific gravity 4.8~5.3; Pyrrhotite, possessing electrical and magnetic properties, brittle, Mohs hardness 3.5~4.5, density 4.58~4.79 g / cm³ 3 Specific gravity 4.6~4.7; pyrite, brittle, Mohs hardness 6~6.5, density 5g / cm³ 3 Specific gravity 4.9~5.2; goethite, hardness 1~5.5, specific gravity 3.3~4.0; hematite, brittle, Mohs hardness 5.5~6.5, specific gravity 4.9~5.3; quartz, non-magnetic, Mohs hardness 7, brittle, density 2.65g / cm³, specific gravity 2.65; feldspar, non-magnetic, Mohs hardness 6~6.5, brittle, density 2.55~2.76g / cm³, specific gravity 2.55~2.76; illite, non-magnetic, Mohs hardness 1~2, specific gravity 2.6~2.9; calcite, non-magnetic, Mohs hardness 3, specific gravity 2.6~2.8.

[0014] It is worth noting that the method provided in this disclosure can efficiently and synergistically enrich zirconium, hafnium, and titanium, and obtain high-grade and high-recovery zirconium-hafnium concentrate and ilmenite concentrate, thereby achieving efficient and comprehensive recovery of zirconium, hafnium, and titanium in the new type of paleofluvial lacustrine zirconium-hafnium placer deposit.

[0015] The principle of the method provided in this disclosure includes: 1) By performing the pretreatment on the ancient river-lacustrine zircon-hafnium placer ore to liberate the high-density minerals and gangue minerals in the ore, and then removing most of the quartz, feldspar, calcite, illite and other minerals in the ore through the gravity separation pre-enrichment, the gravity separation pre-enrichment concentrate containing mainly high-density minerals such as zircon, ilmenite, argillaceous manganese ore, magnetite, pyrite, pyrrhotite and other high-density minerals is obtained; 2) By grinding the gravity separation pre-enriched concentrate to liberate high-density minerals such as zircon, ilmenite, argillaceous manganese ore, magnetite, pyrrhotite, and pyrite in the ore, and then removing sulfur-containing minerals from the ore by the desulfurization flotation, the sulfide mineral concentrate (e.g., pyrrhotite, pyrite, etc.) and the desulfurization tailings (e.g., zircon, ilmenite, magnetite, etc.) are obtained. 3) First, utilizing the differences in the magnetoelectric properties of minerals, the desulfurization tailings are subjected to weak magnetic separation to remove strongly magnetic minerals from the ore, yielding weak magnetic separation concentrate (mainly magnetite, etc.) and weak magnetic separation tailings (mainly zircon, ilmenite, argillaceous manganese ore, and small amounts of quartz, feldspar, etc.); second, utilizing the differences in the magnetic properties of minerals, the weak magnetic separation tailings are subjected to strong magnetic separation to separate the weakly magnetic minerals from the non-magnetic minerals in the ore, yielding strong magnetic separation concentrate (mainly ilmenite, argillaceous manganese ore, and small amounts of quartz, feldspar, etc.) and strong magnetic separation tailings (mainly zircon, quartz, feldspar, etc.); then, utilizing the differences in the specific gravity and particle size of the ore, the strong magnetic separation tailings are subjected to gravity separation to obtain zirconium-hafnium concentrate and gravity-separated zirconium-hafnium tailings; 4) First, the strong magnetic separation concentrate is classified to obtain the coarse-grained concentrate and the fine-grained concentrate; second, based on the differences in specific gravity and particle size between ilmenite, rhodochrosite, and quartz and feldspar, the coarse-grained concentrate is subjected to coarse-grained gravity separation to enrich the coarse-grained ilmenite and rhodochrosite in the ore, resulting in the gravity separation titanium pre-enriched concentrate and the gravity separation titanium pre-enriched tailings; then, based on the differences in specific gravity between ilmenite, rhodochrosite, and quartz and feldspar, etc. The difference in magnetic properties allows for the enrichment of fine-grained ilmenite and rutile manganese ore in the fine-grained concentrate through fine-grained strong magnetic separation, resulting in the magnetically separated titanium pre-enriched concentrate and the magnetically separated titanium pre-enriched tailings. This achieves the separation of ilmenite and rutile manganese ore from gangue minerals such as quartz and feldspar. Finally, the obtained gravity-separated titanium pre-enriched concentrate and the magnetically separated titanium pre-enriched concentrate are combined for titanium flotation to obtain the ilmenite concentrate and titanium flotation tailings.

[0016] In some embodiments, the pretreatment of paleofluvial lacustrine zirconium-hafnium placer ore to liberate it and obtain pretreated minerals includes: crushing the paleofluvial lacustrine zirconium-hafnium placer ore to obtain crushed minerals; pre-sorting and classifying the crushed minerals to obtain oversize and undersize minerals; and pre-grinding the oversize minerals to obtain pre-ground mineral products. The pre-ground mineral products are returned to the pre-sorting and classification process; and the undersize minerals are used as the pretreated minerals.

[0017] In some examples, the particle size of the crushed mineral is -3 mm.

