JPS5976835A - Dry refining method of lead - Google Patents

Abstract

PURPOSE:To separate and recover Sn incorporated in molten Pb from the molten Pb after absorbing the same in granular soda salt by adding the sodium salt together with S to the molten Pb and stirring the same at a specific temp. CONSTITUTION:SnS or PbS is added to molten Pb contg. Sn as a valuable metal, in such a way that S is incorporated therein at 0.05-1.0wt%, and further sodium salt such as NaOH, NaNO3, NaCl or the like is added thereto. The temp. of the molten Pb is maintained at 450-550 deg.C and the molten Pb is stirred for 4-10hr. The sodium salt particles of 2-3mm. diameter absorbing the Sn incorporated in the Pb float on the molten Pb and therefore such particles are separated and recovered from the molten Pb with a bucket type scraper. The granular sodium salt which is easy to handle on account of the small deliquescence property, and permits the direct extraction and recovery of the valuable metal such as Sn without disintegration is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating valuable metals such as FC and Bn contained in a ship as soda salt, and in particular, to facilitate the recovery of separated valuable metals from Nuda town. This invention relates to a method for dry refining lead by forming soda salt in the form of particles.

Various methods are used to recover valuable metals or remove impurities contained in ships, depending on the type and amount of S elements contained. Elements generally contained in ships include FiCu + Te * Zne BnaAn
There are many types of elements such as + 8b + Bl *^* + Au, and the methods for separating these elements can be roughly divided into dry methods and wet methods. The wet method is mainly an electrolytic method, and there is no difference in treatment method compared to the dry method. Various methods have been proposed for refining lead using a dry method, depending on the type of element to be removed, such as elution, oxidation, and addition of zinc, calcium, etc. Usually first elution is Cu#Ts
is removed, followed by removal of 8n, As, and Sb. The oxidation method is adopted as a method to remove Sn r As + Bb from lead, but the Harris method is a method that accelerates the oxidation reaction by adding soda salt and recovers the removed valuable metals. There is a law. The principle of the Harris method is to use a Harris pot, which is designed to allow good contact between soda salt and lead, to add caustic soda (NaOH) and saltpeter (NaNO2) to molten crude lead.
A fluid molten salt layer is created on the top surface of the molten lead by adding common salt (NaCt), and Sn is added to the molten salt layer.
It oxidizes and absorbs HAs + Sb. Compared to other oxidation methods, the Harris method has lower i-fees and labor costs.
It has advantages such as no need for smoke ash treatment and low volatilization loss. However, the valuable metal salts produced by the Harris method (
Harris salt (hereinafter referred to as Harris salt) is extremely hard and absorbent when solidified by cooling, so it has disadvantages in handling. In particular, when recovering valuable metals such as Sn contained in Harris salt, strong alkaline dust is generated during the crushing process during water extraction, and the crushing and sieving system is clogged by the moisture-absorbing portions on the surface.

The present invention solves the above-mentioned drawbacks, and makes it possible to directly produce particle-shaped sorter salts that have low deliquescent properties, are easy to handle, and can be directly used for the extraction and recovery treatment of valuable metals such as 8N without being crushed. The purpose is to provide a dry refining method.

According to the present invention, sulfur or sulfur compounds are contained in molten lead containing valuable metals including Sn at a ratio of 10.05 to 1 weight per sulfur content, the temperature is maintained at 450 to 550C, and soda By adding salt and stirring, the sodium salt of the valuable metal can be directly produced in the form of particles.

The present inventors have developed Pb from which most of the Cu has been removed in advance.
90.5 mold side% T Sn 4.5 parts%, As
O,5 type steel 26゜Sb 4.0% heavy weight molten crude lead is prepared by adding sulfur or sulfur compounds in which the amount of R gold in the crude lead is varied in advance. For example, JP-A-5
Using a pot equipped with a stirrer equipped with an air suction pipe that surrounds the shaft of the impeller and extends in close proximity to the impeller, heat the mixture to a temperature of about 500'C as described in 6-150140. Add caustic soda at temperature, stir;
Sn and As removal tests were conducted. The amount of caustic sorter added was determined by the following formula, which is applied in the conventional Harris method.

