阅读说明：本技术 一种高锑粗锡分离提纯的方法 (Method for separating and purifying high-antimony crude tin ) 是由 李一夫 张环 杨斌 刘大春 徐宝强 田阳 陈秀敏 徐俊杰 周生安 于 2021-07-28 设计创作，主要内容包括：本发明涉及一种高锑粗锡分离提纯的方法,属于有色金属火法冶炼技术领域。对高锑粗锡进行真空气化处理,使粗锡中的易挥发杂质元素最大限度的气化,气化挥发形成的混合金属蒸气；将得到的混合金属蒸气通过导入与真空气化炉相连的分级冷凝器,分别控制分级冷凝器冷凝区域温度为550～700℃、300～450℃和100～250℃,分别得到粗铅、粗锑和粗砷产品,以及气化挥发留下的精锡产品。本方法解决了锑元素在锡精炼系统中循环的问题,流程短,无“三废”产生,最大限度地回收了有价金属,处理成本低廉,金属回收率和直收率高,作业环境好,过程安全可控。(The invention relates to a method for separating and purifying high-antimony crude tin, belonging to the technical field of pyrometallurgy of non-ferrous metals. Carrying out vacuum gasification treatment on the high-antimony crude tin to ensure that volatile impurity elements in the crude tin are gasified to the maximum extent, and gasifying and volatilizing to form mixed metal steam; and introducing the obtained mixed metal steam into a grading condenser connected with a vacuum gasification furnace, and respectively controlling the temperature of a condensation area of the grading condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃ to respectively obtain crude lead, crude antimony and crude arsenic products and refined tin products left after gasification and volatilization. The method solves the problem of antimony element circulation in a tin refining system, has short flow, no three wastes, recycles valuable metals to the maximum extent, has low treatment cost, high metal recovery rate and direct recovery rate, good operation environment and safe and controllable process.)

1. A method for separating and purifying high-antimony crude tin is characterized by comprising the following steps:

step 1, carrying out vacuum gasification treatment on high-antimony crude tin, and gasifying and volatilizing to form mixed metal steam;

and 2, introducing the mixed metal vapor obtained in the step 1 into a fractional condenser connected with a vacuum gasification furnace, respectively controlling the temperature of a condensation area of the fractional condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃, respectively obtaining crude lead, crude antimony and crude arsenic products, and leaving refined tin products after gasification and volatilization.

2. The method for separating and purifying the high-antimony crude tin according to claim 1, characterized in that: in the step 1, the content of the high-antimony crude tin Sn is 70-95 wt%, the content of Sb is 5-18 wt%, the content of Pb is 0.5-10 wt%, and the content of As is 0.1-5 wt%.

3. The method for separating and purifying the high-antimony crude tin according to claim 1, characterized in that: in the step 1, the temperature in the vacuum gasification treatment is 900-1400 ℃, the system pressure is 1-100 Pa, and the gasification time is 30-200 min.

Technical Field

The invention relates to a method for separating and purifying high-antimony crude tin, belonging to the technical field of pyrometallurgy of non-ferrous metals.

Background

Most of domestic and overseas tin smelting enterprises adopt a fire refining process to gradually remove impurities in crude tin, and the main processes of the process comprise the steps of removing iron and arsenic by condensation, removing copper (sulfur slag) by adding sulfur, removing arsenic and antimony (aluminum slag) by adding aluminum, removing lead and bismuth by crystallization separation, and carrying out vacuum distillation treatment on soldering tin. The aluminum slag generally contains 6-12% of aluminum, 10-15% of antimony, 1-3% of arsenic and 55-70% of tin, belongs to hazardous waste, and can generate virulent arsine when being improperly disposed, so that people die.

The aluminum slag is mostly smelted by an electric furnace to produce tin-antimony-arsenic smoke dust (containing 30-35% of tin, 0.5-1% of arsenic and 2-4% of antimony), electric furnace slag and high-antimony crude tin (containing 80-85% of tin, 3-12% of antimony and 1-2% of arsenic). The arsenic-antimony-containing smoke dust is subjected to dearsenization treatment and then returns to reduction smelting, and antimony enters a tin smelting system again to cause accumulation, so that the normal operation of a tin smelting process is influenced.

