阅读说明：本技术 一种阳极泥高收率环保锡回收工艺 (High-yield environment-friendly tin recovery process for anode slime ) 是由 曹海宙 赵瀚翔 王江绪 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种阳极泥高收率环保锡回收工艺,方法步骤如下：S1：将阳极泥放入煅烧装置中进行煅烧；S2：向煅烧后的阳极泥中加入硝基苯甲酸和盐酸进行氧化浸出,过滤分离,得到SnCl-2浸出液；S3：向S2的浸出液中加入海绵铅粉,进行氧化还原反应,反应结束后通过净化剂对反应后的溶液进行净化,再过滤分离出净化液；S4：以S2中的溶液为电解液,以惰性电极为阴极和阳极,通过电解沉积锡。本发明解决了现有的阳极泥回收锡工艺的效率低、污染严重等问题。(The invention discloses a high-yield environment-friendly tin recovery process for anode slime, which comprises the following steps: s1: putting the anode mud into a calcining device for calcining; s2: adding nitrobenzoic acid and hydrochloric acid into the calcined anode mud for oxidation leaching, and filtering and separating to obtain SnCl 2 Leaching liquor; s3: adding sponge lead powder into the leachate of S2, carrying out oxidation-reduction reaction, purifying the solution after the reaction by using a purifying agent after the reaction is finished, and filtering and separating out a purified solution; s4: and (4) taking the solution in the S2 as an electrolyte, taking inert electrodes as a cathode and an anode, and depositing tin by electrolysis. The invention solves the problems of low efficiency, serious pollution and the like of the conventional process for recovering tin from anode mud.)

1. The high-yield environment-friendly tin recovery process for anode slime is characterized by comprising the following steps:

s1: putting the anode mud into a calcining device for calcining;

s2: adding nitrobenzoic acid and hydrochloric acid into the calcined anode mud for oxidation leaching, and filtering and separating to obtain SnCl₂Leaching liquor;

s3: adding sponge lead powder into the leachate of S2, carrying out oxidation-reduction reaction, purifying the solution after the reaction by using a purifying agent after the reaction is finished, and filtering and separating out a purified solution;

s4: and (4) taking the solution in the S2 as an electrolyte, taking inert electrodes as a cathode and an anode, and depositing tin by electrolysis.

2. The process as claimed in claim 1, wherein the calcination temperature in S1 is 350-450 ℃ and the time is 2-3 h.

3. The process of claim 1, wherein the calcining device in S1 comprises a furnace body with a containing space, a sealing door is arranged on one side of the furnace body, one end of the sealing door is hinged with the furnace body, the other end of the sealing door can open or seal the furnace body around the hinged part, a support is fixedly arranged at the lower end of the furnace body, a heating assembly for roasting is further arranged at the bottom of the furnace body, the heating assembly comprises a plurality of sliding grooves formed at the bottom of the furnace body, telescopic sleeves with openings at the lower ends are arranged in the sliding grooves, the telescopic sleeves penetrate through the bottom of the furnace body and are in sliding connection with the sliding grooves, heating blocks for roasting are inserted in the telescopic sleeves, an electric push rod is further arranged outside the bottom of the furnace body, one end of the electric push rod is fixedly connected with the telescopic sleeves and is used for driving the telescopic sleeves to displace along the sliding grooves, the other end of the electric push rod is fixedly arranged on a mounting rack fixedly connected with the bottom of the furnace body, and one side of the furnace body is sequentially communicated with a condensation pipe and a tail gas treatment assembly.

4. The process for recovering the high-yield environment-friendly tin from the anode slime as recited in claim 3, wherein a circular bottom plate is further arranged at the bottom of the furnace body, the bottom plate is rotatably connected with the bottom of the furnace body, a rotary cylinder for driving the bottom plate to rotate around a central shaft is fixedly arranged at the lower end of the bottom plate, the other end of the rotary cylinder is fixedly arranged on the bracket, and the heating assembly is arranged on the bottom plate.

5. The process of claim 3, wherein the two ends of the condenser pipe are respectively communicated with a condenser pipe inlet pipe and a condenser pipe outlet pipe, two partition plates which are radially distributed are further fixedly arranged in the inner cavity of the condenser pipe, a condensation cavity for cooling gas is enclosed between the two partition plates and the inner wall of the condenser pipe, a condensate outlet and a condensate inlet which are communicated with the condensation cavity are fixedly arranged on the side wall of the condenser pipe, a plurality of vent pipes are further communicated between the two partition plates, and the two ends of each vent pipe respectively penetrate through the two partition plates.

