JPS60131828A - Method for recovering rhenium from waste acid - Google Patents

Abstract

PURPOSE:To recover efficiently rhenium from a waste acid produced as a by- product in a stage for refining a nonferrous metal by treating the waste acid by specified systems in order. CONSTITUTION:Gaseous SO2 generated in a stage for refining a nonferrous metal such as copper is scrubbed with water, and part of produced sulfuric acid is periodically drawn as waste sulfuric acid. This waste acid contg. Re, Hg, Mo, Bi, As, etc. is treated with a resin having strong Hg adsorbing power such as ''VR-2200HT'' of UNICHIKA K.K. to remove the Hg, and it is treated with an anion exchange resin such as ''Dia Ion PA408'' of MITSUBISHI KASEI KOGYO K.K. to adsorb the Re, Mo, Bi and As. An aqueous NaOH soln. is passed through the resin to remove the Mo and As by elution, and about 3-9N hydrochloric acid is passed to elute the Re and Bi. The eluted Re is then recovered from the eluate as rhenium sulfide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering rhenium, and in particular, in recovering rhenium contained in waste acid using an ion exchange resin tower, the present invention involves repeated use of an ion exchange resin. This invention relates to a method for recovering rhenium that achieves efficient recovery of rhenium.

Rhenium is a rare metal that is slightly associated with molybdenum ore molybdenite and copper ore, but it is an important additive used in catalyst bulk, thermocouples, super heat-resistant alloys, high vacuum electron tube materials, etc. It is a metal.

Waste acid is one of the promising raw materials for industrially recovering 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 impurities include Hg-
%M (ISBl and A1 are typical.

Although not much systematic research has been conducted on industrial recovery methods for rhenium, one promising method is Re2O.
A method has been proposed in which a raw material containing 3 is dissolved in an aqueous solution, rhenium is adsorbed to the resin by an ion exchange method using an anion exchange resin, and the adsorbed rhenium is eluted.

The present inventors conducted systematic research on a rhenium recovery method based on a rhenium recovery method using the above-mentioned anion exchange resin, targeting waste acid as a rhenium recovery source.

In this method, problems to be solved include separation of rhenium from accompanying impurities other than rhenium, regeneration and repeated use of the resin, efficient elution of rhenium from the resin, and effective recovery of rhenium from the eluate. However, as a result of extensive research, we succeeded in establishing an industrially useful rhenium recovery method.

In the waste acid, in addition to R, Hg SMo, B1 and A
m is included as an impurity, but when waste acid is passed through a rhenium adsorption resin column, these impurities are also adsorbed together with Re. Among the adsorbed impurities, Hg is difficult to elute;
It has been found that the Re adsorption rate deteriorates during repeated use of the resin tower. Therefore, it has been found that it is extremely advantageous for smooth operation of the rhenium recovery system to remove Hg before passing the waste acid through the adsorption resin tower.

-The waste acid thus dekgred contains Re, Mo, and B.
It contains i and As, and these are adsorbed by the resin.

It has been found that Me and As can be removed from the resin very effectively by passing sodium hydroxide through the resin column. It is very convenient to first desorb and remove Mo and As from the resin in this way because it facilitates subsequent operations.

Then, the Re and Bi adsorbed on the resin and the remaining small amounts of Mo and As are eluted from the resin.

The applicant has already proposed the use of a hydrochloric acid solution containing a metal chloride as an eluent to elute Rs from an anion exchange resin (Japanese Patent Application No. 82576/1982), and this method is also adopted in the present method. It is preferable to do so. The resulting 1 mm liquid mainly contains Re and nt, with a small amount of M.
It is accompanied by l and As.

It has been found that the most effective way to recover R from the eluate is to recover Re in the form of sulfide.

Almost all of B., Mo, and As become sulfides, but almost all of B1 remains in the sulfide solution, making it possible to effectively separate Re and Bl.

The resin after elution can be regenerated by a lift in the next cycle.

The above-mentioned Hg removal process, adsorption process, and non-#H# (Mo').

Am) By combining the removal process, elution process, and sulfurization process 8 leak regeneration process, R in the waste acid can be efficiently recovered in the form of sulfide, and the resin can be used repeatedly. In this way, an integrated process for recovering 'Re' from waste acid was established for the first time in the industry.

