JPS5827984B2 - bunrifusenhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a separate flotation method for recovering high grade molybdenum sulfide ore from porphyry copper ore type ores.

Generally, molybdenum sulfide ore is a mineral that floats very easily, but the Mo grade in ore deposits is extremely low and usually 0.0.
It is on the order of n%, but rarely 0. Some are on the order of n%.

In the case of 0, n% order, a process in which molybdenum sulfide ore is suspended alone from the beginning (hereinafter referred to as process A) is adopted, but in the case of O, On% order, molybdenum sulfide ore is first suspended together with copper sulfide ore. The copper-molybdenum bulk concentrate was recovered as a copper-molybdenum concentrate, and its Mo grade was reduced to 0. After increasing the content to n% order, a process (hereinafter referred to as process B) in which sulfide steel and associated minerals are suppressed and molybdenum sulfide ore is suspended by various means as described below is applied.

In order to recover high-grade molybdenum ore in either process A or B, it is necessary to carry out leaning and regrinding to suppress copper sulfide and its associated minerals.

The inhibitor used in this cleaning step is generally a cyanide compound such as ferrocyanate, ferricyanate, or assimilated soda, or a sulfide of phosphorus or arsenic. There are also rare flosses that suppress ore).

Since these inhibitors are utilized, the flotation operation during cleaning is almost the same in both processes A and B.

However, in process B, copper and molybdenum bulk flotation is performed prior to molybdenum preferential flotation, but in this flotation, scavengers such as xanthates, dithiophosphates, and mercaptans and sources such as pine oil are used. Due to the use of foaming agents, all the minerals subjected to molybdenum preferential flotation tend to float strongly, which means that they are difficult to suppress. It takes.

Therefore, in the case of the B process, it is common to use strong suppression measures in the roughing step that precedes the cleaning step.

For example, as a physical method, the pulp of the bulk concentrate is filtered through a dewatering stream in order to neutralize the effect of the flotation agent used in bulk flotation; if it is insufficient, the washing is repeated with fresh water; Evaporative blowing is performed to decompose the reagent; alternatively, the bulk concentrate is dewatered and then roasted at a suitable temperature;
Methods such as decomposing the reagent and selectively oxidizing the surface of the copper mineral have been used.

However, dewatering of bulk concentrate requires only one
Each time the process is carried out, it is equivalent to adding one more dehydration system to the copper ore processing plant, which is not economical and the effect of removing reagents is insufficient.

The method of steam injection or roasting directly desorbs or decomposes the flotation agent adsorbed on minerals, so it is not very effective, but the disadvantage is that it requires larger equipment and increases running costs due to fuel consumption, etc. be.

In addition, as a chemical means, combinations of cyanide compounds and oxidizing agents such as hypochlorous acid and hydrogen peroxide have been used, but despite the large amounts used, their effects are insufficient. be.

The present invention eliminates the drawbacks of the conventional methods as described above, is functionally powerful, has low running costs, is simple in terms of equipment, and can be easily used not only in roughing steps but also in cleaning steps. The purpose of this project was to economically recover high-grade molybdenum sulfide ore by developing a method for suppressing copper sulfide ore and its associated minerals.

The present inventors have discovered that when a direct current is passed through ore slurry, the floating motion changes very significantly depending on the material of the electrode used when applying the current, and they have already filed a patent application for
It is proposed in No. 7188.

According to this, the suppression tendency based on the energization treatment due to the difference in the electrode material of copper sulfide ore and molybdenum sulfide ore is almost the same, but the suppression effect of molybdenum sulfide ore is not as pronounced as in the case of copper sulfide ore. By utilizing these relationships, it is possible to separate copper sulfide ore and molybdenum sulfide ore, and this effect is particularly noticeable when the electrode is made of Fe group or aluminum.

However, a more detailed study of these relationships revealed the following.

In other words, when applying electricity to copper, molybdenum, and the products of the roughing step or cleaning step, it is extremely effective when the electricity application time is within a certain range; When the temperature exceeds 1, the suppression rate of molybdenum sulfide ore increases as well as the suppression rate of copper sulfide ore, but this is a phenomenon in which the molybdenum grade increases slowly.

This is because part of the iron sulfide ore contained in the copper sulfide ore is activated by oxygen generated when electricity is applied.

As a result of various studies on countermeasures against this problem, the present inventors have found that when a relatively small amount of cyanide is used in combination with a constant energization treatment, the above-mentioned drawbacks are improved and a very remarkable separation flotation effect is exhibited. , which led to the achievement of the present invention.

The energization treatment referred to here means that the slurry 11 before flotation is
．． Add 01 to 0.2 mol of electrical conduction aid, Fe group or A
An electrode containing I group as a main component is inserted into the slurry, and the pH is 10.
1 kg of ore in the slurry under the following conditions:
This means applying a current of 0 to 7000 corons.

In order to save power, it is desirable that the current conduction aid be a strong electrolyte, but substances that interfere with the suppressing effect should not be used, such as hydroxides such as KOH, Ca(OH)2, NH4OH, etc. HNO3, H2SO4, HCI, CH3
Acids such as CO0H and the above hydroxides and inorganic or organic salts of the above acids are preferable, but halogen salts of alkali metals or alkaline earth metals, or ammonium salts of the above acids are preferable.