[0018] In some examples, the particle size of the undersize mineral is -0.5 mm, and the particle size of the pre-ground mineral product is -0.5 mm.

[0019] It should be understood that the paleofluvial-lacustrine zirconium-hafnium placer deposits are hosted in Cenozoic strata, with the main rock assemblage consisting of fine sandstone and conglomerate, and the clastic material is generally not well sorted. Among them, the fine sandstone has small grains and a high degree of liberation between heavy minerals and gangue minerals; while the conglomerate has large grains, and the heavy minerals and gangue minerals have not been effectively liberated, making it difficult for physical beneficiation methods to separate the heavy minerals from the gangue minerals.

[0020] Based on this, in some of the above embodiments, by first performing the pre-selection and classification on the crushed minerals, and then pre-grinding the minerals on the sieve, it is possible to ensure that the high-density minerals and gangue minerals in the conglomerate are effectively liberated, while further preventing the already liberated fine sandstone from being ground again, thereby further improving the subsequent separation effect of high-density minerals and gangue minerals.

[0021] In some embodiments, the pre-concentration of the pretreated minerals to obtain pre-concentrated gravity concentrate and pre-concentrated gravity tailings includes: particle size classification of the pretreated minerals to obtain coarse-grained minerals and fine-grained minerals; coarse-grained gravity pre-concentration of the coarse-grained minerals to obtain coarse-grained gravity concentrate and coarse-grained gravity tailings; and fine-grained gravity pre-concentration of the fine-grained minerals to obtain fine-grained gravity concentrate and fine-grained gravity tailings. Specifically, the coarse-grained gravity concentrate and the fine-grained gravity concentrate are combined to form the pre-concentrated gravity concentrate; and the coarse-grained gravity tailings and the fine-grained gravity tailings are combined to form the pre-concentrated gravity tailings.

[0022] In some examples, the fine-grained minerals have a particle size of -0.074 mm.

[0023] In some of the above embodiments, by first performing particle size classification on the pretreated minerals, and then performing coarse-grained gravity separation pre-enrichment and fine-grained gravity separation pre-enrichment on the obtained coarse-grained minerals and fine-grained minerals respectively, it is possible to utilize the differences in ore specific gravity and further utilize the differences in ore particle size, thereby further improving the removal effect of minerals such as quartz, feldspar, calcite, and illite in the ore.

[0024] In some embodiments, the method further includes returning the reseparated zirconium hafnium tailings to the particle size classification.

[0025] In some embodiments, the weight percentage of minerals with a particle size of -0.074 mm in the grinding product is 40% to 60%.

[0026] It should be noted that "the weight percentage of minerals with a particle size of -0.074mm in the grinding product is 40%~60%" can also be understood as "the fineness of the grinding is -0.074mm 40%~60%", and the two have the same meaning.

[0027] It is understood that the purpose of the desulfurization flotation is to remove sulfur-containing minerals from the grinding products. In order to achieve the above purpose, a variety of reagents and methods can be used, and those skilled in the art can make appropriate selections according to actual needs. This disclosure does not limit them.

[0028] In some examples, the reagents used in the desulfurization flotation include sulfide mineral collectors and frothers.

[0029] For example, the sulfide mineral collector includes at least one of butyl xanthate, bixanthate, butylamine black powder, and biblack powder.

[0030] For example, the amount of the sulfide ore collector used is 50~200g / t·feed.

[0031] For example, the foaming agent includes at least one of No. 2 oil, pine oil, camphor oil, and methylpentanol.

[0032] For example, the amount of the foaming agent used is 30~100g / t·feed.

[0033] In some embodiments, the magnetic field strength of the weak magnetic separation is 2000~3000 Oe.

[0034] In some embodiments, the background magnetic field strength of the strong magnetic separation is 0.6~1.4T.

[0035] In some embodiments, the fine-grained concentrate has a particle size of -0.038 mm.

[0036] In some embodiments, the background magnetic field strength of the fine-particle strong magnetic separation is 0.8~1.4T.

[0037] It is understood that the purpose of titanium flotation is to separate titanium minerals from other impurity minerals in the titanium pre-enriched concentrate. In order to achieve the above purpose, a variety of reagents and methods can be used, and those skilled in the art can make appropriate selections according to actual needs. This disclosure does not limit them.

[0038] In some examples, the reagents used in the titanium flotation include modifiers, inhibitors, collectors, and auxiliary collectors.

[0039] For example, the titanium flotation method includes: adding the adjuster to the titanium pre-enriched concentrate to adjust the pH value to ±3.5, adding the inhibitor, the collector and the auxiliary collector, and then stirring and flotation to selectively float and enrich the titanium minerals in the froth product to obtain the ilmenite concentrate, and discharging the unfloated portion as the titanium flotation tailings.

[0040] For example, the modifier includes dilute sulfuric acid.

[0041] For example, the dosage of the modifier is 2000~4000g / t·feed.

[0042] For example, the inhibitor includes at least one of water glass, sodium fluorosilicate, and oxalic acid.

[0043] For example, the dosage of the inhibitor is 500~3000g / t·feed.

[0044] For example, the collector includes MOH.

