JPS60131829A - Method for recovering rhenium - Google Patents

Abstract

PURPOSE:To recover efficiently rhenium as rhenium sulfide from a soln. contg. rhenium and bismuth by subjecting the soln. to sulfurization treatment at a specified concn. of hydrochloric acid. CONSTITUTION:Waste contg. Mo, Bi, As, etc. besides Re produced as a by- product in a stage for smelting molybdnum ore or the like is treated with an ion exchange resin to prepare a soln. contg. Bi and Re acidified with hydrochloric acid. A sulfurizing agent such as gaseous hydrogen sulfide is blown into the soln. while keeping the concn. of hydrochloric acid at >=3N to convert most of the Re into sulfide (Re2S7-base rhenium sulfide) without converting the Bi into sulfide. The resulting sulfide in the soln. is then collected.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering rhenium from an acidic hydrochloric acid solution containing rhenium and bismuth.

Rhenium is a rare metal that is slightly associated with molybdenum ore and copper ore, but it is an important element used in catalyst additives, thermocouples and super heat-resistant alloys, and materials for high-vacuum electron tubes. It is metal.

Although there are few reports on industrial recovery methods for rhenium, one promising method is to flow an aqueous solution containing rhenium through a resin column containing an anion exchange resin, adsorb rhenium onto the resin, and then remove the adsorbed rhenium. A method of elution has been proposed. A hydrochloric acid solution is used as the eluent. At the same time that rhenium is adsorbed, impurities contained in the starting solution are also adsorbed by the resin, and during elution, they are distributed into the elution solution together with rhenium. Since rhenium is only slightly accompanied by the above-mentioned special magnet, the rhenium recovery source is mainly waste generated in the non-ferrous smelting process, and therefore Me, Bi, As, etc. are inevitably included as impurities.

Among these impurities, impurities other than Bi can be desorbed from the resin by performing an appropriate treatment before the elution process, but Bi remains in the resin together with R and is released into the solution together with Re during elution. enter. Therefore, R. and Bi coexist in the hydrochloric acid acidic eluent, and it is necessary to establish a technique for separating the paint.

In response to these needs, the present invention provides R
・Provides a method for separating Bi and Bi.

In a hydrochloric acid solution containing R and BI, the concentration of hydrochloric acid is 5N.
It has been found that when sulfiding is carried out while maintaining the above conditions, almost all of R becomes sulfide, but almost all of B1 remains in the sulfurized condensate, and the present invention is based on this knowledge. .

To summarize, the present invention is characterized in that rhenium is recovered as rhenium sulfide while bismuth remains in the solution after sulfurization by subjecting a hydrochloric acid acidic solution containing rhenium and bismuth to sulfurization treatment at a hydrochloric acid concentration of 3N or more. A method for recovering rhenium is provided.

Hereinafter, the present invention will be specifically explained in connection with an integrated process for recovering rhenium from waste acid, but the present invention is not limited to this process, and rhenium and bismuth are finally recovered. It is clear that the present invention is applicable to any purification system in which a hydrochloric acid containing solution is recovered and from which it is desired to recover rhenium.

Waste acid is one of the promising raw materials for industrial recovery of rhenium. Waste acid is water-washed when sulfur dioxide gas generated in the smelting process of non-ferrous metals such as copper is used to produce sulfuric acid, and a portion of the sulfuric acid produced during that process is periodically extracted. be. The rhenium contained in the raw ore is mixed into the waste acid along with other impurities. Other typical impurities include ag, Mos Bi, and Am.

The applicant has succeeded in establishing a consistent method for recovering rhenium from waste acid. This method consists of the following steps: (a) a demercury step to remove mercury from the waste acid; and (b) the demercury-depleted waste acid is passed through a resin column containing an anion exchange resin to remove rhenium. , an adsorption step in which molybdenum, bismuth, and arsenic are adsorbed onto the resin; (c) an impurity removal step in which sodium hydroxide is passed through the resin tower to mainly remove molybdenum and arsenic; and (d) an impurity removal step in which mainly rhenium and arsenic are removed from the resin. (e) a sulfurization step to recover rhenium contained in the elution solution as rhenium sulfide; and (f) a regeneration step to regenerate the resin as necessary.

This method first removes Hgs Mo5B 1 and As impurities that are obstacles to the recovery of rhenium from waste acid.
, are removed before the adsorption step, and then the anions are R and B.
i is mainly eluted, and R. is recovered in the form of sulfide from the eluate. For demercury removal, a chelate resin such as Unitika U.R-2200HT is used. The anion exchange resin is Diaion 5A20A manufactured by Mitsubishi Chemical Industries.

