WO2012137359A1 - Process for producing titanium dioxide concentrate - Google Patents

Abstract

The present invention enables a high-grade concentrate in which titanium dioxide has been highly concentrated to be inexpensively produced from a low-grade titanium dioxide ore. A powdery titanium dioxide ore is subjected to reverse flotation (A) and flotation (B) in this order. In the reverse flotation (A), a concentrate is sedimented in an aqueous solution to which a cationic collector and starch have been added and which has a pH adjusted to 10 or higher. In the flotation (B), a concentrate is floated in an aqueous solution to which an anionic collector, hydrofluoric acid, and a frothing agent have been added and which has a pH adjusted to 2-3. It is preferred that the reverse flotation (A) and the flotation (B) should be preceded by a step in which a powdery titanium dioxide ore obtained through particle size regulation (F) is subjected to gravity concentration (G) and magnetic separation (H) in this order, and that the reverse flotation (A) and the flotation (B) should be succeeded by a step in which the concentrate separated through flotation in the flotation (B) is subjected to gravity concentration (C), drying (D), and magnetic separation (E) in this order.

Description

Method for producing titanium dioxide concentrate

In order to obtain a concentrate with increased titanium dioxide concentration, preferably a high grade concentrate with high concentration of titanium dioxide ore by benification of titanium dioxide ore. The present invention relates to a method for producing titanium dioxide concentrate.

Titanium metal and titanium dioxide used for industrial products are produced from concentrates in which titanium dioxide ore (natural ore) such as rutile ore is beneficiated to concentrate titanium dioxide at a high concentration.
Examples of conventional techniques for obtaining a concentrate enriched with titanium dioxide by beneficiating titanium dioxide ore include the following.
(1) A method for separating and removing gangue components (quartz, magnetite, monazite, zircon, etc.) in ore by combining gravity concentration, magnetic separation, electrostatic separation, etc. For example, Non-Patent Document 1)
(2) A chemical method that combines acid leaching, which is mainly performed to remove iron, and high-temperature reduction for forming TiO ₂ -slag (for example, Patent Document 1).
(3) Method combining magnetic ore flotation, flotation, electrostatic ore, high temperature reduction, etc. (for example, Patent Document 2)

Special table 2009-511755 gazette JP 55-59853 A

Institute of Pollution Resources, Institute of Industrial Science and Technology, Kenji Hamada, “Nonmetallic Mineral Mineral Mining”, Ceramic Association, July 10, 1974, p. 193-197

However, among the above conventional techniques, the methods (1) and (3) are limited in increasing the concentration of titanium dioxide in the concentrate, and there is a problem that it is difficult to obtain high-grade titanium dioxide concentrate. In particular, for rutile ore produced in the state of Minas Gerais, Brazil, because kyanite (SiO ₂ · Al ₂ O ₃ ) coexists, it is very difficult to obtain high-grade concentrate by the conventional method. In addition, the methods (2) and (3) have a limit in increasing the titanium dioxide concentration of concentrate at low cost.
Therefore, an object of the present invention is to obtain a concentrate with a high concentration of titanium dioxide from a low-grade titanium dioxide ore, and preferably to reduce a high-grade concentrate with a high concentration of titanium dioxide. The object is to provide a method for producing titanium dioxide concentrate that can be obtained at low cost.

In order to solve the above-mentioned problems, the present inventors have studied about a method capable of obtaining high grade concentrate at low cost by using only physical beneficiation. By subjecting titanium dioxide ore to reverse flotation and flotation in order under specific conditions, it is more preferable to adjust the particle size before and after the reverse flotation + flotation process. By combining processes such as (gravity concentration) and magnetic separation in a specific form, a high-grade concentrate in which titanium dioxide is concentrated at a high concentration can be obtained from low-grade titanium dioxide ore. Low enough for Kyanite to coexist It found that it is possible to obtain a high-grade concentrate from any place of titanium dioxide ore.

The present invention has been made on the basis of such findings and has the following gist.
[1] A method for obtaining a concentrate in which the concentration of titanium dioxide is increased by beneficiating titanium dioxide ore, and reverse flotation (A) and flotation (B) are sequentially applied to the powdered titanium dioxide ore. In reverse flotation (A), a cation scavenger and starch are added, and the concentrate is settled and separated in an aqueous solution whose pH is adjusted to 10 or more. In flotation (B), anion is used. A method for producing a titanium dioxide concentrate, comprising adding a scavenger, hydrofluoric acid, and a foaming agent, and floating-separating the concentrate in an aqueous solution adjusted to a pH of 2 to 3.
[2] The production method of [1], wherein the concentrate separated by floatation in the flotation (B) is subjected to specific gravity separation (C), drying treatment (D), and magnetic separation (E) in that order. To produce titanium dioxide concentrate.

