JPS60238174A - Flotation of rare earth mineral - Google Patents

Abstract

PURPOSE:To separate and recover mineral high in rare earth element content with high yield, by using a compound containing a sulfonic group and a carboxyl group as a collector and together using a depressant to perform flotation at a specific pulp temp. CONSTITUTION:In separating rare earth mineral from a complicated ore containing rare earth mineral and fluorite by a flotation process, not only a compound having both of a sulfonic group and a carboxyl group in the molecule thereof (e.g., sulfosuccinate) is used as a collector but also a depressant (e.g., sodium silicate) is together used and pulp temp. is set to 30-70 deg.C to selectively float and recover rare earth mineral. By this method, mineral high in rare earth element content can be separated and recovered even from a complicated ore containing fluorite or barite and low in rare earth element content.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for flotation of rare earth minerals, and in particular, to flotation of rare earth minerals (typically bastnaesite: LnCO, F.
...Ln represents a rare earth element) and hematite (Fe
203), limonite (Fe()OH), barite (Ba
SO4), fluorite (CaF2), quartz (Sin, ), calcite (CaCO3), dolomite ((Ca, Mg)C
og ], apatite r Ca, (PO,'), (F-
CI-0H) 1-Nigiline (Na2F e S 50
6), amphibole, mica, stochinthianite (SrC
O8), pyrite (F e St), ilmenai)
The present invention relates to a method for separating and concentrating rare earth minerals at high concentrations from complex ores containing various minerals such as (FeTIOa).

[Conventional technology]

Rare earth elements are used in glass, sejax, alloys, electronic components,
It is attracting attention as a new material in various fields such as catalysts, and demand for it continues to grow. More than 200 types of minerals containing rare earth elements are known, but the most important mineral resources among them are bastnaesite,
They are considered to be monazite [(Ln, Th%Y)PO,) and xenotime ((Ln, Y)PO4). As for its reserves, for example, it is estimated that about 5 million tons of bastnaesite is found in Mountain Pass Mt., California, USA, and it is a complex mineral along with gangue minerals such as bastnaesite, barite, calcite, quartz, and melk. It exists as.

Bastnaesite, etc. in these complex ores are dispersed in the ore in the form of fine iron beams, so in order to separate bastnaesite, etc. from the ore, it is necessary to pass through 100 meshes, for example, at least 96 pieces. It was necessary to pulverize the mineral to a fine powder and separate it from the gangue minerals by a complex flotation method as described below.

In other words, the typical flotation method currently in use is to maintain the pulp at around 98°C and add soda ash to adjust the pH to about 9.5.
In this method, the oleic acid-based scavenger and anthonium geninsulfonate (inhibitor for carbonate minerals and sulfate minerals) are added, and after rough selection, the process is divided into five stages of fine selection. YO #) Obtained about 63% concentrate [S, Il, D
ayton: Mining World (1956
Month, pp. 43-45)].

[Problem that the invention seeks to solve]

The conventional flotation method described above can be applied with some degree of efficiency to complex ores containing a relatively small amount of fluorite as a gangue mineral, but it is difficult to remove rare earth minerals from complex ores containing a large amount of fluorite. It was difficult to flotate with satisfactory efficiency. Under these circumstances, the present invention aims to provide a flotation method that can efficiently separate and concentrate rare earth minerals even from complex ores containing large amounts of fluorite and barite.

[Means for solving problems]

The present invention provides a novel flotation method that satisfies the above-mentioned objectives, and in which rare earth minerals are separated from complex ores containing rare earth minerals and fluorite by flotation, a sulfone group is added in the molecule as a scavenger. The main idea is to use a compound having both a carboxyl group and an inhibitor, set the pulp temperature at 30 to 70°C, and selectively suspend and recover rare earth minerals.

[Effect]

The effects of the present invention will be explained in detail below following the experimental history. In the experiment, we used bastnaesite, a typical epilithic earth mineral.

Recognizing that in order to efficiently separate bastnaesite in complex ores, the present inventors first need to find the optimal scavenger, we investigated the buoyancy of typical minerals contained in complex ores. To clarify, bastnaesite, fluorite, barite,
High-purity products of hematite and quartz were prepared, and the particle sizes were adjusted to 149 to 210 μm), and the relationship between pulp pn and the floatability of each mineral was investigated using various scavengers. As a scavenger, sodium dodecylbenzenesulfonate (DBSNa) and sodium dodecyl sulfate (DSN
sr), sodium oleate (Na07) and dodecylammonium chloride (DAC), and the flotation rate was determined using a Halmond tube.