In summary, the present invention relates to rhenium, mercury, molybdenum,
This is a method for recovering rhenium as rhenium sulfide from waste acids containing bismuth and arsenic. (c) an impurity removal step in which sodium hydroxide is passed through the resin column to mainly remove molybdenum and arsenic; and (d) an elution step in which mainly rhenium and bismuth are eluted from the resin. (e) A sulfurization process for recovering rhenium contained in the elution solution as rhenium sulfide; (1) A regeneration process for regenerating the resin as necessary. provide.

The present invention will be explained in detail below.

- The drawing is a 74-sheet of the method according to the invention. As mentioned above, waste acid produced in non-ferrous metal smelting plants is an important source of rhenium recovery, with a rate of 5 to 6 ottq/l depending on the source.
Contains rhenium. However, in addition to Re, the waste acid also contains Hg N Me , B1 and B1. The main thing is that it contains impurities and beasts.

Impurities are an obstacle to Re recovery.

The present invention basically uses an anion exchange resin to adsorb R. However, the above impurities are also adsorbed along with R. Among the impurities, Mo, old, and AI can be removed from the resin later, but H is extremely difficult to remove. Therefore, Hg accumulates in the resin, which deteriorates the adsorption efficiency of R@. Therefore, according to the present invention, mercury removal from waste acid is first measured.

For example, Unitika U R-, 220, OHT can be used to remove mercury.
Amb@rlite I RA, like Amb@rlite I RA
This can be achieved almost completely by passing the waste acid through a resin with strong adsorption power for mercury, such as an IJI &#1 based anion exchange resin such as -400. Hg can be removed using a suitable removal agent such as hydrochloric acid.

The mercury-depleted waste acid is then passed through a resin column containing an anion exchange resin. Anion exchange resins are naturally required to have strong adsorption properties for rhenium; for example, Diaion SA2・oA %Diaion PAS
16% Jl' Iaion PA40 B (trade name, manufactured by Mitsubishi Chemical Industries, Ltd.) can be effectively used. Rhenium is strongly adsorbed by the anion exchange resin in amounts up to 10 t/L resin, and 90 to 95% of the rhenium in the waste acid is adsorbed and collected.

Simultaneously with the adsorption of rhenium, a portion of Mo and most of Bi and As in the waste acid are adsorbed.

After flowing the waste acid, it is preferable to pass dilute sulfuric acid of about 100 f/L through the resin, for example, to wash the resin, and then wash the resin with washing water.

Re) The resin that has adsorbed Mo, B1, and As is then switched to an impurity removal step, in which mainly Me and As are removed. As a removal liquid, s 0-20
0 f/l, preferably 60 to 150 f/jf) Na
An OH solution is used. Although some loss of rhenium to the liquid after impurity removal is unavoidable, more than 95% of the adsorbed MO is removed and nearly 90% of the adsorbed As is removed while virtually all of the rhenium remains adsorbed on the resin. . Although a small amount of adsorbed Bi is also removed, the substantial amount remains adsorbed.

Upon completion of the impurity removal step, it is preferable to wash the resin with water.

The resin column is then switched to an elution step in which the adsorbed components are desorbed from the resin. As the melt 111w1, one must be selected that can easily desorb rhenium and other components strongly adsorbed to the resin, yet does not destroy the resin. In the present invention, since most of Mo and Mo have already been removed, the burden of the elution step is reduced. Although hydrochloric acid can be used as an eluent, the applicant has used a hydrochloric acid solution containing metal chlorides as an eluent*.
We have previously developed an elution method to be used as i, and have obtained good results.

Therefore, it is preferable to employ this method also in this method.

As the metal chloride, chlorides of copper, cadmium, or zinc are particularly preferable, and zinc is particularly preferable in consideration of the sulfurization treatment 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 30 to 150
The t/L level is sufficient. It is sufficient that the amount of liquid for elution is 3 to 9 times the volume of the resin. By adding a metal chloride, nearly 100% elution is possible with the amount of solution A compared to an eluent using only hydrochloric acid, and sufficient elution is possible even without highly acidic hydrochloric acid.

A substantial amount of Re and Bi adsorbed on the resin in the elution step enters the elution contact solution, and the remaining MO and B completely enter the solution after dissolution 11i. Therefore, the melt W which is mainly composed of Re and Bl and accompanied by Me and AI! After 1 day, soap is obtained.

Since the ion exchange resin after elution has become C1fi due to the use of hydrochloric acid, a regeneration step is required to return it to an OH type for repeated use. Regeneration can be easily carried out by flowing sodium hydroxide or the like. Thereafter, the next cycle is started after thorough water washing.