The main treatment methods of the high-antimony crude tin comprise the following three methods: (1) the crude tin with high copper, antimony, lead and bismuth is produced by mixing and smelting copper slag and aluminum slag, and the babbitt alloy is prepared by adopting a method of separating lead and bismuth by vacuum distillation, but the babbitt alloy has small market demand, generally achieves the purpose of fixed production and has lower sale price. (2) An electrolytic method: firstly, casting a high-antimony crude tin alloy into an anode plate, and carrying out electrolytic solution treatment at the concentration of 70g/L, Sn²⁺The concentration is 60g/L and the current density is 120A/m²The electrolysis is carried out at normal temperature under the condition of (1), 99.99 percent of cathode tin is produced at the cathode, and antimony is finally producedAnd then the anode sludge and the electrolytic waste liquid are added. The anode mud has complex components, is not easy to comprehensively treat valuable metals such as antimony, tin and the like, and meanwhile, the electrolytic waste liquid contains a large amount of arsenic elements, thereby having great harm to the environment. (3) High-temperature-low-temperature two-stage continuous vacuum distillation method: the method is characterized in that crude tin and a tin-lead-antimony alloy I (Sn 25-30%, Pb30% and Sb 25%) are produced by carrying out one-time high-temperature vacuum distillation on the high-antimony crude tin, and a tin-antimony alloy (Sb15.45%) and a lead-antimony alloy (Sb40%) are produced by carrying out low-temperature vacuum distillation on the tin-lead-antimony alloy I.

The patent with publication number CN 1156184A discloses a method for separating antimony from antimony-containing crude tin, wherein the content of antimony in the antimony-containing crude tin is about 10%, the process is carried out in a vacuum furnace, the furnace temperature is controlled at 1300 ℃, the residual pressure in the furnace is less than 13Pa, and the distillation time is 30-120 minutes. The method effectively separates the impurity antimony, reduces the content of the impurity antimony in the product to more than 1 percent, but the practice of vacuum distillation production of crude tin shows that when the distillation temperature is higher than 1200 ℃, tin can be volatilized in large quantity, and the existence of Sb between tin and antimony is known from a phase diagram of Sn-Sb binary alloy₂Sn₃The intermetallic compounds, and therefore also part of the tin, are carried out of the melt during the evaporation of antimony, and the resulting tin-lead-antimony alloy still requires further processing, which finally results in a severe reduction in the direct yield of metallic tin. The patent publication No. CN 101696475B discloses a method for separating a lead-tin-antimony ternary alloy, wherein the lead-tin-antimony ternary alloy is treated by a vacuum distillation method, the distillation temperature is controlled to be 900-1200 ℃, the distillation time is 40-60 min, the vacuum degree is 5-15 Pa, and three components in the alloy are subjected to one-step distillation treatment, so that high-boiling-point tin is kept in a liquid state, and low-boiling-point lead-antimony is volatilized from the alloy in a gaseous state, and is separated from liquid tin. The method is an extension of the aforementioned publication No. CN 1156184A, and is used for treating tin-lead-antimony alloy, but the obtained residue is crude tin, and still needs to be returned to a tin refining system for purification, and Sn-Pb-Sb ternary alloy in volatile matters still coexists and is not easy to be further treated, so that the direct recovery rate of metal is not high, and the purpose of separately recovering the multicomponent alloy cannot be achieved. Patent application No. 201510059683.2 discloses a vacuum steaming method for antimony-containing crude tin alloyThe main process of the method is that the coarse tin alloy containing antimony is continuously vacuum distilled to obtain refined tin and tin-lead-antimony alloy, and then the tin-lead-antimony alloy is secondarily continuously vacuum distilled and is fractionally condensed to obtain the tin-lead-antimony alloy and the lead-antimony alloy. The temperature required by the method is 1500-1700 ℃ when one-time continuous vacuum distillation is carried out, the energy consumption is high, the conventional vacuum distillation furnace is difficult to realize the high-temperature environment, a special vacuum furnace is required, and the universality of equipment is not high. On the other hand, since the system temperature is higher than the boiling point of tin under vacuum (1521 ℃), metallic tin is volatilized in a large amount, resulting in a low direct yield. The patent with application number 201510060061.1 discloses a method for separating antimony from tin-antimony alloy by vacuum distillation, which comprises the steps of continuously vacuum distilling the tin-antimony alloy to obtain crude tin and tin-antimony mixed metal vapor, and then carrying out fractional condensation to respectively obtain crude antimony and the tin-antimony alloy. The method has the defects that the continuous vacuum distillation temperature is too high (1000-1700 ℃), and products meeting the requirements can be obtained only by repeating the process for many times, so that the labor intensity and the cost are increased. The patent with the application number of 202010547990.6 discloses a method for opening a circuit of antimony in tin smelting by combining a pyrogenic process and a wet process, which is characterized in that aluminum slag generated by adding aluminum to remove arsenic and antimony in the crude tin refining process is smelted by an electric furnace to obtain high-antimony crude tin, then vacuum distillation is carried out to obtain vacuum crude tin and tin-lead-antimony alloy, the crude tin is subjected to electrolytic refining to obtain refined tin, and the tin-lead-antimony alloy is subjected to secondary vacuum distillation to respectively obtain secondary vacuum crude tin and lead-antimony alloy. The method recovers tin in an economical way, but the content of antimony (Sb) in the obtained vacuum crude tin is still high<3 wt.%), a large amount of antimony enters the anode slime during the electrolytic refining process, and subsequent treatment is not easy.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a method for separating and purifying high-antimony crude tin. The method solves the problem of antimony element circulation in a tin refining system, has short flow, no three wastes, recycles valuable metals to the maximum extent, has low treatment cost, high metal recovery rate and direct recovery rate, good operation environment and safe and controllable process. The invention is realized by the following technical scheme.