[0045] For example, the amount of the collector used is 1000~3000g / t·feed.

[0046] For example, the auxiliary collector includes diesel fuel.

[0047] For example, the dosage of the auxiliary collector is 20~100g / t·feed.

[0048] The beneficial effects of this disclosure are: 1. The present disclosure provides a method for efficiently recovering zirconium, hafnium, and titanium from paleofluvial lacustrine zirconium-hafnium placer deposits. This method not only enables efficient synergistic enrichment of zirconium, hafnium, and titanium in the ore, but also yields high-grade and high-recovery zirconium-hafnium concentrate and ilmenite concentrate, ultimately greatly improving the utilization rate of zirconium, hafnium, and titanium in the ore.

[0049] 2. This disclosure provides a method for the efficient recovery of zirconium, hafnium, and titanium from paleofluvial zirconium-hafnium placer deposits. The entire process employs a combination of gravity separation, magnetic separation, and flotation for separation. The ore dressing water can be directly returned to the production process, resulting in low production costs and an environmentally friendly approach.

[0050] 3. The present disclosure provides a method for the efficient recovery of zirconium, hafnium, and titanium from ancient fluvial and lacustrine zirconium-hafnium placer deposits. The process technology is clean, efficient, economical, and reasonable, and can be easily transformed and industrialized on a large scale, with significant economic and social benefits. Attached Figure Description

[0051] To more clearly illustrate the technical solutions in this disclosure, the accompanying drawings used in some embodiments of this disclosure will be briefly described below. Obviously, the drawings described below are merely drawings of some embodiments of this disclosure, and those skilled in the art can obtain other drawings based on these drawings. Furthermore, the drawings described below can be regarded as schematic diagrams and are not intended to limit the actual process of the methods involved in the embodiments of this disclosure.

[0052] Figure 1 This is a flowchart illustrating the principle of a method for efficiently recovering zirconium, hafnium, and titanium from paleofluvial lacustrine zirconium-hafnium placer deposits, according to an embodiment of this disclosure. Detailed Implementation

[0053] The technical solutions in some embodiments of this disclosure will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments provided in this disclosure, all other embodiments obtained by those skilled in the art are within the scope of protection of this disclosure.

[0054] Unless the context otherwise requires, throughout the specification and claims, the term "comprising" is interpreted as open and encompassing, that is, "including, but not limited to".

[0055] In describing some embodiments, the expressions "at least one of A, B and C" and "at least one of A, B or C" may be used, both of which have the same meaning and include the following combinations of A, B and C: only A, only B, only C, a combination of A and B, a combination of A and C, a combination of B and C, and a combination of A, B and C. Example 1

[0056] A method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zirconium-hafnium placer deposits is disclosed. The raw ore is derived from paleoriver-lacustrine zirconium-hafnium placer deposits in Xinjiang. Multiple chemical analyses show that the ZrO2 grade is 0.21%, HfO2 grade is 50 ppm, TiO2 grade is 0.39%, S grade is 0.139%, TFe2O3 grade is 4.26%, Al2O3 grade is 10.84%, SiO2 grade is 60.82%, K2O grade is 3.58%, and CaO grade is 6.66%.

[0057] The main process of the above-mentioned mineral processing method is as follows: Figure 1 As shown, it includes the following steps: S1. The raw ore is crushed to obtain crushed minerals with a particle size of -3mm (i.e., a composite sample of the -3mm raw ore). S2. The crushed minerals are classified to obtain oversize minerals with a particle size of +0.5mm and undersize minerals with a particle size of -0.5mm; S3. Grind the minerals on the sieve to a particle size of -0.5mm to obtain a pre-ground product, and return the pre-ground product to the classification step in S2; S4. The minerals under sieve are classified to obtain coarse-grained minerals with a particle size of +0.074 mm and fine-grained minerals with a particle size of -0.074 mm; S5. Perform coarse-grained gravity separation on the coarse-grained minerals to obtain coarse-grained gravity concentrate and coarse-grained gravity tailings; S6. Fine-grained minerals are subjected to fine-grained gravity separation to obtain fine-grained gravity concentrate and fine-grained gravity tailings; S7. Combine the coarse gravity concentrate and the fine gravity concentrate into a pre-enriched concentrate, and perform two-stage grinding to a fineness of -0.074mm 40% to obtain the second-stage regrinding product. S8. The product from the second regrinding stage is subjected to flotation desulfurization. The flotation reagents are 50 g / t·feed of butyl xanthate as a collector for sulfide minerals and 30 g / t·feed of frother No. 2 oil, to obtain sulfide mineral concentrate and desulfurized tailings. S9. The desulfurization tailings are subjected to weak magnetic iron removal with a magnetic field strength of 2000 Oe to obtain weak magnetic concentrate and weak magnetic tailings. S10. The weak magnetic separation tailings are subjected to strong magnetic separation with a background magnetic field strength of 0.6T to obtain strong magnetic separation concentrate and strong magnetic separation tailings; S11. Perform gravity separation on the tailings from the strong magnetic separation to obtain zirconium hafnium concentrate and gravity-separated zirconium hafnium tailings, and return the obtained gravity-separated zirconium hafnium tailings to the classification step in S4; S12. The high-intensity magnetic separation concentrate is classified to obtain a coarse-grained concentrate with a particle size of +0.038mm and a fine-grained concentrate with a particle size of -0.038mm; S13. Perform coarse gravity separation on the coarse-grained concentrate to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings; S14. Fine-grained concentrate is subjected to fine-grained magnetic separation with a background magnetic field strength of 0.8T to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings. S15. The gravity separation titanium pre-enriched concentrate and the magnetic separation titanium pre-enriched concentrate are combined for ilmenite flotation. 2000g / t·feed of dilute sulfuric acid is added to adjust the pH to about 3.5. Then, 500g / t·feed of sodium fluorosilicate inhibitor, 2000g / t·feed of collector MOH, and 20g / t·feed of auxiliary collector diesel are added. The flotation equipment is used for stirring, pulp conditioning and flotation operations, so that the titanium minerals selectively float and are enriched in the froth product to obtain ilmenite concentrate. The unfloated part is discharged as titanium flotation tailings.