6. The process of claim 3, wherein the tail gas treatment assembly comprises a plurality of filter screens positioned in an inner cavity of the tail gas treatment assembly, an adsorbent is filled between every two adjacent filter screens, the gas inlet end of the tail gas treatment assembly is communicated with the gas outlet end of the condensation pipe, the other end of the tail gas treatment assembly is detachably provided with an end cover, and the end cover is communicated with an exhaust pipe.

7. The process for recovering the high-yield environment-friendly tin from the anode mud as claimed in claim 3, wherein a dust collection box body is further arranged between the tail gas treatment assembly and the condensation pipe, a dust collection box gas inlet pipe and a dust collection box gas outlet pipe which are communicated with an inner cavity of the dust collection box body are arranged on the dust collection box body, the dust collection box gas inlet pipe is communicated with a gas outlet end of the condensation pipe, and the dust collection box gas outlet pipe is communicated with a gas inlet end of the tail gas treatment assembly.

8. The process for recovering the anode slime with high yield and environment friendliness as claimed in claim 1, wherein the mass-to-volume ratio of the anode slime, the nitrobenzoic acid and the hydrochloric acid in the S2 is 1g:1-3ml:8-12 ml.

9. The process for recovering the high-yield environment-friendly tin from the anode slime as recited in claim 1, wherein the purifying agent in the S3 is a solution of sodium bicarbonate, calcium hydroxide and sulfuric acid mixed according to a mass ratio of 1:0.5-1: 0.1-0.5.

10. The process of claim 1, wherein the reaction conditions for purification in S3 are as follows: the temperature is 50-100 deg.C, and the time is 30-90 min.

Technical Field

The invention relates to the technical field of tin recovery, in particular to a high-yield environment-friendly tin recovery process for anode slime.

Background

Tin belongs to an important strategic metal and is widely applied to the fields of electronics, chemical engineering, aerospace, national defense, military industry and the like. China is one of the most important tin producing, consuming and trading countries in the world and has the capability of completely controlling the international market. Tin is a resource which is relatively short in countries such as the United states, Japan, Europe and the like, and is taken as a strategic substance by many countries, and is strictly controlled, managed and reserved.

The existing treatment process for tin-containing materials such as tin anode slime at home and abroad can be divided into a wet method and a fire method. In the aspect of typical pyrogenic process treatment, chinese patent CN200910227066.3 describes that tin anode slime is mixed with a reducing agent and a flux, and then is subjected to reduction smelting in a reverberatory furnace to obtain a lead-tin alloy. The direct yield of lead and tin is 82-88%, the slag yield is 25-35%, the tin content in slag is 3-10%, and the lead content in slag is 0.4-1.4%; thunder et al treat high tungsten-tin mud by a molten pool smelting-continuous fuming method, the tin volatilization rate is 96%, the direct yield is 93.5%, the slag throwing content is 0.2%, the coal consumption is 4.6t/t metallic tin, and the smoke dust content is 60%.

In the aspect of a typical wet processing technology, Chinese patent CN200910114413.1 describes a method for recovering tin, antimony and lead from tin slag and enriching indium: using mixed liquor of hydrochloric acid, sodium chloride and hydrazine hydrate as leachate, carrying out potential control two-stage countercurrent reduction on tin slag powder containing tin, antimony, indium and arsenic oxides to leach antimony, neutralizing and hydrolyzing the leachate in the first stage to obtain crude antimony white, leaching lead from the leached slag in the second stage by using sodium chloride, cooling and crystallizing the leached slag in the second stage to obtain crude lead chloride, and washing sodium from the leached slag to obtain indium-containing tin concentrate containing 49.5-55.6% of tin and 1.04-1.2% of indium. The direct yield of tin is 98 percent, and the direct yield of indium is 95 percent; zhangliang et al uses tin-containing slag as raw material, and adopts alkali dissolution-leaching-impurity removal-concentration crystallization process to directly prepare sodium stannate product, and makes research on preparation parameters and conditions, and under the optimized condition the tin yield can be obtained, and is 86.3%.

However, for the existing technology for recovering tin from anode slime, the risks of low recovery efficiency, serious pollution and the like still exist.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides an anode slime high-yield environment-friendly tin recovery process, which solves the problems of low efficiency, serious pollution and the like of the conventional anode slime tin recovery process.