A method for separating and purifying high-antimony crude tin comprises the following steps:

step 1, carrying out vacuum gasification treatment on high-antimony crude tin to ensure that volatile impurity elements in the crude tin are gasified to the maximum extent, and gasifying and volatilizing to form mixed metal steam;

and 2, introducing the mixed metal vapor obtained in the step 1 into a fractional condenser connected with a vacuum gasification furnace, respectively controlling the temperature of a condensation area of the fractional condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃, respectively obtaining crude lead, crude antimony and crude arsenic products, and leaving refined tin products after gasification and volatilization.

In the step 1, the content of the high-antimony crude tin Sn is 70-95 wt%, the content of Sb is 5-18 wt%, the content of Pb is 0.5-10 wt%, and the content of As is 0.1-5 wt%.

In the step 1, the temperature in the vacuum gasification treatment is 900-1400 ℃, the system pressure is 1-100 Pa, and the gasification time is 30-200 min.

The grading condenser is made of quartz materials, and is provided with a resistance wire heating body and circulating cooling water for controlling the condensation temperature.

The Sn content of the refined tin product treated by the method is more than 99.9 percent, the Pb content in the crude lead is 90-95 percent, the Sn content is 4-10 percent, the Sb content is 0.3-3 percent, the As content is less than 1 percent, the Sb content in the crude antimony is 90-98 percent, the Pb content is 0.7-10 percent, the As content is less than 1 percent, and the As content in the crude arsenic is 98-99 percent.

The metal recovery rate of the tin, the lead, the antimony and the arsenic is more than 97 percent.

The invention has the beneficial effects that:

the method realizes the purpose of purifying and refining the crude tin in one step, simultaneously separately recovers valuable metals such as lead, antimony, arsenic and the like, solves the problem of the circulation of antimony in a tin refining system, greatly reduces the operation cost of enterprises, generates no three wastes in the treatment process, and has the advantages of safe and reliable whole process, convenient operation, simple required equipment, low cost, high metal recovery efficiency and friendly operation environment.

Drawings

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

Detailed Description

The invention is further described with reference to the following drawings and detailed description.

Example 1

As shown in figure 1, the method for separating and purifying the high-antimony crude tin comprises the following steps:

step 1, carrying out vacuum gasification treatment on 1kg of high-antimony crude tin (the composition of the components is shown in table 1), so that volatile impurity elements in the crude tin are gasified to the maximum extent, and mixed metal steam is formed by gasification and volatilization; wherein the temperature in the vacuum gasification treatment is 1400 ℃, the system pressure is 100Pa, and the gasification time is 200 min;

TABLE 1

Element(s)	Sn	Pb	Sb	As
					Content (wt%)	71.65	8.46	16.72	3.17

Step 2, introducing the mixed metal vapor obtained in the step 1 into a fractional condenser connected with a vacuum gasification furnace, respectively controlling the temperature of a condensation area of the fractional condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃, and respectively obtaining crude lead, crude antimony and crude arsenic products and refined tin products left after gasification and volatilization; the graded condenser is made of quartz materials, and is provided with a resistance wire heating unit and circulating cooling water for controlling the condensation temperature.