[0058] It should be noted that the tailings are obtained by combining the coarse gravity separation tailings in S5, the fine gravity separation tailings in S6, the sulfide concentrate in S8, the weak magnetic separation concentrate in S9, the gravity separation titanium pre-enrichment tailings in S13, the magnetic separation titanium pre-enrichment tailings in S14, and the titanium flotation tailings in S15.

[0059] The results showed that in the zirconium-hafnium concentrate, the ZrO2 grade was 64.34% and the ZrO2 recovery rate was 61.28%; the HfO2 grade was 0.83% and the HfO2 recovery rate was 33.20%; the TiO2 grade was 0.19% and the TiO2 recovery rate was 0.10%; and the S grade was 0.02 ppm and the S recovery rate was 0.00%. In the ilmenite concentrate, the ZrO2 grade was 0.89% with a ZrO2 recovery rate of 0.78%, the HfO2 grade was 0.017% with a HfO2 recovery rate of 0.63%, the TiO2 grade was 46.20% with a TiO2 recovery rate of 21.83%, and the S grade was 0.02 ppm with a S recovery rate of 0.00%. In the tailings, the ZrO2 grade is 0.06% and the ZrO2 recovery rate is 40.35%, the HfO2 grade is 10.4ppm and the HfO2 recovery rate is 67.35%, the TiO2 grade is 0.24% and the TiO2 recovery rate is 78.65%, and the S grade is 0.14% and the S recovery rate is 100.00%. Example 2

[0060] A method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zircon-hafnium placer deposits is disclosed. The raw ore is derived from paleoriver-lacustrine zircon-hafnium placer deposits in Xinjiang. Multiple chemical analyses show that the ZrO2 grade is 0.15%, HfO2 grade is 35 ppm, TiO2 grade is 0.3%, S grade is 0.149%, TFe2O3 grade is 4.4%, Al2O3 grade is 10.9%, SiO2 grade is 62.5%, K2O grade is 3.6%, and CaO grade is 7.2%.

[0061] The main process of the above-mentioned mineral processing method is as follows: Figure 1 As shown, it includes the following steps: S1. The raw ore is crushed to obtain crushed minerals with a particle size of -3mm (i.e., a composite sample of the -3mm raw ore). S2. The crushed minerals are classified to obtain oversize minerals with a particle size of +0.5mm and undersize minerals with a particle size of -0.5mm; S3. Grind the minerals on the sieve to a particle size of -0.5mm to obtain a pre-ground product, and return the pre-ground product to the classification step in S2; S4. The minerals under sieve are classified to obtain coarse-grained minerals with a particle size of +0.074 mm and fine-grained minerals with a particle size of -0.074 mm; S5. Perform coarse-grained gravity separation on the coarse-grained minerals to obtain coarse-grained gravity concentrate and coarse-grained gravity tailings; S6. Fine-grained minerals are subjected to fine-grained gravity separation to obtain fine-grained gravity concentrate and fine-grained gravity tailings; S7. Combine the coarse gravity concentrate and the fine gravity concentrate into a pre-enriched concentrate, and perform two-stage grinding to a fineness of -0.074mm 60% to obtain the second-stage regrinding product. S8. The product from the second regrinding stage is subjected to flotation desulfurization. The flotation reagents are 100 g / t·feed of butyl xanthate as a collector for sulfide minerals and 50 g / t·feed of pine oil as a frother, to obtain sulfide mineral concentrate and desulfurized tailings. S9. The desulfurization tailings are subjected to weak magnetic iron removal with a magnetic field strength of 3000 Oe to obtain weak magnetic concentrate and weak magnetic tailings. S10. The weak magnetic separation tailings are subjected to strong magnetic separation with a background magnetic field strength of 1.4T to obtain strong magnetic separation concentrate and strong magnetic separation tailings; S11. Perform gravity separation on the tailings from the strong magnetic separation to obtain zirconium hafnium concentrate and gravity-separated zirconium hafnium tailings, and return the obtained gravity-separated zirconium hafnium tailings to the classification step in S4; S12. The high-intensity magnetic separation concentrate is classified to obtain a coarse-grained concentrate with a particle size of +0.038mm and a fine-grained concentrate with a particle size of -0.038mm; S13. Perform coarse gravity separation on the coarse-grained concentrate to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings; S14. Fine-grained concentrate is subjected to fine-grained magnetic separation with a background magnetic field strength of 1.2T to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings. S15. The gravity separation titanium pre-enriched concentrate and the magnetic separation titanium pre-enriched concentrate are combined for ilmenite flotation. 3000g / t·feed of dilute sulfuric acid is added to adjust the pH to about 3.5. Then, 2000g / t·feed of gangue mineral inhibitor water glass, 2000g / t·feed of collector MOH, and 50g / t·feed of auxiliary collector diesel are added. The flotation equipment is used for stirring, pulp conditioning and flotation operations, so that the titanium minerals selectively float and are enriched in the froth product to obtain ilmenite concentrate. The unfloated part is discharged as titanium flotation tailings.

