JPS60211023A - Wet treatment of mineral containing manganese dioxide - Google Patents

Abstract

PURPOSE:To make metallic manganese soluble and to recover it by a wet process by immersing a mineral contg. manganese dioxide such as manganese dioxide ore, manganese nodules or electrolytic manganese dioxide in an acid in the presence of a carbohydrate such as a saccharide or starch to leach out manganese from the mineral. CONSTITUTION:When a mineral contg. manganese dioxide such as manganese dioxide ore, manganese nodules or electrolytic manganese dioxide is immersed in an acid such as sulfuric acid to leach out manganese from the mineral, a carbohydrate such as a saccharide or starch is added. The carbohydrate acts as a very effective auxiliary for dissolving a useful metal such as manganese, so the metal is made soluble at a low temp. and recovered very effectively by a wet process at a reduced cost.

Description

[Detailed description of the invention] The present invention relates to a wet treatment WI method for metalworking manganese oxide minerals,
More specifically, it relates to a wet processing method for solubilizing and leaching valuable metals such as manganese from manganese oxide minerals that are widely produced, including manganese nodules produced from the ocean floor.

Conventionally, reduction roasting methods have been used to solubilize valuable metals such as manganese in manganese oxide minerals.
The drawback is that harsh conditions such as high temperatures are required for solubilization.

The present inventors have conducted various studies in order to create a wet treatment method that is industrially more advantageous than conventional reduction roasting methods when solubilizing metalworking manganese oxide minerals.
We have completed the present invention by discovering that the presence of carbohydrates such as starch makes Mn easily soluble even when acid leaching of metalworking manganese oxide minerals is performed under relatively mild conditions.

Thus, the present invention was made based on the knowledge that carbohydrates act as extremely effective solubilizers for manganese dioxide.

That is, the present invention resides in a wet processing method for a metal manganese oxide mineral, which is characterized by acid leaching the metal manganese oxide mineral in the presence of a carbohydrate to solubilize valuable metals such as manganese.

In the present invention, for example, metallurgical manganese oxide minerals include Mn, N1%C01CLI, l
``When containing valuable metals such as Mn and Fe,
It is thought that the matrix is easily destroyed and the valuable metals dispersed in the matrix also become easily soluble in acids.

The metallurgical manganese oxide mineral as used in the present invention refers to a mineral containing manganese dioxide, and includes, for example, manganese nodule, natural manganese dioxide, electrolytic manganese dioxide, and the like.

The carbohydrate used in the present invention may be saccharide, starch, etc., and may be in either liquid or powder form. In addition, carbohydrates as used in the present invention refer to a group of organic compounds, mainly saccharides, with similar structures and properties.Specifically, carbohydrates are mainly composed of monosaccharides and their oxidation products, such as aldonic acids and saccharides. Including phosphoric acid, sugar acid, sugar alcohol which is a reduction product, similar cyclic inodites, deoxy sugar which has lost an oxygen atom, anhydro sugar which is a dehydration product, and amino sugar which is an amino substituted product. There are various substituents, various ethers, esters, etc., and oligosaccharides such as trisaccharides, trisaccharides, and tetrasaccharides, polysaccharides, and others that have glycosidic bonds formed through the hemiacetal hydroxyl group. The amount of carbohydrate present is related to the pure MnO2 content and shape of the raw metal manganese oxide mineral, but for example, pure MnO21.0 (0.3 per
(1(7) addition), it was confirmed that almost 100% of other valuable metals including manganese were extracted in acid leaching (90 to 100°C) using 3 mol/J of H2804.

From this, the amount of carbohydrates present is pure Mn 02i,o
A range of 0.01 to 1.0 g/g is preferred.

In the present invention, although it is still not theoretically clear whether carbohydrates act as reducing agents in wet processing or whether they act due to other special phenomena, Even under relatively mild conditions, manganese dioxide can be solubilized within a short FRM without any additives.

The acid used for acid leaching is preferably sulfuric acid in view of ease of post-treatment, no need for expensive equipment, or low cost; in this case, 1 to 10 mol/J.
, preferably 1 to 3 mol/J of dilute sulfuric acid, which is present in a slight excess over the theoretical amount required to solubilize the manganese dioxide mineral, allows metal extraction to be carried out in a short time at 100°C or below. It is possible to achieve close to 100%. In particular, nearly 100% of valuable metals such as Ni, Co, and Cu in manganese nodules can be extracted, making it possible to dramatically improve the extraction rate.