The assay product components of the crude lead, antimony and arsenic products obtained after the treatment by the method are shown in the table 2. The metal recovery rates of tin, lead, antimony and arsenic are respectively 98.7%, 99.1%, 98.8% and 99.4%.

TABLE 2 ingredients Table (wt%)

Example 2

As shown in figure 1, the method for separating and purifying the high-antimony crude tin comprises the following steps:

step 1, carrying out vacuum gasification treatment on 1kg of high-antimony crude tin (the composition of the components is shown in table 3), so that volatile impurity elements in the crude tin are gasified to the maximum extent, and mixed metal steam is formed by gasification and volatilization; wherein the temperature in the vacuum gasification treatment is 900 ℃, the system pressure is 1Pa, and the gasification time is 30 min;

TABLE 3

Step 2, introducing the mixed metal vapor obtained in the step 1 into a fractional condenser connected with a vacuum gasification furnace, respectively controlling the temperature of a condensation area of the fractional condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃, and respectively obtaining crude lead, crude antimony and crude arsenic products and refined tin products left after gasification and volatilization; the graded condenser is made of quartz materials, and is provided with a resistance wire heating unit and circulating cooling water for controlling the condensation temperature.

The assay product components of the crude lead, antimony and arsenic products obtained after the treatment by the method are shown in the table 4. The metal recovery rates of tin, lead, antimony and arsenic are respectively 99.0%, 97.3%, 98.2% and 99.6%.

TABLE 4 ingredients Table (wt%)

Example 3

As shown in figure 1, the method for separating and purifying the high-antimony crude tin comprises the following steps:

step 1, carrying out vacuum gasification treatment on 1kg of high-antimony crude tin (the composition of the components is shown in table 5), so that volatile impurity elements in the crude tin are gasified to the maximum extent, and mixed metal steam is formed by gasification and volatilization; wherein the temperature in the vacuum gasification treatment is 1200 ℃, the system pressure is 10Pa, and the gasification time is 30 min;

TABLE 5

Element(s)	Sn	Pb	Sb	As
					Content (wt%)	94.29	1.27	3.49	0.95

Step 2, introducing the mixed metal vapor obtained in the step 1 into a fractional condenser connected with a vacuum gasification furnace, respectively controlling the temperature of a condensation area of the fractional condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃, and respectively obtaining crude lead, crude antimony and crude arsenic products and refined tin products left after gasification and volatilization; the graded condenser is made of quartz materials, and is provided with a resistance wire heating unit and circulating cooling water for controlling the condensation temperature.

The assay product components of the crude lead, antimony and arsenic products obtained after the treatment by the method are shown in the table 6. The metal recovery rates of tin, lead, antimony and arsenic are respectively 99.0%, 97.3%, 98.2% and 99.6%.

TABLE 6 ingredients of the product table (wt%)

Example 4

As shown in figure 1, the method for separating and purifying the high-antimony crude tin comprises the following steps:

step 1, carrying out vacuum gasification treatment on 1kg of high-antimony crude tin (the composition of the components is shown in table 7), so that volatile impurity elements in the crude tin are gasified to the maximum extent, and mixed metal steam is formed by gasification and volatilization; wherein the temperature in the vacuum gasification treatment is 1200 ℃, the system pressure is 10Pa, and the gasification time is 100 min;

TABLE 7

Element(s)	Sn	Pb	Sb	As
					Content (wt%)	90.76	0.82	8.25	0.17

Step 2, introducing the mixed metal vapor obtained in the step 1 into a fractional condenser connected with a vacuum gasification furnace, respectively controlling the temperature of a condensation area of the fractional condenser to be 550-700 ℃, 300-450 ℃ and 100-250 ℃, and respectively obtaining crude lead, crude antimony and crude arsenic products and refined tin products left after gasification and volatilization; the graded condenser is made of quartz materials, and is provided with a resistance wire heating unit and circulating cooling water for controlling the condensation temperature.

The assay product components of the crude lead, antimony and arsenic products obtained after the treatment by the method are shown in Table 8. The metal recovery rates of tin, lead, antimony and arsenic are respectively 98.6%, 98.9%, 99.2% and 99.1%.

TABLE 8 ingredients Table (wt%)

While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.