阅读说明：本技术 一种可实现有价金属回收的锡冶炼方法 (Tin smelting method capable of realizing valuable metal recovery ) 是由 罗银华 刘金录 郭文成 孙建华 郑海森 冯万义 张国华 柴东辉 袁野 杨鹏 于 2021-07-08 设计创作，主要内容包括：本发明公开了一种可实现有价金属回收的锡冶炼方法,在锡冶炼的过程中,实现对有价金属的回收,具体的操作方法为：将原料放入烟化炉中进行熔炼,并加入硫精矿进行吹炼,锡和易挥发的有价金属通过烟化炉烟尘的方式进行收集回收,不易挥发的有价金属进入冰铜中,然后对冰铜和炉渣进行澄清分离,完成对不易挥发的有价金属回收。本发明通过对物料合理的控制,在吹炼的过程中完成对锡的冶炼,同时将易挥发的有价金属通过烟化炉的烟尘进行回收,不易挥发的有价金属通过冰铜萃取的方式进行回收,同时避免了冰铜直接随炉渣排放遇水时所产生的放炮现象,降低了冶炼的安全风险。(The invention discloses a tin smelting method capable of realizing valuable metal recovery, which realizes valuable metal recovery in the tin smelting process, and comprises the following specific operation methods: the raw materials are put into a fuming furnace for smelting, sulfur concentrate is added for converting, tin and volatile valuable metals are collected and recovered in a smoke dust mode of the fuming furnace, the non-volatile valuable metals enter matte, then the matte and slag are clarified and separated, and the non-volatile valuable metals are recovered. According to the invention, through reasonable control of materials, tin smelting is completed in the blowing process, volatile valuable metals are recovered through smoke dust of the fuming furnace, and valuable metals which are not easy to volatilize are recovered through a matte extraction mode, so that the blasting phenomenon generated when matte is directly discharged along with slag and meets water is avoided, and the safety risk of smelting is reduced.)

1. A tin smelting method capable of realizing valuable metal recovery is characterized by comprising the following steps: the method comprises the following steps:

s1: adding tin mineral materials containing valuable metals and copper-containing sulfur slag into a fuming furnace for smelting;

s2: in the smelting process, adding sulfur concentrate for blowing, wherein copper and sulfur are smelted to form copper matte, valuable metals which are not easy to volatilize are enriched into the copper matte, and tin and the volatile valuable metals are volatilized through vulcanization and are collected and recovered through smoke dust;

s3: in the blowing process, detecting the content of tin in the slag in the fuming furnace, and finishing the blowing when the grade of the tin is less than or equal to 0.3 percent;

s4: after the blowing is finished, opening a slag tap of the fuming furnace, and putting the slag melt into a dilution furnace for clarifying and separating slag and matte;

s5: after clarification and separation, the slag liquid on the upper layer surface of the depletion furnace is discharged through a slag tap at the upper part of the depletion furnace and is quenched into waste slag; the matte extracted with the valuable metals on the lower layer of the dilution furnace is discharged through a discharge port at the lower part of the dilution furnace, and the valuable metals are recovered through the extraction of the matte.

2. The tin smelting method capable of realizing valuable metal recovery according to claim 1, characterized in that: when smelting is performed in the step S1, quartz stone is added as a solvent to reduce the viscosity of the molten metal, and the ratio of iron to silicon is adjusted according to the iron content of the raw material in the fuming furnace so that the ratio of iron to silicon is: 1.0 to 2.0.

3. The tin smelting method capable of realizing valuable metal recovery according to claim 2, characterized in that: in the step S2, the usage amount of the sulfur concentrate is calculated according to the following ratio of S: sn is controlled to be 0.54-0.6.

4. The tin smelting method capable of realizing valuable metal recovery according to claim 3, characterized in that: in the step S2, during blowing, the sulfur concentrate is added in four time intervals, and the time interval of each time interval is 25-40 minutes.

5. The tin smelting method capable of realizing valuable metal recovery according to claim 4, characterized in that: the quantities of the sulfur concentrates added in the four periods are respectively as follows: 40-50% of the total amount is added in the first period; 25-35% of the total amount is added in the second time period; 10-15% of the total amount is added in the third time period; the adding amount of the additive is 5 to 10 percent of the total amount in the fourth period.

6. The tin smelting method capable of realizing valuable metal recovery according to claim 5, characterized in that: the temperature of the fuming furnace is controlled to be 1150-1250 ℃.

Technical Field

The invention relates to the technical field of tin smelting, in particular to a tin smelting method capable of realizing valuable metal recovery.