Valuable metals in the present invention include Mn1Ni and Go.

Refers to metals contained in manganese oxide minerals such as C1l and l”e.

Hereinafter, the present invention will be explained in detail based on Examples and Comparative Examples. In addition, all the content values in Table 1 are weight %.

1 to 10 and 1 to 3 Metalworking manganese oxide minerals (-1
00 mesh) to each 10 g of carbohydrates, 3 g/9 for carbohydrates, 5 Q/Q for nodules, electrolytic manganese dioxide, and natural manganese dioxide, and react at 90 to 100°C for 60 minutes. I let it happen. For comparison, metal manganese oxide minerals having the same composition and particle size as above were reacted with dilute sulfuric acid under the same conditions in the absence of carbohydrates.

The extraction rate of Mll is shown in Table 2 and FIG. In addition, when manganese nodules are used (Comparative Example 1 and Examples 1 to 4), the extraction rate of valuable metals other than Mn is also listed, and when natural manganese dioxide is used (Comparative Example 2 and Examples 1 to 4), the extraction rate of valuable metals other than Mn is also listed. For Examples 5 to 7), the extraction rates of Mn and Fe are also listed.

As shown in Table 2 and FIG. 1, in each metal manganese oxide mineral, the extraction rate of valuable metals is low in sulfuric acid leaching in the absence of carbohydrates (Comparative Examples 1 to 3).

On the other hand, the presence of carbohydrates significantly improves the extraction rate of valuable metals (Examples 1 to 10). In particular, in Examples 1 to 4 in which manganese nodules were used as the metallurgical manganese oxide mineral, the effect of improving the extraction rate of valuable metals such as Cu, Ni, and CO was remarkable. The amount of carbohydrate present needs to increase or decrease depending on the purity of MnO2 in each manganese dioxide mineral, but it is approximately 0.39 per gram of pure MnO2.
The amount is sufficient to achieve the desired effect.

As explained above, the wet treatment method of the present invention in which carbohydrates are present when solubilizing metal manganese oxide minerals can solubilize valuable metals such as Mn in metal manganese oxide minerals at a high level. Moreover, acid elution can be carried out under relatively mild conditions. Therefore, the wet treatment method of the present invention can be suitably used as a method for solubilizing valuable metals in manganese oxide minerals.

[Brief explanation of the drawing]

FIG. 1 is a line diagram showing the extraction rate of valuable metals in each manganese dioxide mineral, and shows Examples 1 to 1o and Comparative Example 1.
- Corresponds to 3. Patent Applicant Mitsui Mining & Mining Co., Ltd. Agent Patent Attorney Tatsuo Ito Attorney Patent Attorney Tetsuya Ito Procedural Amendment October 4, 1980 Patent Office Commissioner Manabu Shiga 1, Indication of Case 1982 Patent Application No. 65941 No. 2, Name of the invention: Wet processing method for metalworking manganese oxide minerals 3, Person making the amendment Patent applicant: Residence: 1-1 Nihonbashi Muromachi, Chuo-ku, Tokyo (618) Mitsui Kinzoku Mining Co., Ltd. Representative: Kimi Mashima Part 3 4, Agent 105 Address: Toranomon Denki Building, 2-8-1 Toranomon, Minato-ku, Tokyo Telephone: (501) 9370 Voluntary amendment 6. Subject of amendment: "Detailed description of the invention in the specification" 7. Contents of amendment 1, Book II, page 3, 13-. Examples include "electrolytic manganese dioxide" in line 14. ′” [Electrolytic manganese dioxide, chemical manganese dioxide, etc. may be mentioned.The present invention is also applicable to products using natural manganese dioxide ore, electrolytic manganese dioxide, and chemical manganese dioxide, such as dry batteries such as manganese batteries and filter media for water purification. Needless to say, it is possible. Correct to J.

Claims (1)

[Scope of Claims] 1. A wet processing method for metallurgical manganese oxide minerals, which comprises acid leaching metallurgical manganese oxide minerals in the presence of carbohydrates to solubilize valuable metals. 2. The wet processing method for metallurgical manganese oxide minerals according to claim 1, wherein the metallurgical manganese oxide minerals are selected from manganese dioxide ore, manganese nodules, and electrolytic manganese dioxide. 3. The wet processing method for metalworking manganese oxide minerals according to claim 1 or 2, wherein the carbohydrate is saccharide or starch. 4. The wet processing method for metalworking manganese oxide minerals according to claim 1, 2, or 3, wherein the valuable metal is manganese.