These electrical conduction aids are 0.0
1-02 mol is added.

If the amount of the energization aid added is less than 0.01 mol to the slurry, a larger amount of current will be required than necessary, and even if the energization aid is added to the slurry at 0.2 mol or more, the effect of the energization treatment will not be significant. There is no improvement and it is also uneconomical.

In the separation flotation method of the present invention, the electrode has a Fe group or Al group as its main component, but it may also be a single metal such as Fe, AI, or Ni, or an alloy mainly composed of the above metals.

These electrodes may be plate-shaped, rod-shaped, lattice-shaped, or fiber-shaped, depending on the intensity of stirring and the target mineral.

In the energization process, it is necessary to apply an electric current of 10 to 7000 coulombs per 1 kg of ore, but desirably, the electric current amount is 1000 to 7000 coulombs in the case of the roughing step, and 10 to 7000 coulombs in the case of the cleaning step.
The amount of current required is 100 coulombs, which is smaller than in the case of a rough step.

When electricity is applied, the pH of the slurry should be adjusted to at least 10 or less, preferably about 6 to 8, in order to obtain the best suppressing effect.

If the pH of the slurry is too low, the electrode will be contaminated with dissolved ions during the night, which is not desirable.

Next, the present invention is characterized in that a cyanide compound is added to the slurry along with the above-described current treatment.

Although the cyanide compound may be added during the energization treatment in an electrically insulated condition imparting tank equipped with a stirring device, it is preferably added to the slurry that has undergone the energization treatment separately in the condition imparting bath.

The cyanide compound is a cyanide compound such as potassium ferrocyanide, sodium ferrocyanide, potassium ferricyanide, or a cyanide such as sodium assimilate or potassium assimilate.

The cyano compounds and cyanides may be used alone or in combination.

These cyanide compounds are 10 to 300% of the raw material ore.
0? / can be added, but preferably 500 to 3000 P/l in the roughing step and 10 to 500 P/l in the cleaning step. /l, preferably 10-100? /1 is good.

If the amount of cyanide added is less than 10 f/ to the raw ore, there will be no sufficient separation and flotation effect;
/ Below, a large amount of expensive chemicals will be used,
It is economically inconvenient.

If the cyanide compound is applied for less than 1 minute, a sufficient separation and flotation effect cannot be expected, so it is preferable to apply the cyanide for more than 1 minute, preferably for about 5 minutes.

The present invention requires the above-mentioned electrification treatment and conditioning using a cyanide compound, and may also be used in combination with conventionally used collectors, foaming agents, and conditioning agents. It is possible.

Further, the separation flotation method of the present invention can be applied to only one of the roughing step and the cleaning step, or to both, to enhance the separation flotation effect.

According to the above-described separation flotation method of the present invention, it is possible to exhibit remarkable effects and recover high-grade molybdenum with a smaller amount of electricity and a smaller amount of addition than in the case of the electrification method alone and the case of cyanide alone.

This superior effect is due to the extremely strong inhibitory action, which sometimes tends to break the floss and increases the amount of foaming agent used.

In such a case, a well-balanced effect can be achieved by selecting an appropriate foaming agent and adding it to the separation flotation operation that uses both the energization method and the cyanide compound in the present invention.

Foaming agents that can meet this demand include two types that have a composition of polyethylene glycol alkyl phenyl ether, which is a condensation of polyethylene glycol with alkylphenols, and have an HLB of 6 to 9 or an HLB of 12 to 15. The nonionic surfactant has a composition in which polypropylene glycol, which is a polymer of propylene oxide, is added with polyethylene glycol, which is a polymer of ethylene oxide, and has an E, 0. There are nonionic surfactants whose % ranges from 10 to 30.

Among these nonionic surfactants, those with specified HLB are 2 to 100 for slurry. /l,
E, 0. The specified percentage is 2-5M for slurry.
'7t, each can be used alone or in combination.

By using the above-mentioned foaming agent, a sufficient separation and flotation effect can be achieved even if the amount of current applied and the addition of cyanide compounds is reduced, and there is also an economical advantage, and the use of harmful reagents can be avoided. There are also pollution benefits from reduction.

Next, the present invention will be explained by examples.

Example 1 The experiment shown in Table 1 was carried out on copper-molybdenum bulk flotation for ores that are very difficult to suppress due to the use of strong flotation agents. Arsenic), the effects of the energization method alone and the method of the present invention were confirmed respectively.

In the table below, (l is the slurry, t is the amount of raw ore, coulomb/kg is the amount of current per 1 kg of flotation feed (ampere 0 hours), MIBC is methyl isobutyl carbinol, PR#102 is Among the nonionic surfactants with polypropylene glycol K polypropylene glycol K, 0.% is 10 to 30%.
% (manufactured by NOF KK).

As shown in Table 1, Test Tsuta 1 and Tsuta 2, the conventional method has no effect even if a large amount of inhibitor (ferrocyanic potash 8 kg/l or arsenic sulfide (→-NaOH) 5 kg/l) is used. In most cases, such a method is not economically possible.