[0062] It should be noted that the tailings are obtained by combining the coarse gravity separation tailings in S5, the fine gravity separation tailings in S6, the sulfide concentrate in S8, the weak magnetic separation concentrate in S9, the gravity separation titanium pre-enrichment tailings in S13, the magnetic separation titanium pre-enrichment tailings in S14, and the titanium flotation tailings in S15.

[0063] The results showed that in the zirconium-hafnium concentrate, the ZrO2 grade was 64.21% with a ZrO2 recovery rate of 59.09%, the HfO2 grade was 0.81% with a HfO2 recovery rate of 32.17%, the TiO2 grade was 0.39% with a TiO2 recovery rate of 0.18%, and the S grade was 0.022 ppm with a S recovery rate of 0.00%. In the ilmenite concentrate, the ZrO2 grade was 0.60% with a ZrO2 recovery rate of 0.56%, the HfO2 grade was 0.012% with a HfO2 recovery rate of 0.48%, the TiO2 grade was 46.10% with a TiO2 recovery rate of 21.18%, and the S grade was 0.018 ppm with a S recovery rate of 0.00%. In the tailings, the grade of ZrO2 is 0.061% and the recovery rate of ZrO2 is 40.35%, the grade of HfO2 is 0.002% and the recovery rate of HfO2 is 67.35%, the grade of TiO2 is 0.24% and the recovery rate of TiO2 is 78.65%, and the grade of S is 0.15% and the recovery rate of S is 100.00%. Example 3

[0064] A method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zircon-hafnium placer deposits is disclosed. The raw ore is from paleoriver-lacustrine zircon-hafnium placer deposits in Xinjiang. Multiple chemical analyses show that the ZrO2 grade is 0.17%, HfO2 grade is 34 ppm, TiO2 grade is 0.35%, S grade is 0.149%, TFe2O3 grade is 4.5%, Al2O3 grade is 11.2%, SiO2 grade is 62.7%, K2O grade is 3.8%, and CaO grade is 7.5%.

[0065] The main process of the above-mentioned mineral processing method is as follows: Figure 1 As shown, it includes the following steps: S1. The raw ore is crushed to obtain crushed minerals with a particle size of -3mm (i.e., a composite sample of the -3mm raw ore). S2. The crushed minerals are classified to obtain oversize minerals with a particle size of +0.5mm and undersize minerals with a particle size of -0.5mm; S3. Grind the minerals on the sieve to a particle size of -0.5mm to obtain a pre-ground product, and return the pre-ground product to the classification step in S2; S4. The minerals under sieve are classified to obtain coarse-grained minerals with a particle size of +0.074 mm and fine-grained minerals with a particle size of -0.074 mm; S5. Perform coarse-grained gravity separation on the coarse-grained minerals to obtain coarse-grained gravity concentrate and coarse-grained gravity tailings; S6. Fine-grained minerals are subjected to fine-grained gravity separation to obtain fine-grained gravity concentrate and fine-grained gravity tailings; S7. Combine the coarse gravity concentrate and the fine gravity concentrate into a pre-enriched concentrate, and perform two-stage grinding to a fineness of -0.074mm 50% to obtain the second-stage regrinding product. S8. The product from the second regrinding stage is subjected to flotation desulfurization. The flotation reagents are 100 g / t·feed of butyl xanthate as a collector for sulfide minerals and 50 g / t·feed of pine oil as a frother, to obtain sulfide mineral concentrate and desulfurized tailings. S9. The desulfurization tailings are subjected to weak magnetic iron removal with a magnetic field strength of 2000 Oe to obtain weak magnetic concentrate and weak magnetic tailings. S10. The weak magnetic separation tailings are subjected to strong magnetic separation with a background magnetic field strength of 1.0T to obtain strong magnetic separation concentrate and strong magnetic separation tailings; S11. Perform gravity separation on the tailings from the strong magnetic separation to obtain zirconium hafnium concentrate and gravity-separated zirconium hafnium tailings, and return the obtained gravity-separated zirconium hafnium tailings to the classification step in S4; S12. The high-intensity magnetic separation concentrate is classified to obtain a coarse-grained concentrate with a particle size of +0.038mm and a fine-grained concentrate with a particle size of -0.038mm; S13. Perform coarse gravity separation on the coarse-grained concentrate to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings; S14. Fine-grained concentrate is subjected to fine-grained magnetic separation with a background magnetic field strength of 1.4T to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings. S15. The gravity separation titanium pre-enriched concentrate and the magnetic separation titanium pre-enriched concentrate are combined for ilmenite flotation. 2000g / t·feed of dilute sulfuric acid is added to adjust the pH to about 3.5. Then, 2000g / t·feed of water glass, a gangue mineral inhibitor, 3000g / t·feed of MOH, a collector, and 50g / t·feed of diesel oil, an auxiliary collector, are added. The flotation equipment is used for stirring, pulp conditioning, and flotation operations, so that the titanium minerals selectively float and are enriched in the froth product to obtain ilmenite concentrate. The unfloated portion is discharged as titanium flotation tailings from the system.