[3] A method for producing a titanium dioxide concentrate according to the above [2], wherein in the magnetic separation (E), dry high magnetic separation is performed at 8000 gauss or more.
[4] In the production method of any one of [1] to [3] above, specific gravity ore (G) and magnetic ore (H) are sequentially applied to the powdered titanium dioxide ore obtained through the particle size adjustment (F). Then, after that, the reverse flotation (A) and the flotation (B) are performed in order, and the manufacturing method of the titanium dioxide concentrate characterized by the above-mentioned.
[5] In the production method of [4] above, in the particle size adjustment (F), a titanium dioxide ore is pulverized and classified to obtain a powdery titanium dioxide ore. .

[6] In the production method according to [4] or [5] above, the concentrate that has undergone specific gravity (G) is subjected to grain size adjustment (I), and then subjected to magnetic ore (H). A method for producing titanium concentrate.
[7] In the manufacturing method according to any one of [2] to [6] above, in the specific gravity (C) and specific gravity (G), the mineral processing using a table type mineral separator, the mineral processing using a spiral mineral separator, and the jig type mineral separator. A method for producing a titanium dioxide concentrate, wherein one or more of the beneficiations are performed.
[8] The method for producing a titanium dioxide concentrate according to any one of the above [1] to [7], wherein the titanium dioxide ore is a rutile ore.
[9] A method for producing a titanium dioxide concentrate according to any one of the above [1] to [8], wherein a titanium dioxide concentrate having a titanium dioxide content of 90% by mass or more is obtained.

According to the present invention, it is possible to obtain a high-grade concentrate in which titanium dioxide is concentrated at a high concentration from a low-grade titanium dioxide ore, and because it does not use chemical and thermal purification techniques, it is carried out at a low cost. can do. For this reason, even if it is from rutile ore in which kyanite (SiO ₂ · Al ₂ O ₃ ) symbiotic from Minas Gerais State, Brazil, the high-quality refined titanium dioxide is concentrated at a high concentration. Ore can be obtained at low cost.

Explanatory drawing which shows the processing flow of one Embodiment of this invention. Explanatory drawing which shows a part of processing flow of more concrete embodiment of this invention. Explanatory drawing which shows a part (continuation of the processing flow of FIG. 2) of the processing flow of more concrete embodiment of this invention. Explanatory drawing which shows a part of processing flow (continuation of the processing flow of FIG. 3) of more concrete embodiment of this invention.

The method for producing a titanium dioxide concentrate according to the present invention is a method for obtaining a concentrate enriched with titanium dioxide by beneficiation of titanium dioxide ore, and reverse flotation of powdered titanium dioxide ore under specific conditions. Basically (A) and flotation (B). Preferably, (1) reverse gravity flotation (A)-flotation (B) as a pre-process of powdered titanium dioxide ore obtained through particle size adjustment (F), specific gravity ore (G) and magnetic ore beneficiation. (H) in order (subsequently, reverse flotation (A) and flotation (B) in order), (2) reverse flotation (A)-flotation (B) as a subsequent process, flotation ( Steps such as subjecting the concentrate separated and floated in B) to specific gravity separation (C), drying treatment (D), and magnetic separation (E) in that order are performed.
In the present invention, the concentrate indicates a “mineral containing titanium dioxide” that is processed or separated in each step in order to obtain a concentrate (product) enriched in titanium dioxide.

In the present invention, the titanium dioxide ore that is the subject of the beneficiation can include a rutile ore as a representative example, but other than that, for example, anatase, plate titanium stone ( one or more of these may be used. In particular, rutile ore symbiotic with kyanite (SiO ₂ · Al ₂ O ₃ ) from Minas Gerais, Brazil is said to be difficult to obtain high-grade titanium dioxide concentrate. Such rutile ore can also be targeted for beneficiation. In the area where this rutile ore is produced, metamorphic gneiss and schist are mainly distributed, and the rutile deposit consists of pegmatato veins penetrating into them. This ore deposit is a weathered residue type in which pegmatato is weathered and rutile is concentrated. The rutile particle size is 0.5 to 0.045 mm, which is about 80% by mass. From the particle size of about 0.15 mm, rutile simple substance separation becomes remarkable.

