JP2001321695A - Collecting agent for concentrating niobium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently recover niobium and to obtain a collecting agent for concentrating niobium having an excellent sorting effect. SOLUTION: This collecting agent for concentrating niobium consists of polyamines expressed by formula (1). In formula (1), R is an 8-22C straight-chain or branched-chain hydrocarbonic radical, (x) is a number of 1 to 5, (y) and (z) are each a number of 0 to 5, however (y) and (z) are never 0 at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a scavenger for niobium beneficiation.

[0002]

BACKGROUND OF THE INVENTION Flotation has long been known as a method for separating minerals and coal. In this method, the ore is usually finely ground, and then turned into a water slurry. Then, the ore is put into a beneficiation tank, a scavenger, a foaming agent, a pH adjuster, and the like are added, followed by stirring and blowing air.
This is a method in which a target substance is attached to foam to separate it.
There is also a reverse flotation method in which undesired minerals are floated after being separated from valuable minerals, and a target substance is settled.

[0003] In such a flotation method, a trapping agent having a function of making the surface of a target substance in a mineral hydrophobic so as to easily adhere to bubbles is used. And cation scavengers. Examples of the anion scavenger include hydrogen sulfide compounds such as alkyl dithiocarbonate, dialkyl dithiophosphate, dialkyl dithiocarbamate, and mercaptobenzothiazole, and oxyhydrogen compounds such as carboxylate, alkyl sulfate, and alkyl sulfonate. As cation scavengers, lower alkylamines, primary amines such as tallowamine, secondary amines such as dialkylamines, primary etheramines, etherdiamines and salts thereof, fatty acids such as tall oil fatty acids and salts thereof are generally used. It is used. In addition, petroleum fractions such as light oil, kerosene, and heavy oil A are used for coal and the like.

[0004] The performance required of these scavengers is to achieve a high recovery rate of the target substance, to have an excellent sorting effect, and to exhibit an excellent dehydration rate in the subsequent dehydration step. However, it has heretofore been difficult to obtain a scavenger that satisfies all of these properties, particularly a scavenger for niobium beneficiation.

[0005] An object of the present invention is to provide a niobium ore trapping agent which sufficiently satisfies the above performance.

[0006]

The present invention is a niobium ore trapping agent comprising a polyamine represented by the formula (1) (hereinafter referred to as polyamine (1)).

[0007]

Embedded image

(Wherein, R is a linear or branched hydrocarbon group having 8 to 22 carbon atoms, x is a number of 1 to 5, y and z are each a number of 0 to 5, provided that y and z are each a number of 0 to 5). Do not become 0 at the same time.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the polyamine (1) of the present invention, R has preferably 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms from the viewpoint of liquidity and workability at room temperature. Further, it may be a hydrocarbon group having a mixed composition. x is preferably 1 to 2, and particularly preferably 1. y and z are preferably numbers such that the sum of them is 1 to 4, and particularly preferably 1 to 3.

[0010] Examples of the polyamine (1) include the following, among which (b), (c), (d), (h),
(i) is preferred, and (b), (c) and (d) are particularly preferred.

[0011]

Embedded image

The polyamine (1) is obtained by reacting a compound represented by the formula (2) (hereinafter referred to as compound (2)) or a compound represented by the formula (3) (hereinafter referred to as compound (3)) with acrylonitrile. After cyanoethylation, it is obtained by performing a hydrogenation reaction.

[0013]

Embedded image

(Wherein, R is as defined above, and m is 1 to
Shows the number 3. As a specific example of the compound (2), N-myristyl-N-
Aminopropylpropylenediamine, N-stearyl-
N-aminopropyl propylene diamine, N-tallow alkyl-N-aminopropyl propylene diamine and the like can be mentioned.

M in the compound (3) is 1 to 3,
2 is preferable, and it may be a mixture. Specific examples of the compound (3) include N-myristylpropylenediamine, N-stearylpropylenediamine, N-tallowalkylpropylenediamine, N-palm oil alkylpropylenediamine, N-tallowalkyldipropylenetriamine, and N-tallowalkyl. Tripropylenetetramine and the like.