[0066] It should be noted that the tailings are obtained by combining the coarse gravity separation tailings in S5, the fine gravity separation tailings in S6, the sulfide concentrate in S8, the weak magnetic separation concentrate in S9, the gravity separation titanium pre-enrichment tailings in S13, the magnetic separation titanium pre-enrichment tailings in S14, and the titanium flotation tailings in S15.

[0067] The results showed that in the zirconium-hafnium concentrate, the ZrO2 grade was 64.18% and the ZrO2 recovery rate was 56.59%; the HfO2 grade was 0.80% and the HfO2 recovery rate was 33.42%; the TiO2 grade was 0.24% and the TiO2 recovery rate was 0.10%; and the S grade was 0.029 ppm and the S recovery rate was 0.00%. In the ilmenite concentrate, the ZrO2 grade was 0.65% with a ZrO2 recovery rate of 0.59%, the HfO2 grade was 0.01% with a HfO2 recovery rate of 0.52%, the TiO2 grade was 46.17% with a TiO2 recovery rate of 19.85%, and the S grade was 0.066 ppm with a S recovery rate of 0.00%. In the tailings, the grade of ZrO2 is 0.07% and the recovery rate of ZrO2 is 42.81%, the grade of HfO2 is 0.002% and the recovery rate of HfO2 is 66.06%, the grade of TiO2 is 0.28% and the recovery rate of TiO2 is 80.06%, and the grade of S is 0.15% and the recovery rate of S is 100.00%.

[0068] Compare with Example 1 Example 1 and Comparative Example 1 were compared. Both examples used the same raw ore. The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 adopted the method described in the literature "Discovery of Paleofluvial-lacustrine Zircon Sand Deposits on the Northern Margin of the Kubai Basin in Xinjiang Achieves a Breakthrough in Zircon Exploration in my country".

[0069] The results showed that only zircon concentrate with a ZrO2 grade of 59.66%, a ZrO2 recovery rate of 12.17%, a HfO2 grade of 0.85%, and an HfO2 recovery rate of 8.16% could be obtained.

[0070] It can be seen that the grade and recovery rate of ZrO2 and HfO2 in the zircon concentrate of Comparative Example 1 are significantly lower than those in the zircon-hafnium concentrate of Example 1, and titanium in the ore was not fully recovered in Comparative Example 1.

[0071] Compare with Example 2 Example 1 and Comparative Example 2 were compared. The difference between Comparative Example 2 and Example 1 is as follows: Replace S2~S3 with: perform a first-stage grinding of the crushed mineral to a particle size of -0.5mm, and then sieve to obtain undersize minerals with a particle size of -0.5mm; Other conditions, such as the raw ore used, the selection and dosage of reagents, and the remaining steps and parameters of the method, are the same as in Example 1 (this comparative example, compared to Example 1, did not perform pre-selection and classification before pre-grinding, which is used to demonstrate that the method of this disclosure is more effective).

[0072] The results showed that in the zirconium-hafnium concentrate, the ZrO2 grade was 64.15% and the ZrO2 recovery rate was 57.30%; the HfO2 grade was 0.77% and the HfO2 recovery rate was 26.54%; the TiO2 grade was 0.22% and the TiO2 recovery rate was 0.11%; and the S grade was 40 ppm and the S recovery rate was 0.00%. In the ilmenite concentrate, the ZrO2 grade is 0.78% and the ZrO2 recovery rate is 0.66%, the HfO2 grade is 0.02% and the HfO2 recovery rate is 0.49%, the TiO2 grade is 46.10% and the TiO2 recovery rate is 20.88%, and the S grade is 0.02% and the S recovery rate is 0.00%. In the tailings, the grade of ZrO2 is 0.09% and the recovery rate of ZrO2 is 42.04%, the grade of HfO2 is 0.004% and the recovery rate of HfO2 is 72.97%, the grade of TiO2 is 0.31% and the recovery rate of TiO2 is 79.01%, and the grade of S is 0.14% and the recovery rate of S is 100.00%.