(In addition, even if dehydration and washing were combined, there was almost no effect.

) In fact, in the case of the electric conductivity alone shown in Test Tsuta 3, it is improved over Tsuta 1 and Tsuta 2.

On the other hand, according to the methods of the present invention in Experiments 1 and 4 and 5, remarkable separation and flotation effects are achieved with a small amount of electricity and a small amount of addition, respectively.

Example 2 Next, the method according to the present invention was confirmed in the cleaning step of molybdenum preferential flotation, and the results are shown in Table 2.

This experiment used floating ore from the fourth cleaning stage of molybdenum preferential flotation.

In the table below, among the nonionic surfactants with the composition of polyethylene glycol alkyl phenyl ether, those with HLB of 12 to 15 are EA #140 (manufactured by Daiichi Pharmaceutical KK) and those with HLB of 6 to 9. The product is EA#73 (manufactured by Daiichi Pharmaceutical KK).

In the comparative example of Experimental Shoe 1 in Table 2, the influence of the residual flotation agent from the previous stage cleaning was strong, so even if a large amount of sodium assimilate was used, the quality did not improve, and there was a lot of molybdenum loss, and the separation was poor.

With the method of the present invention, Tsuta 1 and Soda 5 can be produced with a small amount of sodium hydroxide.
The quality is improved better than the comparative example, and molybdenum loss is also reduced.

Particularly, when EA #140 or EA #75 is used in combination, the separation performance is further improved, but this embodiment exhibits the ★★ effect with a much smaller amount of electricity than in the case of a rough inge step.

Example 3 The ore used in the experiment was copper and molybdenum concentrate recovered from a porphyry copper deposit by flotation, and contained chalcopyrite, chalcocite, pyrite, molybdenite sulfide, silicic gangue, and the like.

This was separated and flotated based on the flow sheet shown in FIG.

The results are shown in Table-3 and Table-4.

Flotation conditions in the method of the present invention Comparative example of flotation results in the method of the present invention 1 Copper molybdenum bulk concentrate was subjected to separate flotation based on the flow sheet shown in FIG.

★★ The results are shown in Table-5 and Table-6.

Flotation conditions in the conventional method Results of flotation in the conventional method As detailed above, the conventional method uses the strongest arsenic sulfide (washing with water, dehydration, rebalfing, 6 times in total, 6 times in total with arsenic sulfide) Even after repeated flotation operations such as .8 kg/t and nine cleanings, the molybdenum concentrate grade was 49.6%.

Since the commercial value of molybdenum concentrate these days is at least 51 Mo% or more, this method still requires several cleanings.

However, even if cleaning is repeated several times to improve the quality, if such a large amount of arsenic sulfide is used, industrialization is not possible from an economic standpoint as well as from a pollution control standpoint.

On the other hand, according to the method of the present invention, industrialization is fully possible.

Example 4 The ore used in the experiment was a copper molybdenum concentrate recovered from a porphyry copper ore type bed by flotation, and was composed of chalcopyrite, chalcopyrite, tetrahedrite, pyrite, molybdenum sulfide, and the like.

Table 7 shows the results of examining the suppression effects of the method according to the present invention and the conventional method in a roughing step.

In Table 7, Sakazuki 1 dest is the effect of ferrocyan on this ore, A2 test is arsenic sulfide ★★ (+Na0
The effect of H) and 7z3 are the effects of the method according to the invention.

In Table 7, flotation conditions other than the suppressing means, foaming agent, scavenger, surfactant, flotation time, etc. are all regulated the same.

Comparison of each suppression method in the roughing step.As is clear from the comparison of each suppression method in Cloth-7, DCl, 000 chlorine/kg energization and ferrocyanic potash 500? /T can be used in conjunction with 7 Erosyanka without energizing! 73 kg/l or arsenic sulfide (+NaOH) 1 kg/l.
・Exceeds the effects of only applying electricity* without adding ferrocyanic potash.

Therefore, the following example is an example of separation using this method.

Conditions for flotation according to the method of the present invention Results of flotation according to the method of the present invention Therefore, for example, when considering the use of ferrocyan as a conventional method, as shown in Table 7, 3.
However, using the method of the present invention,
This percentage is the amount required to turn molybdenum into the final product.
It is.

Since the cost of energization is considerably lower than that of ferrocyane, the method according to the invention is very inexpensive in terms of cost.

Reducing the use of other harmful reagents also has the advantage of preventing L. caries pollution.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet for separation flotation according to the method of the present invention, and FIG. 2 is a flow sheet for separation flotation according to the conventional method.

Claims (1)

[Claims] 1 In the separation flotation method for recovering high-grade molybdenum sulfide ore from porphyry copper ore, 0.01 to 0.2 mol of a conduction aid is added to the slurry Il before flotation, and Fe group or Al group An electrode mainly composed of PH is inserted into the slurry, and the PH
1 kg of ore in slurry with direct current under conditions of 10 or less
After applying a current of 10 to 7,000 corons per unit, or during energization, cyanide is applied to the raw ore at a rate of 10 to 3,000 corons.
A separation flotation method characterized by adding /l.