Generally, titanium dioxide ore (natural mineral) such as rutile ore has a TiO ₂ content of 2% by mass or less. In the present invention, TiO ₂ is highly concentrated from titanium dioxide ore having such a TiO ₂ content. The object is to obtain a concentrate (preferably a concentrate having a TiO ₂ content of 90% by mass or more, more preferably 95% by mass or more). From the standpoints of production cost and processing efficiency, the titanium dioxide ore (natural mineral) used as a raw material in the present invention preferably has a TiO ₂ content of 0.5% by mass or more.
The ore gangue component separated and removed in the series of steps of the present invention is, for example, quartz (SiO ₂ ), kyanite (SiO ₂ .Al ₂ O ₃ ), zircon (ZrSiO ₄ ), monazite (( Ce · Th) PO ₄ ), garnet (3FeO · Al ₂ O ₃ · 3SiO ₂ ), bauxite (Al ₂ O ₃ · 3H ₂ O), and the like. As a result of the separation and removal of these gangue components, TiO ₂ A highly concentrated concentrate is obtained.

FIG. 1 shows a processing flow of an embodiment of the present invention. In this embodiment, for ore (original ore), particle size adjustment (F), specific gravity beneficiation (G), particle size adjustment (I), magnetic beneficiation (H), reverse flotation (A), flotation (B) The specific gravity beneficiation (C), the drying process (D), and the magnetic beneficiation (E) are performed in this order to obtain a high-grade titanium dioxide concentrate.
In the particle size adjustment (F), which is the first step, classification, crushing and pulverization are performed on the original ore (raw ore), and the ore is adjusted to a particle size suitable for beneficiation. Here, ore washing (water washing) may be performed also for classification. Usually, classification in this particle size adjustment (F) is performed in two or more stages, but it is preferable to use a cyclone separator which is a wet classifier for final classification. In the particle size adjustment (F), it is preferable to adjust the ore to a particle size of 1 mm or less (preferably 0.020 mm or more and 1 mm or less).

The specific gravity beneficiation (G) is applied to the powdery titanium dioxide ore obtained through the particle size adjustment (F), and is intended to separate and remove low specific gravity minerals. As the specific gravity separator, a table type mineral separator, a jig type mineral separator (jig concentrator), a spiral mineral separator (spiral concentrator) or the like can be used, but a spiral mineral separator using centrifugal gravity is particularly preferable.
Grain size adjustment (I) is carried out as necessary. The concentrate refined by the specific gravity beneficiation (G) is further refined by classification and pulverization, and further refined (reverse flotation beneficiation). (A) and a particle size suitable for flotation (B)). In the particle size adjustment (I), the ore is preferably adjusted to a particle size of 0.25 mm or less (preferably 0.020 mm or more and 0.25 mm or less). Moreover, it is preferable to use a cyclone separator which is a wet classifier for classification in this step.
Magnetic beneficiation (H) is performed on the concentrate through the specific gravity beneficiation (G) or particle size adjustment (I) to remove the main iron oxide (magnetized material). This magnetic beneficiation preferably uses a wet magnetic beneficiator.

Reverse flotation (A) and flotation (B) are sequentially performed on concentrates that have undergone the magnetic separation (H). The reverse flotation process (A) is mainly aimed at removing almost all the remaining quartz, and the subsequent flotation process (B) separates gangue composed mainly of kyanite and zircon. The purpose is to remove.
In the reverse flotation (A), a cation scavenger and starch are added, and the concentrate is settled and separated in an aqueous solution whose pH is adjusted to 10 or more. In this reverse flotation, the gangue is separated as a float (floss) and the concentrate is recovered as a sediment (sink). Therefore, the surface of the gangue that should be separated and removed as a float is removed. A cation scavenger for changing to hydrophobicity and generating bubbles, and starch for making the concentrate hydrophilic to facilitate sedimentation are added. Minerals containing a large amount of heavy elements are easily bonded to starch, become hydrophilic in the combined state, and are less likely to adhere to bubbles, and thus settle easily. Further, the pH of the aqueous solution is adjusted to 10 or more in order to disperse each mineral particle and suppress aggregation and sedimentation of gangue.

As the cation collector, an amino collector such as a monoamino collector or a diamino collector is particularly preferable, and among them, a monoamino collector (for example, trade name “EDA3”, Clariant SA) is most preferred. The addition amount is preferably about 200 to 300 g / t (g / t: addition amount per ton of solid content of the object to be treated. The same applies hereinafter). If the amount added is small, the effect of the addition is small, while if it is too large, the concentrate tends to float.
The amount of starch added is preferably about 300 to 600 g / t. If the addition amount is small, the effect of the addition is small. On the other hand, if the addition amount is too large, the gangue is likely to settle.
When the pH of the aqueous solution in which the reverse flotation (A) is performed is less than 10, the dispersion of the gangue is hindered. On the other hand, even if the pH exceeds 11, the dispersion of the gangue is not greatly changed, but the amount of the pH adjuster used is increased. It is preferable that Usually, an alkali such as caustic soda is added as a pH adjuster.