[0073] It can be seen that, compared with Example 1, the recovery rates of ZrO2 and HfO2 in the zirconium-hafnium concentrate in Comparative Example 2 are reduced, and the recovery rate of TiO2 in the ilmenite concentrate is also reduced. This is because: directly grinding the crushed minerals to a particle size of -0.5mm through a single grinding process causes the ore in the already liberated fine sandstone to be ground again, which affects the subsequent separation effect of high specific gravity minerals and gangue minerals, ultimately leading to a reduction in the recovery rate of mineral processing.

[0074] Compare with Example 3 Example 1 and Comparative Example 3 were compared. The difference between Comparative Example 3 and Example 1 is as follows: Replace S4~S7 with: perform gravity separation on the undersize minerals to obtain pre-enriched concentrate and gravity separation tailings, perform two-stage grinding on the pre-enriched concentrate, and grind to a fineness of -0.074mm 40% to obtain the second-stage regrinding product. Other conditions, such as the raw ore used, the selection and dosage of reagents, and the remaining steps and parameters of the method, are the same as in Example 1 (compared to Example 1, this comparative example does not perform coarse-grained gravity separation pre-enrichment and fine-grained gravity separation pre-enrichment on the undersize minerals after particle size classification, but directly performs gravity separation on the undersize minerals to demonstrate that the method disclosed in this invention is more effective).

[0075] The results showed that in the zirconium-hafnium concentrate, the ZrO2 grade was 64.22% and the ZrO2 recovery rate was 57.52%; the HfO2 grade was 0.76% and the HfO2 recovery rate was 26.42%; the TiO2 grade was 0.28% and the TiO2 recovery rate was 0.13%; and the S grade was 60 ppm and the S recovery rate was 0.00%. In the ilmenite concentrate, the ZrO2 grade was 0.81% with a ZrO2 recovery rate of 0.63%, the HfO2 grade was 0.02% with a HfO2 recovery rate of 0.47%, the TiO2 grade was 45.80% with a TiO2 recovery rate of 18.94%, and the S grade was 0.027 ppm with a S recovery rate of 0.00%. In the tailings, the grade of ZrO2 is 0.09% and the recovery rate of ZrO2 is 41.85%, the grade of HfO2 is 0.004% and the recovery rate of HfO2 is 73.12%, the grade of TiO2 is 0.32% and the recovery rate of TiO2 is 80.93%, and the grade of S is 0.14% and the recovery rate of S is 100.00%.

[0076] It can be seen that, compared with Example 1, the recovery rates of ZrO2 and HfO2 in the zirconium-hafnium concentrate in Comparative Example 3 are reduced, and the recovery rate of TiO2 in the ilmenite concentrate is also reduced. This is because: direct gravity separation of undersize minerals only utilizes the difference in specific gravity between ores, but does not utilize the difference in particle size between ores. This will reduce the removal effect of minerals such as quartz, feldspar, calcite, and illite, ultimately leading to a decrease in the recovery rate of mineral processing.

[0077] Compare with Example 4 Example 1 and Comparative Example 4 were compared. The difference between Comparative Example 4 and Example 1 is as follows: 1) Replace S13 with: Perform coarse magnetic separation on the coarse-grained concentrate with a background magnetic field strength of 0.8T to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings. 2) Replace S14 with: Perform fine-grained gravity separation on the fine-grained concentrate to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings; Other conditions, such as the raw ore used, the selection and dosage of reagents, and the remaining steps and parameters of the method, are the same as in Example 1 (compared to Example 1, this comparative example replaces coarse-grained gravity separation with coarse-grained strong magnetic separation and fine-grained strong magnetic separation with fine-grained gravity separation to demonstrate that the method disclosed herein is more effective).

[0078] The results showed that in the zirconium-hafnium concentrate, the ZrO2 grade was 64.27% and the ZrO2 recovery rate was 61.39%; the HfO2 grade was 0.83% and the HfO2 recovery rate was 33.19%; the TiO2 grade was 0.25% and the TiO2 recovery rate was 0.13%; and the S grade was 0.05 ppm and the S recovery rate was 0.00%. In the ilmenite concentrate, the ZrO2 grade was 0.85% with a ZrO2 recovery rate of 0.63%, the HfO2 grade was 0.02% with a HfO2 recovery rate of 0.47%, the TiO2 grade was 45.60% with a TiO2 recovery rate of 18.29%, and the S grade was 0.033 ppm with a S recovery rate of 0.00%. In the tailings, the grade of ZrO2 is 0.08%, the recovery rate of ZrO2 is 37.98%, the grade of HfO2 is 0.003%, the recovery rate of HfO2 is 66.19%, the grade of TiO2 is 0.32%, the recovery rate of TiO2 is 81.58%, and the grade of S is 0.14%, the recovery rate of S is 100.00%.

[0079] It can be seen that, compared with Example 1, the recovery rate of TiO2 in the ilmenite concentrate in Comparative Example 4 is reduced. This is because: the fine-grained concentrate is subjected to gravity separation, and due to the fine particle size of the ore, the separation efficiency in the hydraulic and mechanical separation processes of gravity separation equipment is reduced, which inevitably makes the recovery of fine minerals in the ore difficult, thus leading to a decrease in the beneficiation recovery rate; in addition, if the coarse-grained ore is subjected to strong magnetic separation, a large amount of electricity is required to form a high background magnetic field intensity, which will inevitably increase the beneficiation cost compared with the gravity separation process.