The polyamine (1) preferably has a solidification temperature of 20 ° C. or lower in that it is liquid at 20 ° C. and excellent in workability.
In addition, the solidification temperature mentioned here is measured by JIS K-2269.

The scavenger of the present invention comprising the polyamine (1) varies depending on the particle size of the niobium fine powder or the niobium-containing ore fine powder as the substance to be captured. 2% by weight is preferred, and particle size 2
0.00 for 60-80% by weight of 00 mesh pass
3 to 0.1% by weight is more preferred. It may be used by mixing with other scavengers.

Regarding the method of adding the scavenger of the present invention, the required amount of the entire scavenger may be added at once, but it is preferable to add the scavenger in several portions. For example, it is effective to repeat the addition 4 to 6 times.

The scavenger of the present invention is preferably used in combination with a foaming agent, a pH adjuster and the like. The foaming agent is required to generate a lot of bubbles in the beneficiation tank, increase the gas-liquid interface, stabilize the foam, and at the same time, remove the foam from the beneficiation tank and quickly eliminate bubbles. Is done. As a foaming agent, pine oil, camphor oil, methyl isobutyl carbinol, glycol ether, tall oil ethylene oxide adduct and the like are used. The pH adjuster is added to carry out flotation at the optimum pH, sulfuric acid, hydrochloric acid,
Sodium carbonate, sodium hydroxide, lime and the like are used.

When the scavenger of the present invention is used as a scavenger for separating niobium from a niobium-containing ore,
It has a particularly excellent effect as compared with conventional scavengers.

[0021]

EXAMPLES In the synthesis examples, the solidification temperature was measured according to JIS K-2269. Parts and percentages are by weight unless otherwise specified.

Synthesis Example 1 N-tallow alkylamine (275 g, 1 mol) was placed in a flask and heated to 60 ° C., and then acrylonitrile (132.5 g, 2.
5 mol) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 95 ° C. for 5 hours to obtain a cyanoethylated product. 357 g of the obtained cyanoethylated product and 4 g of Raney nickel were placed in an autoclave, the temperature was raised to 130 ° C., hydrogen was introduced, and a hydrogenation reaction was carried out for 5 hours while maintaining a constant pressure of 1.47 MPa. After the completion of the reaction, the system was cooled, and Raney nickel was removed by filtration.
By distillation and purification, N-tallow alkyl-N-aminopropylpropylenediamine (a compound in the formula (2) where R = tallow alkyl group) was obtained.

The obtained amine (196 g, 0.5 mol) was placed in a flask, heated to 60 ° C., and then treated with acrylonitrile (13.3 g).
g, 0.25 mol) was added dropwise over 2 hours. After dropping, 95 ° C
For 5 hours to obtain a cyanoethylated product. 153 g of the obtained cyanoethylated product and 2 g of Raney nickel were put into an autoclave, the temperature was raised to 130 ° C., hydrogen was introduced, and 1.47 MPa
The hydrogenation reaction was performed for 5 hours while maintaining the pressure at a.
After completion of the reaction, the reaction mixture was cooled, Raney nickel was removed by filtration, and purification by distillation was performed to obtain N-tallow alkyltetramine (in the formula (1), R = tallow alkyl group, x = y = 1,
z = 0) was obtained. The solidification temperature of the obtained N-tallow alkyltetramine was 3 ° C.

Comparative Synthesis Example 1 N-tallow alkyl propylene diamine (332 g, 1 mol)
Into a flask and heated to 60 ° C, then add acrylonitrile
(53.0 g, 1.0 mol) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 95 ° C. for 5 hours to obtain a cyanoethylated product. 304 g of the obtained cyanoethylated product and 4 g of Raney nickel were put in an autoclave, and a hydrogenation reaction was carried out under the same conditions as in Synthesis Example 1. After cooling the reaction product to 60 ° C and replacing hydrogen in the system with nitrogen, acrylonitrile (53.0 g, 1.0 mol)
To carry out a hydrogenation reaction. afterwards,
Further, acrylonitrile (26.5 g, 0.5 mol) was reacted to carry out a hydrogenation reaction, and Raney nickel was removed by filtration to obtain N-tallow alkylpolyamine.