In flotation (B), an anion collector, hydrofluoric acid and a foaming agent are added, and the concentrate is floated and separated in an aqueous solution adjusted to pH 2 to 3. In this flotation, the concentrate is collected as suspended matter (floss) and the gangue is separated as sediment (sink). For this reason, the concentrate and other heavy minerals (gangue) are separated. An anion scavenger is added to provide selectivity, and hydrofluoric acid (inhibitor) is added to make it hydrophilic by adsorbing on the surface of the gangue to be separated and removed. A foaming agent is added to generate bubbles. Further, the pH of the aqueous solution is adjusted to 2 to 3 in order to secure the floatability of the concentrate by promoting the adsorption of the anion scavenger.

As the anion collector, a phosphonic acid collector (for example, trade name “Flotinor 1683”, manufactured by Clariant SA) is particularly preferable. The addition amount is preferably about 150 to 200 g / t. If the amount added is small, the effect of the addition is small. On the other hand, if the amount is too large, heavy minerals other than concentrate (portal stones) tend to float.
Moreover, as a hydrofluoric acid, hydrogen fluoride, hydrogen fluoride salt, etc. are preferable, for example, and 1 or more types of these can be used. The amount added is preferably about 600 to 1000 g / t. If the addition amount is small, the effect of the addition is small.

As the foaming agent, petroleum-based foaming agent (trade name “MIBC”, manufactured by Shell Sekiyu KK), synthetic alcohol-based foaming agent (trade name “AEROFROTH 65”, manufactured by Cytec), etc. are particularly preferable. Can be used. The amount added is preferably about 1 to 2 g / t. If the amount added is small, the effect of the addition is small. On the other hand, if the amount is too large, minerals other than concentrate (ganite content) tend to float.
When the pH of the aqueous solution in which the flotation (B) is performed is less than 2, adsorption of the scavenger tends to decrease. On the other hand, when the pH exceeds 3, other minerals other than concentrate (the gangue) are likely to float. Become. Usually, an acid (such as a hydrochloric acid solution) is added as a pH adjuster.
In addition, since a small amount of TiO ₂ is contained in the sedimentation of the flotation (B), it may be recovered and re-entered into the flotation (B) system.
Examples of the flotation machine used in the reverse flotation (A) and the flotation (B) include an agitaire type flotation machine and a Denver A type flotation machine, but any type may be used. In an ordinary flotation machine, minerals and air (bubbles) are mixed by stirring with an agitator such as an impeller while pressing air into a treatment tank containing an aqueous solution (slurry) containing minerals. Air bubbles are attached to the part and floated and separated as floss, and the remaining mineral is settled as a sink.

Specific gravity beneficiation (C) is carried out on concentrate (floss) obtained by the above flotation (B), mainly kayanite, zircon, etc. that could not be separated and removed by flotation (B) The purpose is to separate and remove the gangue. Normally, a vibration table (for example, a James table, a Wilfrey table, etc.) is used as a specific gravity sorter, but when a fine-grained mineral is used as in this specific gravity (C), A James table is particularly preferred.
In the drying process (D), the concentrate recovered by the specific gravity beneficiation (C) is dried. This drying process (D) is performed in order to facilitate the magnetic separation of the next step, and generally, the high magnetic separation machine has a dry specification. In this drying treatment, the concentrate is usually dried until the water content becomes about 1 to 2% by mass. A rotary dryer or the like can be used as the dryer.

Magnetic separation (E) is performed on the concentrate dried by the drying process (D). This magnetic separation (E) is mainly intended to separate and remove monazite, and dry high magnetic separation is preferably performed with a magnetic force of 8000 gauss or more. Generally, it is difficult to remove monazite when the magnetic force is less than 8000 gauss. The upper limit of the magnetic force of a general magnetic separator is about 10000 Gauss.
By this magnetic separation (E), a titanium dioxide concentrate having a TiO ₂ content of 90% by mass or more (preferably 95% by mass or more) can be obtained as a non-magnetic product.

In general, rutile ore in which kyanite (SiO ₂ · Al ₂ O ₃ ) coexists among titanium dioxide ores is considered to be very difficult to separate from kyanite and titanium dioxide. By combining reverse flotation (A) and flotation (B) under specific conditions, it is more preferable to adjust the particle size before and after the reverse flotation (A) + flotation (B) process, specific gravity or magnetic separation, etc. By combining the steps in a specific form, the gangue content including kyanite can be efficiently separated and removed, and a high-grade titanium dioxide concentrate can be obtained.

2 to 4 show a processing flow of a specific embodiment of the present invention. Hereinafter, this specific embodiment will be described in the order of steps.
・ Granularity adjustment (F)
As shown in FIG. 2, ore (original ore) having a predetermined particle size (for example, 100 mm or less) is charged into a drum washer 20 having a predetermined mesh (for example, 20 mm) through a vibration feeder 25, and this drum washer At 20, it is classified while being washed with water, and an undersize (e.g., −20 mm) ore is sent to a sieve 22 as the next step. On the other hand, the oversize ore (for example, +20 mm) is pulverized by a crusher 21 made of corn crusher or the like and re-loaded into the drum washer 20. The drum washer 20 also serves to loosen the ore with water.