The results are shown in Figures 1 to 4).The degree of floating rate and the pH range showing the highest floating rate vary depending on the type of scavenger and the type of mineral, but which scavenger is used. Even in this case, under the conditions in which bastnaesite floats, fluorite and barite also show higher buoyancy, so it is not possible to selectively float only bastnaesite. However, when DBSNa, DSNa and Na01 are used among the above scavengers, when hematite and quartz are floated under the condition that the scavenger concentration is I x 10-' mol)-
Only fluorite and barite can be floated outside the bastnasite 14 site, and a certain bastnaesite concentration effect can be expected. In addition, there is a sulfone group (-8
on-), and DBNa has a sulfate group (on-) in its molecule.
804), the effects of both scavengers are similar, but the sulfone group-containing compound is slightly better in improving the floating rate for fluorite, barite, and bastnaesite.

Also, Mail which has a carboxyl group in the molecule is also
It exhibits a selective flotation rate improvement effect on seed minerals.

Therefore, we conducted an experiment thinking that if a compound having both a sulfone group and a carboxyl group in one molecule was used as a scavenger, it would be possible to further improve the buoyancy of the three minerals mentioned above. Examples of metal compounds having both a sulfone group and a carboxyl group in one molecule include sulfonated higher fatty acid salts (for example, R-(CH!)n-COONm) and sulfosuccinates, but in the following experiments, representative compounds were used. We investigated its performance as a scavenger using sulfosuccinate.

Figure 5 shows the results. It shows the floating rate of each mineral when the pulp pH is changed.

As is clear from this result, when sulfosuccinate is used as a scavenger, it is possible to selectively float only bastnaesite, fluorite, and barite, without floating quartz or hematite at all. The most effective selective floating rate improvement effect is DBSNa.

It is far superior to DSNa and NaOI.

By the way, Table 1 below shows the results of an ore flotation experiment when a complex ore containing bastnaesite was finely pulverized and Mail or sulfosuccinate was used as a scavenger, and the concentration effect of bastnaesite was This can be determined based on the Ce concentration.

As is clear from Table 1, sulfosuccinate is Mai
It shows a much superior rare earth element concentration effect compared to 1, and this effect can be further enhanced by using an appropriate amount of an inhibitor.

However, as explained in FIG. It is not possible to separate only nessite by floating it, and there are limits to the effect of concentrating rare earth elements.

Therefore, we thought that there might be conditions that could reduce the buoyancy rate of fluorite and barite, and conversely increase the buoyancy rate of bastnasite. Further consideration was given. As a result, when an inhibitor was used together with a sulfosuccinate scavenger, the buoyancy of fluorite and barite changed significantly depending on the pulp temperature.
New findings were obtained in that as the pulp temperature rises, fluorite and barite become significantly more difficult to float. That is, Fig. 6 shows
When sodium silicate (inhibitor) is used in combination with sulfonic acid salt (scavenger) (also listed when no inhibitor is used)
This is a graph showing the relationship between the pulp temperature and the floating rate of fluorite and barite.The floating rate of fluorite and barite is 1 when the pulp temperature is 1! i: t - It becomes significantly lower by increasing the temperature to 80°C or higher. Figure 7 shows the results of an experiment similar to the above except that aluminum chloride was used as the inhibitor. As is clear from this figure, in the case of barite, when aluminum chloride is used as an inhibitor and the pulp temperature is raised to 80° C. or higher, the flotation rate decreases rapidly. On the other hand, in the case of fluorite, even if aluminum chloride is used as an inhibitor and the pulp temperature is increased, the floating rate hardly decreases.

Therefore, when attempting to suppress the floating of fluorite, aluminum chloride must not be added alone as an inhibitor, but must be used in combination with sodium silicate.

Incidentally, Figure 8 shows the effect of suppressing fluorite when the amount of aluminum chloride added is changed in a pulp system containing sodium silicate as an inhibitor. As is clear from this figure, appropriate amounts of sodium silicate and aluminum chloride are used together as inhibitors, and the pulp temperature Jt'ftBO'C
If the temperature is increased above, the floating of fluorite can be effectively suppressed.