The invention provides a high-yield environment-friendly tin recovery process for anode slime, which comprises the following steps:

s1: putting the anode mud into a calcining device for calcining;

s2: adding nitrobenzoic acid into the calcined anode mudOxidizing and leaching with hydrochloric acid, filtering and separating to obtain SnCl₂Leaching liquor;

s3: adding sponge lead powder into the leachate of S2, carrying out oxidation-reduction reaction, purifying the solution after the reaction by using a purifying agent after the reaction is finished, and filtering and separating out a purified solution;

s4: and (4) taking the solution in the S2 as an electrolyte, taking inert electrodes as a cathode and an anode, and depositing tin by electrolysis.

Preferably, the calcination temperature in S1 is 350-450 ℃ and the time is 2-3 h.

Preferably, the calcining device in S1 includes a furnace body having an accommodating space, a sealing door is disposed on one side of the furnace body, one end of the sealing door is hinged to the furnace body, the other end of the sealing door can open or seal the furnace body around the hinged portion, a support is fixedly disposed at the lower end of the furnace body, the bottom of the furnace body further includes a heating assembly for calcining, the heating assembly includes a plurality of sliding slots formed at the bottom of the furnace body, a telescopic sleeve with an opening at the lower end is disposed in the sliding slots, the telescopic sleeve penetrates through the bottom of the furnace body and is slidably connected with the sliding slots, a heating block for calcining is inserted in the telescopic sleeve, an electric push rod is further disposed outside the bottom of the furnace body, one end of the electric push rod is fixedly connected with the telescopic sleeve for driving the telescopic sleeve to displace along the sliding slots, and the other end of the electric push rod, and one side of the furnace body is sequentially communicated with a condensation pipe and a tail gas treatment component.

Preferably, the bottom of the furnace body is further provided with a circular bottom plate, the bottom plate is rotatably connected with the bottom of the furnace body, a rotary cylinder used for driving the bottom plate to rotate around a central shaft is fixedly arranged at the lower end of the bottom plate, the other end of the rotary cylinder is fixedly arranged on the support, and the heating assembly is arranged on the bottom plate.

Preferably, the condenser pipe both ends communicate respectively has condenser pipe intake pipe and condenser pipe outlet duct, still the fixed baffle that is provided with two radial distributions in the inner chamber of condenser pipe, the inner wall of condenser pipe, two enclose between the baffle and become the condensation chamber that is used for the gas cooling, the condenser pipe lateral wall fixed be equipped with condensate outlet and condensate entry of condensation chamber intercommunication, two still communicate between the baffle has a plurality of breather pipes, the both ends of breather pipe link up two respectively the baffle.

Preferably, the tail gas treatment component is including being arranged in a plurality of filter screens of its inner chamber, and it has the adsorbent to fill between the adjacent filter screen, the inlet end of tail gas treatment component with the end intercommunication of giving vent to anger of condenser pipe, the end cover is installed to tail gas treatment component other end detachably, the intercommunication has the blast pipe on the end cover.

Preferably, a dust collecting box body is further arranged between the tail gas processing assembly and the condensing pipe, a dust collecting box air inlet pipe and a dust collecting box air outlet pipe which are communicated with an inner cavity of the dust collecting box body are arranged on the dust collecting box body, the dust collecting box air inlet pipe is communicated with an air outlet end of the condensing pipe, and the dust collecting box air outlet pipe is communicated with an air inlet end of the tail gas processing assembly.

Preferably, the mass volume ratio of the anode mud, the nitrobenzoic acid and the hydrochloric acid in the S2 is 1g:1-3ml:8-12 ml.

Preferably, the purifying agent in S3 is a mixed solution of sodium bicarbonate, calcium hydroxide and sulfuric acid according to the mass ratio of 1:0.5-1: 0.1-0.5.

Preferably, the reaction conditions for purification in S3 are: the temperature is 50-100 deg.C, and the time is 30-90 min.

Compared with the prior art, the invention has the beneficial technical effects that:

(1) according to the method, nitrobenzoic acid and hydrochloric acid are added into the calcined material for oxidation leaching, wherein the nitrobenzoic acid can oxidize a part of tin into tetravalent tin ions, and the tetravalent tin ions can oxidize tin in the raw material into divalent tin ions, so that the tin is leached by the hydrochloric acid in the form of SnCl2, and the subsequent treatment of tin is facilitated; in addition, high-temperature calcination is carried out before hydrochloric acid leaching, so that the subsequent hydrochloric acid leaching efficiency can be further improved.