The ore under the sieve (for example, −20 mm) in the drum washer 20 is applied to a sieve 22 (for example, 1 mm) having a smaller sieve, and the ore under the sieve (for example, −1 mm) is applied to the cyclone separator 24 which is the next step. Sent. The ore (for example, +1 mm) on the sieve is pulverized again by the wet pulverizer 23 and then sieved again by the sieve 22. As the wet pulverizer 23, a ball mill, a rod mill, a vibration mill, or the like can be used. The ore (for example, -1 mm) under the sieve 22 is classified by a cyclone separator 24 that is a wet classifier, and a fine particle (for example, -0.020 mm) has a predetermined particle size (for example, 0.020 mm) as a classification point. To be separated. The reason why the fine powder is separated and removed in this way is to remove the clay content in the ore. The classification by the first-stage cyclone separator 24 is controlled by the pressure on the entry side (for example, 1 kg / cm ² ), and the mud containing a lot of alumina (Al ₂ O ₃ ) and silica (SiO ₂ ) is used as overflow water. It is discharged out of the system and processed as tailings.

・ Specific gravity beneficiation (G)
As shown in FIG. 3, the ore having a predetermined particle size (for example, 0.020 to 1 mm) that has been classified by the cyclone separator 24 is concentrated in the concentrate C (concentrate), intermediate by the two-stage specific gravity separators 30 and 31. The product M (mid ring) and tailings T (tailing) are separated. Specific gravity separators include table type and jig type, but spiral mineral separators using centrifugal gravity are particularly preferable. In the present embodiment, the first stage uses a luffer spiral beneficiary machine, and the second stage uses a low grade spiral beneficiary machine and a medium grade spiral beneficiary machine. The concentrate sent to the next process is obtained by the flow of the intermediate M and tailings T. The tailings to be discarded are mainly clay and quartz.

・ Granularity adjustment (I)
The concentrate (ore) that has been selected by the specific gravity separation (G) is classified by a cyclone separator 40 (second-stage cyclone separator) that is a wet classifier, and a predetermined particle size (for example, 0.25 mm) is classified. As a result, coarse particles (for example, +0.25 mm) are separated. The classification by the second-stage cyclone separator 40 is controlled by the pressure on the entry side (1 kg / cm ² ), and the fine concentrate (for example, -0.25 mm) concentrate is sent to the magnetic separation (H) as the next step. It is done. Coarse (for example, +0.25 mm) concentrate is pulverized by a wet pulverizer 41 and then classified by a third-stage cyclone separator 42 which is a wet classifier to classify a predetermined particle size (for example, 0.020 mm). As a point, fine powder (for example, -0.020 mm) is separated. On the other hand, the coarse ore concentrate (for example, +0.020 mm) is recycled to the second-stage cyclone separator 40.

・ Magnetic separation (H)
The concentrate having a predetermined particle size (for example, 0.020 to 0.25 mm) that has been classified by the cyclone separator 40 having the particle size adjustment (I) is subjected to magnetic separation by the wet magnetic separator 41. Here, for example, a wet magnetic separator with a drum-type permanent magnet having a magnetic force of about 1000 gauss is used, and magnetically separated and magnetically separated materials are separated. The discarded magnetic deposits are mainly iron oxides having ferromagnetism, and the non-magnetic deposits are recovered as concentrate.

・ Reverse Flotation (A)-Flotation (B)
The concentrate (non-magnetized material) separated by the magnetic separation (H) is stored in the conditioner tanks 11a and 11b as shown in FIG. Etc.). As mentioned earlier, this reverse flotation process separates the gangue content as a floating substance (floss) and collects the concentrate as a sediment (sink). Therefore, it should be separated and removed as a floating substance. A cation scavenger for adsorbing on the surface of the gangue is added to improve hydrophobicity and foaming properties, and starch is added to make the concentrate hydrophilic to facilitate settling. Further, the pH of the aqueous solution is adjusted to 10 or more (preferably 11 or less) in order to promote the dispersion of the mineral particles.
The concentrate (slurry) whose components have been adjusted in the conditioner tank 11a and the conditioner tank 11b is sent to the flotation machine 10 for reverse flotation, and the gangue composed mainly of quartz is separated as a flotation. It is removed (discarded) and the concentrate is recovered as sediment (sink).