Next, in order to clarify the effect that the concentration of inhibitory suction had on the flotation rate of fluorite and barite, we conducted a flotation experiment with varying concentrations of inhibitor. ,1
The results shown in Figure 0 were obtained. According to this result, when using sodium silicate as an inhibitor, its concentration t-2
By setting the concentration to 000 MI/1 or more, the floating rate of fluorite and barite can be suppressed to a low level, and when aluminum chloride is used as an inhibitor, by setting the aluminum ion concentration to 2 oomy/1 or more. The floating rate of fluorite and barite can be suppressed to a low level.

The above experiment confirmed that the floating rate of fluorite and barite can be suppressed, but it is unclear what kind of floating behavior bastnaesite exhibits under such conditions. This remains unclear.

Therefore, we conducted an experiment to clarify the buoyancy of bastnaesite under conditions that can sufficiently suppress the buoyancy of fluorite and barite, and found that it showed a very unique tendency as shown in Figure 11.12. was confirmed. In other words, in the case of bastnaesite, in a pulp system using a combination of sulfosuccinate and an inhibitor, the flotation rate increases rapidly as the temperature increases, and when the pulp temperature ranges from 30 to 70°C, fluorite and barite increase. Bastnaesite also shows a higher flotation rate than Ishiyoshi.

That is, in a pulp system in which a compound having a sulfone group and a carboxyl group in the same molecule is used as a scavenger and an inhibitor is also used, if the pulp temperature is set in the range of 30 to 70°C, fluorite and barite can be removed. It is possible to suppress the floating rate of stones to a low level and selectively increase only the floating rate of rare earth minerals.Using this phenomenon, it is possible to selectively increase the floating rate of rare earth minerals from complex ores including fluorite and barite. It can be separated and recovered with high yield.

〔Example〕

Complex ore containing rare earth minerals (Ce content: 4.52% (C
e+L a+P r+Nd ) content: 9.25%) was finely pulverized to a particle size of 50 μm or less, and flotation was performed six times under the conditions shown in Table 2. A sulfosuccinate (trade name: Aeropromoter 845, manufactured by American Cyanamid, USA) was used as a scavenger, and sodium silicate and aluminum chloride were used in combination as inhibitors.

The results are shown in Table 2.

As is clear from Table 2, if flotation is carried out at a pulp temperature of around 50°C using sulfosuccinate as a scavenger and an inhibitor, rare earth minerals can be efficiently and selectively suspended. By repeating flotation about 5 times, the rare earth element concentration can be increased to 55% or more.

[Effect of revelation]

The present invention is constructed as described above, but the key point is that a compound containing sulfonic acid and carboxylic acid is used as a scavenger, and an inhibitor is used in combination to carry out flotation at a pulp temperature of 30 to 70°C. Additionally, minerals with high rare earth element content can be separated and recovered in high yield even from complex ores containing fluorite, barite, etc. and low rare earth element content.

[Brief explanation of drawings]

Figures 1 to 5 are graphs showing the relationship between the floating rate of various minerals and pulp pH when various scavengers are used;
．． Figure 7 is a graph showing the relationship between the floating rate of fluorite and barite and pulp temperature when a sulfosuccinic acid scavenger and an inhibitor are used together, and Figure 8 is a graph showing the relationship between the floating rate of fluorite and barite and the pulp temperature when a sulfosuccinic acid scavenger and an inhibitor are used together. A graph showing the relationship between the A1 ion concentration and the floating rate of fluorite in the F thread, Figures 9 and 10 are graphs showing the relationship between the concentration of the inhibitor and the floating rate of fluorite and barite, Figure 11゜1
Figure 2 is a graph showing the relationship between the buoyancy rates of bastnaesite, fluorite, and barite and pulp temperature. Applicant Kobe Steel Co., Ltd. Representative Patent Attorney Hisashi Ueki, Ui゛°Pa, -1 ゛・Nξ ■＋ Ho Ryu (company) 赴 夀書 (Mr.) Noh Hyōka ([President]) 枇 Slim F! ＃He hesitate (Ryo) 耽 摺 美 (cold) 迴 擢 謬 MAI) 枇 dan 晧 (亭) 赴擢餠 まし) Noh 擲 1 (ゆ) 咄 Slimming Mochi まし) vague 擢 (about todan (Yu)

Claims (1)

[Claims] When separating rare earth minerals from complex ores containing rare earth minerals and fluorite by the flotation method, a compound having both a sulfone group and a carboxyl group in the molecule is used as a scavenger, and a suppressor is also used. and reduce the pulp temperature to 30
A method for flotation of rare earth minerals, characterized by selectively floating and recovering rare earth minerals at a temperature of ~70°C.