Added N*OH (Rg) = 1, 92
Snit (Kf) in the ship:)+2.90X [As fel in the ship: (%)] The results are shown in Fig. 1 and 1P. Sn HAs H8 in n1 Zusha production ship
An example of the change in the content of b with respect to the stirring time is shown below for S-containing 1
The graph shows the case where N is 0.5% by weight. Although sb does not change much in #1, the content of Sn and As decreases almost linearly, and the true removal of Sn is effectively carried out.

Table 1 shows the relationship between the properties of the produced soda salt, the S content of crude lead, and the rotation speed of the stirrer.

1’S 1 f5 ×: Becomes a liquid that is smoothed into granules.

It becomes a granular sorter salt with a diameter of 022-3 group.

According to this result, the conditions for the formation of granular soda salt depend on the stirring root rotation speed and the S content, and although the rotation speed of the stirrer is quite good, considering the rotation speed of the stirrer in actual drilling, In order to stably obtain granular soda salt, it is necessary that the S content be at least 0.05 weight t9. Moreover, if the S content exceeds 1% by weight, bulky soda salt will be produced, which will be difficult to handle, and the amount of lead contained in the soda will also increase, which is not preferable. Therefore, in order to obtain granular soda salt, an S content of 0.5 to 1% by weight is appropriate.

As for the sulfur compound to be added, SnS or PbS are effective, and simple sulfur may be used, but Cu1Fi and 5b
2Ss was ineffective in producing granular soda salt.

The reaction temperature is 450-550r, preferably 450r
~500C is appropriate. Below 450C, the removal rate of 8n, etc. is slow, and above 550C, the formation of pbo increases, and excessive PbO mixes with soda salt and becomes lump-like, making it unsuitable. Also, if the temperature exceeds 500C, combustion will occur on the surface of the generated soda salt, so the most preferable temperature is 450C.
~500C.

As the soda salt to be added, caustic soda (NaoH) is suitable if the above-mentioned stirrer with an air suction pipe is used.
Similar to the conventional Harris method, saltpeter (NaNO3) and common salt (Ia CL ) can also be used together.

Note that the initially added S was replaced by N@ during the purification procedure described above.
Since it is mixed into the granular sorter width produced as ws, it does not remain in the refining pot.

The granular sorter 1 produced in this way can be taken out by a nokkerato etc. and separated into molten lead and a volume X.

This granular soda salt has no deliquescent properties, and can be recovered at a high yield by linosilving it with water without force or pulverization, stirring, solid-liquid separation, and leaching valuable metals such as Sn with water. is possible.

As described in detail above, according to the lead dry refining method of the present invention, all valuable groups contained in crude lead, especially 3y1. As
It is possible to purify lead by effectively removing Sn, and the produced soda salt containing the removed Sn is obtained in the form of non-deliquescent granules, which is convenient for storage and handling, especially in the produced sorter. This method has a great effect in that there is no need to grind it when recovering Sn, etc. from salt t).

The present invention will be explained below with reference to Examples.

Example I Pb 90.5wt196' HSn 4.5wt%
, As O, 5% by weight, 8b 4. The S content in the pot is 3s*-1 for 8.5t of molten lead with a composition of Qit%.
Add PBS to 1i'lX and add NuOH4 in a pot equipped with a stirrer equipped with an impeller and an air suction tube.
20 kg was added and stirred. Reaction temperature is 450-500
The pot was heated from the outside like CK, and stirring continued for 4 hours. The rotation speed of the stirrer was 155 rpm.

Products include SnO, 25% by weight, As 0.05
7.5 tons of 1% lead by weight and 1.4 tons of granular soda salt of 1% 5N261I were obtained. Most of the granular soda salt floating on the melting vessel was in the form of pellets with a particle size of 4-t2 to 3wR, and could be easily separated using a packet scraper.