The concentrate (sediment) collected by the reverse flotation (A) is stored in the conditioner tanks 13a and 13b, where the components are adjusted for the flotation (addition of water and additives, etc.). As mentioned earlier, in this flotation, the concentrate is recovered as a float (floss) and the gangue is separated as a sediment (sink). For this reason, concentrate and other heavy minerals An anion scavenger is added to make the (pulse component) selective, and hydrofluoric acid (inhibitor) is added to make it hydrophilic by adsorbing on the surface of the gangue to be separated and removed Furthermore, a foaming agent is added to generate bubbles. Further, the pH of the aqueous solution is adjusted to 2 to 3 in order to ensure the floatability of the concentrate.

The concentrate (slurry) whose components have been adjusted in the conditioner tank 13a and the conditioner tank 13b is sent to the flotation machine 12, where flotation is performed, and the gangue content mainly composed of kyanite and zircon is deposited (sink). As a result, the suspended matter (floss) is recovered as concentrate.
In addition, there are Agitair type floating beneficiator and Denver type A flotation beneficiary machine, but any of the beneficiary machines is used for reverse flotation (A) or flotation (B). May be. The sediment (sink) is settled by a thickener and dehydrated by a dehydrating means (such as a dewatering screen). Moreover, the overflow water treated by the thickener is recycled as process water. In FIG. 4, 14 is a dehydrating screen.

・ Specific gravity beneficiation (C)
The concentrate (floss) recovered by the flotation (B) is sent to a vibration table 60 that is a specific gravity separator, and further separated into concentrate and tailing. Usually, as the vibration table 60, a James table is used.
・ Drying treatment (D)
The concentrate recovered by the specific gravity separation (C) is dried by a dryer 70 such as a rotary dryer.
・ Magnetic separation (E)
The concentrate dried by the drying process (D) is magnetically selected by a dry high magnetic separator 80 to obtain a concentrate that is a non-magnetic deposit. As the dry type high magnetic separator 80, a rare earth roll separator is preferable.
By passing through the above steps, a titanium dioxide concentrate having a TiO ₂ content of 90% by mass or more (preferably 95% by mass or more) can be obtained.

In the present invention, the processes other than the reverse flotation (A) and the flotation (B) are optional. For example, various processes as shown in FIG. 1 and FIGS. 2 to 4 are appropriately combined as necessary. Can be implemented. Also, in the embodiments of FIG. 1 and FIGS. 2 to 4, the specific gravity ore (G), the particle size adjustment (I) and the magnetic ore beneficiation (H) are omitted, and the reverse floating beneficiation is performed on the ore that has undergone the particle size adjustment (F) (A) and flotation (B) may be performed sequentially. Alternatively, in the embodiment of FIG. 1 and FIGS. 2 to 4, the specific gravity (C), the drying process (D) and the magnetic ore (E) are omitted, and instead, the reverse flotation (A) and the flotation ( B) may be repeated two or more times. That is, the following embodiments (1) to (3) can be obtained. In the particle size adjustment (F) in the embodiments (1) and (3) below, the particle size of the ore is made sufficiently smaller than the particle size adjustment (F) in the embodiments of FIG. 1 and FIGS. 0.025 mm or less).
(1) Grain size adjustment (F) → Reverse flotation (A) → Flotation (B) → Specific gravity (C) → Drying (D) → Magnetic ore (E)
(2) Grain size adjustment (F)-> specific gravity beneficiation (G)-> particle size adjustment (I)-> magnetic beneficiation (H)-> [reverse flotation (A)-> flotation (B)] is repeated twice or more (3) particle size Repeat adjustment (F) → [reverse flotation (A) → flotation (B)] two or more times

The rutile ore from Minas Gerais, Brazil, was selected according to the processing conditions shown in FIGS. 2 to 4 under the following conditions. Table 1 shows the raw ore grade and concentrate (product) grade.

Supply ore (grain size of 100 mm or less) mined from the mountain to the drum washer 20 having a sieve size (opening) of 20 mm through the vibration feeder 25 at 500 t / h (t / h: tonnage per hour; the same applies hereinafter) While classifying. The +20 mm ore was crushed with a crusher 21 (cone crusher) to −20 mm and re-loaded into the drum washer 20. The -20 mm ore was sieved with a sieve 22 having a mesh size of 1 mm, and the +1 mm ore was pulverized with a wet pulverizer 23 (ball mill) and sieved again with the sieve 22. The crushing step was a closed circuit, and the total amount of ore was -1 mm ore, but the ore supplied to the cyclone separator 24 in the next step was 500 t / h.