Diaion PA516, Diaion PA 408
can be used effectively. As a removal solution for removing Mo and As from the resin, it is effective to use a NaOH solution of around 1oot7. As the eluent, hydrochloric acid or hydrochloric acid containing a metal chloride is used. In particular, the elution effect of hydrochloric acid containing metal chlorides is excellent. As the metal chloride, copper, cadmium or zinc chloride is particularly preferred;
Among these, zinc is particularly preferred in consideration of the sulfurization treatment performed in the subsequent step. Zinc can be easily purified. Hydrochloric acid concentrations of 3 to 9 normal can be used. The amount of metal chloride added is sufficient at a level of 30 to 150 f/z. It is sufficient to use liquid melon for elution in an amount of 3 to 9 times the volume of resin. Since the ion exchange resin after elution is in C1 state due to the use of hydrochloric acid, a regeneration step is required to return it to oH form for repeated use.

Regeneration can be easily carried out by flowing sodium hydroxide or the like.

Through these steps, an eluate is finally obtained. After elution, the substantial amounts of Re and Bl that had been adsorbed on the resin have migrated into the solution, and the remaining small amounts of Mo and A have also migrated into the solution.
s is also imported. Therefore, the eluate mainly contains R. and B1, and M.

It is an acidic solution of hydrochloric acid accompanied by a small amount of Am. This is an example of a hydrochloric acid solution containing rhenium and bismuth that is the subject of the present invention.

According to the present invention, a sulfurization treatment is carried out for selective recovery of rhenium from an acidic solution containing rhenium and bismuth. By blowing, for example, hydrogen sulfide gas as a sulfiding agent while stirring the solution, almost all of the rhenium becomes sulfide, while almost all of the bismuth remains in the sulfurized liquid. In this case, the hydrochloric acid concentration is important; if the hydrochloric acid concentration is lower than 3N, bismuth is likely to be sulfurized and the separation effect will be reduced. The generated rhenium sulfide is considered to be a sulfide close to Relay when the S/R1 molar ratio is calculated from the quality of the product. As for the sulfiding conditions, a combination of conditions sufficient to completely sulfurize the rhenium in the liquid may be selected by considering the flow rate of the blown gas, the blown time, the stirring speed, the concentration of hydrochloric acid, etc.

Reference Example A practical example of obtaining eluate from waste acid according to the above-mentioned process is described for reference. A waste acid having the following composition that had been previously demercured was used.

408) was passed through a resin column containing 1501, and an adsorption step, an impurity removal step, and an elution step were performed in sequence.

Each process condition and analysis result are shown.

Adsorption step resin amount: 150 ml of waste acid: 5 mB Washing: 100 f/sulfuric acid 761 Then washing water 3
oot adsorption resin adsorption liquid removal liquid: 2.5 N NaOH1501 washing water = 5
oot Resin after impurity removal liquid elution step Eluent: HCI (6N) + ZnC1z (100f/
L) 180 Washing water: 5 oot Elution resin elution liquid extraction example The elution extraction liquid (acidic with 6N hydrochloric acid) obtained in the reference example was sulfurized. As sulfurizing agents, H and S were blown into the eluate for 30 minutes. During the blowing, the liquid was stirred at 300 rpm. The analysis results of recovered sulfide are shown.

In this way, 138t of Re in the eluate was recovered as sulfide, while 30α4t of 302v of Bi remained in the solution after sulfurization. Mo and Am are also sulfided throughout the ship, but this can be minimized by more complete impurity removal treatment.

Therefore, very high purity rhenium could be recovered very easily.

Comparative Example When the same sulfiding treatment was performed with the hydrochloric acid concentration reduced to 2.5N, the amount of bismuth in the sulfide increased. The limit hydrochloric acid concentration was set at 3N, with the permissible limit for the amount of bismuth mixed in as 1%.

As described above, the present invention enables simple and efficient recovery of rhenium from a solution containing rhenium and bismuth that is finally obtained by treating waste acids and other rhenium recovery sources.

Procedural Amendment Document March 2, 1980, Case of Kazuo Wakasugi, Commissioner of the Japan Patent Office Patent Application No. 236259 of 1988 Name of the invention Relationship with the case of the person amending the method of recovering rhenium Name of patent applicant Nippon Mining Co., Ltd. Agent Address: 103-103 Address: Oil and Fat Industry Hall, 3-13-11 Nihonbashi, Chuo-ku, Tokyo Telephone number: 273-6436 Address: The specification of Patent Application No. 1988-256259 is amended as follows.

t Page 5, line 10 [UR-2200) Correct 1TJ to jUR-2200HJ.

2 Page 9, line 9 (place of table showing liquid after impurity removal (II
) in the column ``58'' to li'12.0J (-) to rs, oJ to ``15.9 Jl'', and line 12 (second line of the elution step). Correct r180jJ to j1200jJ.

Claims (1)

[Claims] 1) A rhenium recovery method characterized in that rhenium is recovered as rhenium sulfide while bismuth remains in the solution after sulfidation by subjecting a hydrochloric acid acidic solution containing rhenium and bismuth to sulfurization treatment at a hydrochloric acid concentration of 3N or higher.