Background

In the process of tin smelting, because tin ore and added sulfur concentrate both contain a certain amount of valuable metals such as gold, silver, copper, lead, antimony and the like, the valuable metals are lost and discarded along with waste residues in a general traditional process, so that the resource waste of the valuable metals is caused, and meanwhile, because the valuable metals contained in the waste residues are easy to cause blasting phenomenon when the waste residues are discharged, the contact between sulfur tin copper matte and water is easy to cause, so that the safety of a tin smelting process is influenced. Therefore, a method for recovering valuable metals in a tin smelting process needs to be researched by the technical personnel in the field, so that the utilization rate of resources is improved, and the process risk is also reduced.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the tin smelting method capable of recycling the valuable metals is provided, the valuable metals are recycled in the tin smelting process, the effective utilization rate of resources is improved, and meanwhile, the phenomenon of blasting caused by contact between copper matte and water in the normal tin smelting process when the fuming furnace discharges slag is avoided.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a tin smelting method capable of realizing valuable metal recovery comprises the following steps:

s1: adding tin mineral materials containing valuable metals and copper-containing sulfur slag into a fuming furnace for smelting;

s2: in the smelting process, adding sulfur concentrate for blowing, wherein copper and sulfur are smelted to form copper matte, valuable metals which are not easy to volatilize are enriched into the copper matte, and tin and the volatile valuable metals are volatilized through vulcanization and are collected and recovered through smoke dust;

s3: in the blowing process, detecting the content of tin in the slag in the fuming furnace, and finishing the blowing when the grade of the tin is less than or equal to 0.3 percent;

s4: after the blowing is finished, opening a slag tap of the fuming furnace, and putting the slag melt into a dilution furnace for clarifying and separating slag and matte;

s5: after clarification and separation, the slag liquid on the upper layer surface of the depletion furnace is discharged through a slag tap at the upper part of the depletion furnace and is quenched into waste slag; the matte extracted with the valuable metals on the lower layer of the dilution furnace is discharged through a discharge port at the lower part of the dilution furnace, and the valuable metals are recovered through the extraction of the matte.

Further, when smelting is performed in step S1, quartz stone is added as a solvent to reduce the viscosity of the molten metal, and the ratio of iron to silicon is adjusted according to the iron content of the raw material in the fuming furnace so that the ratio of iron to silicon is: 1.0 to 2.0.

Further, in the step S2, the usage amount of the sulfur concentrate is calculated according to the ratio of S: sn is controlled to be 0.54-0.6.

Further, in the step S2, during the blowing, the sulfur concentrate is added in four time intervals, and the time interval of each time interval is 25-40 minutes.

Further, the amounts of the sulfur concentrate added in the four periods are respectively as follows: 40-50% of the total amount is added in the first period; 25-35% of the total amount is added in the second time period; 10-15% of the total amount is added in the third time period; the adding amount of the additive is 5 to 10 percent of the total amount in the fourth period.

Further, the temperature of the fuming furnace is controlled to be 1150-1250 ℃.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, through reasonable control of materials, smelting of tin is completed in the blowing process, volatile valuable metals are recovered through smoke dust of the fuming furnace, meanwhile, the extractability of matte is effectively utilized, and valuable metals which are not easy to volatilize are recovered through the matte extraction mode.

Drawings

FIG. 1 is a process diagram of the present invention.

Detailed Description

The present invention will be further described with reference to the following description and examples, which include but are not limited to the following examples.

As shown in fig. 1:

a tin smelting method capable of realizing valuable metal recovery realizes the recovery and utilization of valuable metals in raw materials and the effective utilization of resources in the smelting process, and simultaneously avoids the blasting phenomenon generated when water is directly discharged along with slag through the clarification and separation of a depleting furnace on matte, and reduces the safety risk of smelting.