The -1 mm ore was classified by the cyclone separator 24, and fine powder (-0.020 mm) was separated using 0.020 mm as the classification point. In this cyclone separator 24, the inflow pressure was set to 1 kg / cm ² so that the classification point was 0.020 mm. The fine powder (-0.020 mm) separated by the cyclone separator 24 was 35 t / h, and this was discarded as tailings. The concentrate (0.020 to 1 mm) sent to the next step was 465 t / h.
Next, it is supplied to the first stage spiral specific gravity sorter 30 and sorted into concentrate C (concentrate), intermediate M (mid ring) and tailing T (tailing). The material was supplied to the spiral-type specific gravity separator 31 for selection. The supply amount to the second-stage specific gravity separator 31 is as follows: concentrate C: 35 t / h (8 mass%), intermediate M: 115 t / h (25 mass%), tailing T: 315 t / h (67 Mass%).

The concentrate (secondary concentrate) obtained by the second-stage specific gravity separator 31 is 25 t / h, the amount discarded as tailing is 440 t / h, and the obtained concentrate is the cyclone separator from the previous process. It was 5.4% by mass of the concentrate supplied from No. 24. The concentrate obtained by this specific gravity separation was classified by the second-stage cyclone separator 40, and + 0.25mm was separated using 0.25mm as the classification point. In this cyclone separator 40, the inflow pressure was set to 1 kg / cm ² so that the classification point was 0.25 mm. The amount of +0.25 mm concentrate produced was 15 t / h, which was pulverized by the wet pulverizer 41 and then classified by the third-stage cyclone separator 42. The classification point of the third-stage cyclone separator 42 was 0.020 mm, −0.020 mm was used as tailings and discharged out of the system, and +0.020 mm was recycled to the second-stage cyclone separator 40. The concentrate (tertiary concentrate) classified by the second-stage cyclone separator 40 and sent to the next process was 23 t / h.

Next, the magnetized material and the non-magnetized material were separated by magnetic separation using a wet magnetic separator 40 equipped with a 1000 gauss drum-type permanent magnet. The ratios of the magnetized product and the non-magnetized product were 98.7% by mass and 1.3% by mass.
The concentrate (magnetized material) selected by magnetic ore beneficiation was sequentially stored in the conditioner tanks 11a and 11b, and the components were adjusted for reverse flotation. In the conditioner tank 11a, a caustic soda (NaOH) solution was added to make the pH value in the range of 10 to 11, and 600 g / t of starch as an inhibitor was added. Next, in the conditioner tank 11b, 300 g / t of “EDA3” was added as a cation scavenger. The conditioning time (time taken to acclimate after adding additives) was 5 minutes.

An agitaire type flotation machine was used as the flotation machine 10, and reverse flotation was performed in two stages (coarse-cleaning). The air pressure supplied into the treatment tank was 2 kg / cm ² , and the rotation speed of the impeller was 1000 rpm.
The sink (precipitate) obtained by this reverse flotation was 15.7 t / h, and the floss (float) was 7 t / h, and the ratios were 69.1 mass% and 30.9 mass%, respectively. This sink (sediment) was sequentially stored in the conditioner tanks 13a and 13b, and the components were adjusted for the flotation. In the conditioner tank 13a, a 50% strength hydrochloric acid solution is added to adjust the pH value to 3, and hydrogen fluoride as an inhibitor is 1000 g / t, and “AEROFROTH 65” (synthetic alcohol-based foaming agent) is used as a foaming agent. 1 g / t was added respectively. Next, in the conditioner tank 13b, 200 g / t of “Flotinor 1683” was added as an anion scavenger. The conditioning time (time taken to acclimate after adding additives) was 5 minutes.
Using an agitaire type flotation machine as the flotation machine 12, flotation was performed in three stages (coarse-selection-re-selection). went. The air pressure supplied into the treatment tank was 2 kg / cm ² , and the rotation speed of the impeller was 1000 rpm.

Here, the floss separated by reverse flotation (floss 1 separated by the first stage “rough fractionation”, floss 2 separated by the second stage “cleaning”) and flotation separated Sink 1 (sink 1 separated in the first stage “rough selection”, sink 2 separated in the second stage “selection”, and sink 3 separated in the third stage “reselection”) Table 2 shows the balance of each component of TiO ₂ , Fe ₂ O ₃ , SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , and Zr ₂ O for the concentrate after reverse flotation-flotation.