In order to recover rhenium from the reed after elution, it is advantageous to carry out a sulfurization treatment to recover rhenium as sulfur. After elution, by blowing in hydrogen sulfide gas while stirring the reed, almost all of R., Mo and AB become sulfides, but almost all of %Bii and t remain in the sulfiding liquid. When the concentration of hydrochloric acid is 3N or more, especially the old one remains in the liquid. In this way, rhenium and bismuth can be separated. When the S 2 /Re molar ratio of the generated rhenium sulfide is calculated from the grade of the product, it is considered to be a sulfide close to R@ 1 Sγ.

The sulfide liquid can be reused as an eluent by removing the 2S in the liquid with air, but since Bl may accumulate, it is necessary to know the permissible concentration.

The entire process cycle is thus completed. Continuous operation is possible by installing multiple resin towers.

Example A waste acid having the following composition was treated according to the present invention.

First, all Hg was removed using a chelate resin UR-2200HT manufactured by Unitika. Thereafter, the adsorption step and subsequent steps were carried out using three resin towers containing 150 L of anion exchange resin (Diaion PA408). Each process condition and analysis result are shown.

Adsorption step resin amount: 1501 Waste acid flow amount + 5 ml Washing: 1 oot / sulfuric acid 761 Then washing water 5 oot Adsorption resin adsorption wet liquid removal solution: 2.5N NaOH 150j Washing water = 3 oot After impurity removal solution Elution step solution 1ijl solution: HCI ( 6N)+ZnC1* (10
09/A) 180 Washing water: 5004 Elution resin elution extraction Sulfurization process Blow in gas ``H3S 450 Time = 30 minutes Stirring: 500 rpm Recovered sulfide (230F) Regeneration process regenerated liquid?2.5N Na0H6001 Washing water: 3oot In total, 13 of the 15Of rhenium in the starting waste acid
8t was successfully recovered in high purity in the form of sulfide.

As described above, the present invention is the first in the industry to establish an efficient integrated process for recovering rhenium from waste acid, and makes an extremely useful contribution to the production of rhenium, a rare substance.

[Brief explanation of drawings]

11. Name of agent: Motohiro Kurauchi 1.゛.5 - Procedural amendment March 2, 1980 Waka Akio, Commissioner of the Patent Office Indication of the case Patent Application No. 256238 of 1980 Name of the invention Waste acid Relationship with the case of the person amending the method for recovering rhenium from Contents of column amendments The specification of Japanese Patent Application No. 58-236238 is amended as follows, as shown in the attached sheet. 1 On page 7, line 8 and page 11, line 8 from the bottom, “UR-
2200HT" are all li'UR-2200
I will correct it as HJl. 2 Page 13, line 4 (the amount of the liquid after removing impurities (9)
) in the column ``5B'' was corrected to ``12. 180j!J will be corrected to "12ooz". Procedural amendment formula June 1980 1911 Patent Office Officer Kazuo Wakasugi Indication of the case 1982 Patent application No. 236268 Name of the invention Relationship with the case of the person amending the method for recovering rhenium from waste acid Patent 11 Co. 1 Name: Agent of Nippon Mining Co., Ltd. 103 Address: 3 Nihonbashi, Chuo-ku, Tokyo No. 13-11 Oils and Fats Ni-gyo Kaikan - 563 on the back - 1 o'clock - = -
1 = - Subject of amendment 1 Inventor of H1 - @Ganjo' arc Specification of the invention and each removal chair H (to) proof book - Detailed description of invention column Contents of amendment The specification of Patent Application No. 1987-256238 is amended as follows. t On page 4, the first line from the bottom that says 17M1J should be corrected to "Mo". 2. On page 9, line 8, ``In the elution method'' should be corrected to ``In the elution method.''

Claims (1)

[Scope of Claims] 1) A method for recovering mustardium waste acid containing rhenium, mercury, sorptan, bismuth, and arsenic as rhenium sulfide, comprising: (f) a demercury step for removing mercury from the waste acid; , (→ an adsorption step in which the mercury-depleted waste acid is passed through a resin column containing an anion exchange resin to adsorb rhenium, molybdenum, bismuth, and arsenic to the resin, and (c) sodium hydroxide is added to the resin column. an impurity removal step in which a liquid is passed through to remove mainly molyptomine and arsenic; (2) an elution step in which mainly rhenium and bismuth are eluted from the resin; and (e) rhenium contained in the eluate is recovered as rhenium sulfide. A method for recovering rhenium from waste acid, which includes a sulfurization step to regenerate the resin, and (f) a regeneration step to regenerate the resin, if necessary.