[0080] Therefore, the method for efficiently recovering zirconium, hafnium, and titanium from paleoriver-lacustrine zirconium-hafnium placer deposits provided in this disclosure achieves at least the synergistic and efficient enrichment of zirconium, hafnium, and titanium from new types of paleoriver-lacustrine zirconium-hafnium placer deposits, and obtains high-grade and high-recovery zirconium-hafnium concentrate and ilmenite concentrate, thereby significantly improving the utilization rate of zirconium, hafnium, and titanium in the ore.

[0081] The above description is merely a preferred embodiment of this disclosure. It should be understood that this disclosure is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the concept described herein through the above teachings or techniques or knowledge in related fields. Any modifications and variations made by those skilled in the art that do not depart from the spirit and scope of this disclosure should be within the protection scope of the appended claims.

Claims

1. A method for efficiently recovering zirconium, hafnium, and titanium from paleofluvial lacustrine zirconium-hafnium placer deposits, characterized in that, include: Pre-treatment was performed on the paleofluvial lacustrine zircon-hafnium placer ore to liberate it, resulting in pre-treated minerals. The pretreated minerals are subjected to gravity separation pre-enrichment to obtain gravity separation pre-enriched concentrate and gravity separation pre-enriched tailings; The gravity separation pre-enriched concentrate is ground to obtain grinding products; The grinding products are subjected to desulfurization flotation to obtain sulfide mineral concentrate and desulfurization tailings; The desulfurization tailings are subjected to weak magnetic separation to obtain weak magnetic concentrate and weak magnetic tailings; The weak magnetic separation tailings are subjected to strong magnetic separation to obtain strong magnetic separation concentrate and strong magnetic separation tailings; The tailings from the strong magnetic separation are subjected to gravity separation to obtain zirconium hafnium concentrate and gravity-separated zirconium hafnium tailings; The high-intensity magnetic separation concentrate is classified to obtain coarse-grained concentrate and fine-grained concentrate; The coarse-grained concentrate is subjected to coarse-grained gravity separation to obtain gravity-separated titanium pre-enriched concentrate and gravity-separated titanium pre-enriched tailings. The fine-grained concentrate is subjected to fine-grained high-intensity magnetic separation to obtain magnetically separated titanium pre-enriched concentrate and magnetically separated titanium pre-enriched tailings; The gravity-separated titanium pre-enriched concentrate and the magnetic-separated titanium pre-enriched concentrate are combined to obtain a titanium pre-enriched concentrate; and The titanium pre-enriched concentrate is subjected to titanium flotation to obtain ilmenite concentrate and titanium flotation tailings.

2. The method according to claim 1, characterized in that, In the aforementioned paleofluvial lacustrine zirconium-hafnium placer ore, the grade of ZrO2 is not less than 0.15%, the grade of HfO2 is not less than 25ppm, and the grade of TiO2 is not less than 0.3%.

3. The method according to claim 1, characterized in that, The pretreatment of paleofluvial lacustrine zirconium-hafnium placer ore to liberate it yields pretreated minerals, including: The paleofluvial lacustrine zirconium-hafnium placer ore was crushed to obtain crushed minerals; The crushed minerals are pre-sorted and classified to obtain oversize and undersize minerals; and The minerals on the sieve are pre-ground to obtain pre-ground mineral products; The pre-ground mineral product is returned to the pre-selection and grading process; the undersized minerals are used as the pre-treated minerals.

4. The method according to any one of claims 1 to 3, characterized in that, The process of pre-concentrating the pretreated minerals to obtain pre-concentrated concentrate and pre-concentrated tailings includes: The pretreated minerals are subjected to particle size classification to obtain coarse-grained minerals and fine-grained minerals; The coarse-grained minerals are pre-enriched by coarse-grained gravity separation to obtain coarse-grained gravity concentrate and coarse-grained gravity tailings; and The fine-grained minerals are pre-enriched by fine-grained gravity separation to obtain fine-grained gravity concentrate and fine-grained gravity tailings; Specifically, the coarse gravity concentrate and the fine gravity concentrate are combined to form the gravity pre-enriched concentrate; the coarse gravity tailings and the fine gravity tailings are combined to form the gravity pre-enriched tailings.

5. The method according to claim 4, characterized in that, The method further includes: The reseparated zirconium-hafnium tailings are returned to the particle size classification.

6. The method according to claim 1, characterized in that, The weight percentage of minerals with a particle size of -0.074 mm in the grinding product is 40% to 60%.

7. The method according to claim 1, characterized in that, The magnetic field strength of the weak magnetic separation is 2000~3000 Oe.

8. The method according to claim 1, characterized in that, The background magnetic field strength of the strong magnetic separation is 0.6~1.4T.

9. The method according to claim 1, characterized in that, The fine-grained concentrate has a particle size of -0.038 mm.

10. The method according to claim 1, characterized in that, The background magnetic field strength of the fine-particle strong magnetic separation is 0.8~1.4T.

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