As shown in Table 2A and Table 2B, in reverse flotation, as Floss 1, Fe ₂ O ₃ : 15.9 mass%, SiO ₂ : 79.34 mass%, Al ₂ O ₃ : 34.22 mass% , P ₂ O ₅ : 35.87 mass%, Zr ₂ O: 58.0 mass% are removed, and Floss 2 is Fe ₂ O ₃ : 2.4 mass%, SiO ₂ : 9.71 mass%, Al ₂ O ₃ : 5.96 mass%, P ₂ O ₅ : 4.28 mass%, and Zr ₂ O: 11.8 mass% were removed. In the subsequent flotation, as the sink 1, Fe ₂ O ₃ : 62.9 mass%, SiO ₂ : 10.59 mass%, Al ₂ O ₃ : 52.92 mass%, P ₂ O ₅ : 48.6 mass% , Zr ₂ O: 18.2% by mass was removed, and as the sink 2, Fe ₂ O ₃ : 14.8% by mass, SiO ₂ : 0.32% by mass, Al ₂ O ₃ : 6.04% by mass, P ₂ O ₅ : 8.83 mass%, Zr ₂ O: 8.1 mass% are removed, and the sink 3 is Fe ₂ O ₃ : 1.3 mass%, Al ₂ O ₃ : 0.45 mass%, P ₂ O ₅ : 0.76 mass% and Zr ₂ O: 0.6 mass% were removed. As a result, a concentrate containing 30.4% by mass of TiO ₂ was obtained.

＊１　フロス１，２：逆浮遊選鉱（Ａ）のフロス
　　　シンク１~３：浮遊選鉱（Ｂ）のフロス
　　　精鉱：逆浮遊選鉱（Ａ）−浮遊選鉱（Ｂ）後の精鉱

* 1 Floss 1, 2: Floss of reverse flotation (A) Sink 1-3: Floss of flotation (B) concentrate: Reverse flotation (A)-concentrate after flotation (B)

Floss (floating matter) obtained by flotation was 12.7 t / h, and because it contained fine particles and fine particles, specific gravity beneficiation was performed with a vibrating table 60 (James table), which is a specific gravity sorter. The concentrate (quaternary concentrate) thus obtained was 9.7 t / h.
Next, after this concentrate was dried with a dryer 70, it was magnetically selected at 9000 gauss in a dry high magnetic separator 80 (rare earth roll separator) to obtain a product titanium dioxide concentrate as a non-magnetized product. The obtained concentrate was 7.5 t / h, and as shown in Table 1, the TiO ₂ content was 94% by mass.

DESCRIPTION OF SYMBOLS 10 Flotation machine 11a, 11b Conditioner tank 12 Flotation machine 13a, 13b Conditioner tank 14 Dehydration screen 20 Drum washer 21 Crusher 22 Sieve 23 Wet crusher 24 Cyclone separator 25 Vibrating feeder 30, 31 Specific gravity separator 40 Wet cyclone separator 41 Wet Crusher 42 Cyclone separator 50 Wet magnetic separator 60 Vibrating table 70 Dryer 80 Dry high magnetic separator

Claims (9)

A method for obtaining a concentrate with an increased concentration of titanium dioxide by beneficiating titanium dioxide ore,
In conducting reverse flotation (A) and flotation (B) in order to powdery titanium dioxide ore,
In reverse flotation (A), a cation scavenger and starch are added, and the concentrate is settled and separated in an aqueous solution whose pH is adjusted to 10 or more.
In the flotation (B), an anion scavenger, hydrofluoric acid, and a foaming agent are added, and the concentrate is floated and separated in an aqueous solution adjusted to pH 2 to 3. Manufacturing method of ore. 2. The titanium dioxide concentrate according to claim 1, wherein the concentrate separated by floatation in the flotation (B) is subjected to specific gravity (C), drying (D), and magnetic separation (E) in this order. Production method. 3. The method for producing a titanium dioxide concentrate according to claim 2, wherein in the magnetic separation (E), dry high magnetic separation is performed at 8000 gauss or more. Specific gravity ore (G) and magnetic ore beneficiation (H) are sequentially applied to the powdered titanium dioxide ore obtained through the particle size adjustment (F), and then reverse flotation (A) and flotation (B) are successively applied. The method for producing a titanium dioxide concentrate according to any one of claims 1 to 3. The method for producing a titanium dioxide concentrate according to claim 4, wherein in the particle size adjustment (F), the titanium dioxide ore is pulverized and classified to obtain powdered titanium dioxide ore. 6. The method for producing a titanium dioxide concentrate according to claim 4 or 5, wherein the concentrate subjected to specific gravity (G) is subjected to particle size adjustment (I) and then subjected to magnetic separation (H). The specific gravity beneficiation (C) and the specific gravity beneficiation (G) are characterized in that at least one of a beneficiation with a table type beneficiary machine, a beneficiation with a spiral beneficiary machine, and a beneficiation with a jig type beneficiary machine is performed. The manufacturing method of the titanium dioxide concentrate in any one of. The method for producing a titanium dioxide concentrate according to any one of claims 1 to 7, wherein the titanium dioxide ore is a rutile ore. The method for producing a titanium dioxide concentrate according to any one of claims 1 to 8, wherein the titanium dioxide concentrate has a titanium dioxide content of 90% by mass or more.

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