This granular sorter salt was leached with water at a pulp concentration of 300 Y/l, resulting in 8n 77.3 V/L, As 2
．． 43 f/L.

sb O, 03yyt, pb < o, o i y
A leachate of yt was obtained.

The water leaching rate of Sn was 99% or more. Furthermore, even if the granular soda salt was left as it was for 1 ton, it did not deliquesce.

Example 2 Pb 90.5 heavy ffL, 9g + Sn 4.5
y# amount%, As O, 5% by weight, Sb 4.0!
PBS was added to 55 tons of molten lead with the composition of ffc X so that the S content in the pot was 30%, and
and N5OH in a pot equipped with a stirrer equipped with an air suction tube.
3.3 t was added and stirred. Reaction temperature is 450-475
Heat the tin from the outside to ℃ and stir for 10 hours.
continued. The rotation speed of the stirrer was 155 rpm.

Sn 0.05% by weight, As O,05 as product
48 tons of lead in weight percent and 10 tons of granular soda salt in weight percent of 5n24.8 weight percent were obtained. Most of the granular soda salts were in the form of pellets with a diameter of 2 to 3 dia.

As a result of water leaching of this granular soda salt at a pulp concentration of 300 t/l, Sn 73.7 f/l, As 2.
50 f/L.

Sb O,02't, pb < o, o ty
A leachate of yt was obtained.

The water leaching rate of Sn was 99% or more. Incidentally, the granular soda salt was allowed to stand for 1 ton and no deliquescent property was observed in the book.

Example 3 Pb 90.5% by weight + 8n 4.5% by weight, As
O, 5 weight, 8b4. Molten lead 5 with a composition of O weight percent
Add S to 5 tons so that the S content in the pot is 0.30% by weight.
Mail (2.8t, NILNO
30.56 t and 93 t of NaCtO were added and stirred. The reaction temperature was heated from the outside of the pot to 450-475C, and stirring was continued for 9 hours. Rotation speed i of stirring paddle
j, 155 rpm.

Sn 0.01 ffIf! as a product! , 9K ,
As O, 05 wt% lead 47t and 5n22.7wt 1
12 tons of 8% granular soda salt were obtained. Most of the granular soda salts were in the form of pellets with a diameter of 2 to 3IIIL1.

As a result of leaching this granular soda salt with water at a pulp concentration of 300 f/l, Sn 67.5 V/l and As 2.4
0 f/L.

sb O, o 4 W/l, pb'< 0.01
A leachate of f/l was obtained.

The water leaching rate of Sn was 99% or more. Further, even when the granular soda salt was left for 1 ton, almost no deliquescent property was observed.

Comparative example Pb 91.0% by weight, Sn 3.5% by weight, As
O, 30% by weight, Sh 4.0% by weight, so, oi
8.5 tons of molten lead with 1% ip-fF was placed in a pot equipped with a stirrer equipped with an impeller and an air suction pipe, and Na0114
20 Kg was added and stirred.

The reaction temperature was maintained at 450-475 tlC and stirring continued for 6 hours. The rotation speed of the stirrer was 155 rpm.

The generated soda salt does not become granular but remains liquid,
Soak - The salt was scattered and the environment was poor. The Sn content of the obtained lead was 1.0% by weight.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an example of changes in the content of Sn, As, and 8b in a pot when the lead dry refining method of the present invention is carried out. Patent applicant: Sumitomo Kincho Mining Co., Ltd. Agent: Patent attorney Kaizu Yasushi: Patent attorney Hirayama - Kodai i ω 0 / 2 341 Ichikan (h
r)

Claims (1)

[Claims] Sulfur or a sulfur compound is contained in a molten vessel containing Sn-containing shoulder metal at a ratio of 0.05 to 1% by weight of sulfur, and while maintaining the temperature at 450 to 5501:, soda salt is added and stirred. 1. A dry method for producing lead, characterized in that a soda salt of the above-mentioned valuable metal is produced in the form of particles.