The N-tallow alkylpolyamine is represented by the formula (1)
R = tallow alkyl group, x = z = 0, a mixture of a compound of y = 2 and a compound of y = 3, which was a solid at 25 ° C. and a solidification temperature of 45 ° C.

Example 1 and Comparative Examples 1 to 5 An aqueous slurry containing 20% of ore (containing 3.0% as niobium) crushed to a particle size of 200 mesh 60% pass (niobium content 0.6%, silica content 3.0%). 0%) to 100 kg
The scavenger of the present invention shown in Table 1 was used in an amount of 50
g (hereinafter abbreviated as g / t) was added, and 60 g / t of a tall oil ethylene oxide 15 mol adduct was added as a foaming agent, and the pH of the slurry was adjusted to 3.0 using sulfuric acid. The flotation was performed for about 1 hour, and the niobium content and the silica content in the obtained flotation floss and the mineral after the flotation were measured by the following methods. As a comparative product, a solid amine (added as a 5% acetate aqueous solution) or a liquid amine shown in Table 1 as an effective component was added at 50 g / t, and the niobium content and the silica content were measured in the same manner. Table 1 shows the results.

<Method for measuring niobium content> Pyrogallol method (JI
SG 1231). That is, 1 g of a sample is 500 ml
Was weighed into a conical beaker, added with hydrochloric acid and nitric acid, decomposed by heating, added with 30 ml of perchloric acid, and then heated to generate a thick white smoke of perchloric acid. After cooling, 10 ml of hydrochloric acid and warm water were added to make the liquid volume 200 ml, and 40 ml of sodium sulfite solution (20%) and a small amount of filter paper pulp were added, followed by boiling for about 10 minutes. After standing for a while, the mixture was filtered using filter paper type 5 C and washed with hot hydrochloric acid (2%). The precipitate was transferred to a porcelain crucible together with the filter paper, dried, and ignited to incinerate the filter paper. After allowing to cool, 5 g of potassium disulfate was added, and the mixture was ignited at about 700 ° C. for 10 minutes to be melted. 5 ml of the solution was taken out into a 100 ml volumetric flask, and 10 ml of a sodium sulfite solution (20%) and 30 ml of a pyrogallol solution (30%) were added. And made niobium color. 430 nm wavelength with blank test solution as control
The absorbance in the vicinity was measured, and the niobium content was determined from a calibration curve prepared in advance. The target value for the niobium content is 70% or more. <Silica content measurement method> The content was determined by the silicomolybdic acid method.
That is, 3 g of sodium hydroxide is added to 0.1 g of a sample, boiled in a nickel beaker, dissolved in water, and adjusted to pH with 1N sulfuric acid.
1.5. It 1N sulfuric acid 10 ml, ammonium molybdate solution _{((NH 4) 6 Mo 7} O 24 · 4H 2 O 5
Dissolve 2.97 g in water and pH 7.3 with sodium hydroxide.
10 ml), and the volume was adjusted to 50 ml with water. Five minutes after the addition of the ammonium molybdate solution, the absorbance at 400 nm was measured with a 1 cm cell using water as a control,
The silica content was determined from a previously prepared calibration curve. The target value for the silica content is 0.5% or less.

[0028]

[Table 1]

[0029]

The scavenger for niobium beneficiation of the present invention is a scavenger which does not need to be prepared in an aqueous solution because it is in a liquid state, is very easy to handle, has a high recovery amount of niobium, and has an excellent sorting effect. .

Claims (1)

[Claims] A scavenger for niobium beneficiation comprising a polyamine represented by the formula (1). Embedded image (Wherein, R is a straight-chain or branched-chain hydrocarbon group having 8 to 22 carbon atoms, x is a number of 1 to 5, y and z are each a number of 0 to 5; It will not be.)