The method comprises the steps of mixing tin middlings containing valuable metals such as copper, gold, silver, lead and antimony with copper-containing sulfur slag generated in a crude tin refining process, putting the mixture into a fuming furnace for smelting, igniting coal when added molten hot slag reaches the capacity of 1/4-1/2 slag packages, gradually adjusting the coal feeding amount along with the addition of liquid materials, and entering normal blowing to enable the temperature in the fuming furnace to reach more than 1150 ℃ (specifically, when the molten slag in the fuming furnace turns over to form small strand gushing, the temperature is up to 1150 ℃, and when the temperature in the furnace is low, furnace burden is up-blown from the furnace in a cotton ball shape). When the temperature in the fuming furnace reaches more than 1150 ℃, adding sulfur concentrate into the furnace, controlling the sulfur concentrate according to a certain amount, and treating the sulfur concentrate amount required by one furnace according to S: sn is controlled to be 0.54-0.6. The sulfur concentrate is added in four time intervals in batches, each time interval is about 25-40 minutes, and generally 40% -50% of the total sulfur concentrate is added in the first time interval, so that higher sulfur potential is caused, and the rapid implementation of volatilization operation is facilitated. When adding one batch of sulfur concentrate, the dense white smoke in the furnace can be seen immediately, and then the white smoke is reduced along with the time extension, and then one batch of sulfur concentrate is added. In the second time interval, 25 to 35 percent of the total sulfur concentrate is added; in the third time interval, about 10 to 15 percent of the total sulfur concentrate is added; in the fourth period, about 5-10% of the total sulfur concentrate is added, and the sulfur concentrate is stopped being added 20 minutes before slag discharging. In the stage, the added raw materials and copper and sulfur in the sulfur concentrate form copper matte, valuable metals (such as gold, silver and the like) which are not easy to volatilize are enriched in the copper matte, meanwhile, a large amount of sulfides, tin and the valuable metals (such as lead, antimony, zinc and the like) which are easy to volatilize can be mostly vulcanized and volatilized to form smoke dust in the stage, and the smoke dust is recovered through a cooler, a bag-type dust remover and other equipment.

At this stage, the fuming furnace blowing process undergoes a sulfidation reaction of tin. When the temperature of the slag reaches 1150 ℃, adding sulfur concentrate into the furnace, and performing thermal decomposition on the sulfur concentrate to generate ferrous sulfide and sulfur steam:

2FeS2＝2FeS+S2

the decomposition pressure of sulfur vapor increases with increasing temperature, followed by the following reaction:

2Sn+S2＝2SnS↑

4SnO+3S2＝4SnS↑+2SO2↑

SnO + FeS ═ SnS ≠ + FeO, and the tin realizes sulfuration volatilization at the stage.

The behavior of the remaining elements at this stage is as follows:

1. lead: under the operating conditions of the fuming furnace, lead can exist in three forms of metallic lead, lead oxide (PbO) and lead sulfide (PbS), and the metallic lead, the PbO and the PbS all have good volatility, wherein the volatility of the lead sulfide is the best, the volatility of the lead oxide is the second, the metallic lead is the worst, and the total volatilization amount of the lead can reach about 90%.

2. Zinc: under the fuming operation condition, zinc exists in three forms of metal zinc, zinc oxide (ZnO) and zinc sulfide (ZnS), the metal zinc has particularly good volatility, the zinc sulfide has poor volatility, and the zinc oxide hardly volatilizes. Because zinc oxide is difficult to reduce and the content of zinc in slag is small, zinc can only volatilize in a metal form under the condition of vulcanization volatilization, and the volatilization rate can reach 60-65%. The remainder of the zinc forms slag (reject slag) in the form of zinc silicate and zinc ferrite.

3. Arsenic, antimony and bismuth can be well volatilized.

4. Copper, gold and silver are present in copper matte.

5. Iron, silicon, etc. form silicate slag (waste slag) in the form of oxides.

In the process of converting, the judgment basis of converting completion is as follows: the tin content of the discarded slag is not higher than 0.3 percent, and the specific judging and detecting method comprises the following steps: and (3) extending the steel needle into the tertiary air inlet for a few minutes, and taking out the steel needle to observe the amount of the white tin dioxide powder condensed on the surface. The tin content of the slag is high when the powder is much, and the end point is not reached: if the powder is less, the tin content of the slag is low and the end point is reached quickly; sampling from a charging hole and sending the sample to a laboratory for rapid analysis, wherein the result can be obtained generally within 15-20 min, adding a batch of pyrite after sampling, and opening the opening for slag discharge when the tin content of the slag is not higher than 0.3% after the test result is obtained.

The lean slag produced under the operation condition of the fuming furnace is put into a lean furnace, the liquid slag and the copper matte are clarified and separated, and an upper layer and a lower layer are formed after a period of precipitation and clarification;

the upper aspect: through sedimentation and clarification, liquid slag floats on the slag, and is discharged through a slag hole at the upper part of the dilution furnace, so that the copper content of the liquid slag is lower, copper matte particles cannot be generated, and the explosion phenomenon cannot be generated during water quenching.

The following layers: after precipitation and clarification, matte is precipitated at the lower part, copper, gold and silver metals are precipitated in the matte, and after the upper liquid slag is discharged, the matte is discharged through a discharge port at the lower part of a dilution furnace, and cast ingots are cooled, so that the recovery of non-volatile valuable metals is completed.

The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.