(2) The heating assembly in the calcining device can be controlled to extend into the furnace body through the electric push rod to roast the anode mud, or the heating assembly is retracted to enable the top of the telescopic sleeve to be flush with the bottom of the bottom plate, so that roasted materials can be conveniently discharged, and in addition, deep heating of the anode mud can be realized through the heating assembly, so that the efficiency of anode mud treatment is improved; the condenser pipe has a good heat exchange effect; the tail gas treatment component that this application set up then has fine adsorption effect to the harmful substance in the gas after the cooling, and the filter screen and the adsorbent that set up still have the effect of filtering the dust, hold back the dust in the dust collecting box, make things convenient for its centralized processing, in addition, can also open the end cover after tail gas treatment component uses a period, then with filter screen and adsorbent in the inner chamber take out clear up and change can, simple and convenient.

Drawings

FIG. 1 is a schematic structural view of a calcination apparatus according to the present invention;

FIG. 2 is an enlarged view of a portion A-A of the calcining apparatus according to the present invention;

FIG. 3 is a schematic structural diagram of a condenser tube according to the present invention;

fig. 4 is a schematic structural diagram of an exhaust gas treatment assembly according to the present invention.

In the figure: 1-furnace body, 2-condenser pipe, 3-dust collection box air outlet pipe, 4-tail gas treatment component, 5-dust collection box body, 6-sealing door, 7-condensate outlet, 8-condenser pipe air inlet pipe, 9-partition plate, 10-vent pipe, 11-condensation cavity, 12-condensate inlet, 13-condenser pipe air outlet pipe, 14-end cover, 15-vent pipe, 16-filter screen, 17-adsorbent, 18-dust collection box air inlet pipe, 19-mounting frame, 20-heating block, 21-telescopic sleeve, 22-chute, 23-bottom plate, 24-rotary cylinder, 25-electric push rod and 26-support.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples.

Referring to fig. 1-4, the calcining apparatus provided by the present invention comprises a furnace body 1 having an accommodating space, a sealing door 6 is disposed on one side of the furnace body 1, one end of the sealing door 6 is hinged to the furnace body 1, the other end of the sealing door 6 can open or seal the furnace body 1 around the hinged portion, a support 26 is fixedly disposed at the lower end of the furnace body 1, the bottom of the furnace body 1 further comprises a heating assembly for calcining, the heating assembly comprises a plurality of sliding grooves 22 formed at the bottom of the furnace body 1, a telescopic sleeve 21 having an opening at the lower end is disposed in the sliding grooves 22, the telescopic sleeve 21 penetrates through the bottom of the furnace body 1 and is slidably connected with the sliding grooves 22, a heating block 20 for calcining is inserted in the telescopic sleeve 21, an electric push rod 25 is further disposed at the outer side of the bottom of the furnace body 1, one end of the electric push rod 25 is fixedly connected with, the other end of the electric push rod 25 is fixedly arranged on a mounting rack 19 fixedly connected with the bottom of the furnace body 1, and one side of the furnace body 1 is sequentially communicated with a condensation pipe 2 and a tail gas treatment component 4.

The heating component arranged in the application can be controlled by the electric push rod 25 to extend into the furnace body 1 to realize the roasting of the anode mud, or the top of the telescopic sleeve 21 is flush with the bottom of the bottom plate 23, so that the roasted material is conveniently discharged, in addition, the deep heating of the anode mud can be realized, thereby improving the efficiency of anode slime treatment, and for the electric push rod 25 in the application, only the measuring range and the bearing capacity need to be considered, when it moves to the maximum range, the heating component is in working position, when the electric push rod 25 moves to the minimum range, it is just retracted until the top of the telescopic sleeve 21 is flush with the bottom of the bottom plate 23, at which time the heating assembly stops working, for the control of the electric push rod 25, it can be controlled by an independent switch, or the control module can be integrated with the control panel of the whole device, and these can be realized by the existing technology. For the control of the heating block, the existing technology can be adopted.

In order to further improve the roasting efficiency of the anode mud, a circular bottom plate 23 is further arranged at the bottom of the furnace body 1, the bottom plate 23 is rotatably connected with the bottom of the furnace body 1, a rotary cylinder 24 for driving the bottom plate 23 to rotate around a central shaft is fixedly arranged at the lower end of the bottom plate 23, the other end of the rotary cylinder 24 is fixedly arranged on the support 26, and the heating assembly is arranged on the bottom plate 23. For the rotary cylinder 24, the bottom plate 23 can be controlled to rotate back and forth between 0 and 90 degrees, after the heating block 20 works for a period of time, the electric push rod 25 is firstly used for controlling the heating block to contract to the minimum range, then the rotary cylinder 24 is used for driving the bottom plate 23 to rotate 90 degrees, the electric push rod 25 is used for extending to the maximum range so as to convey the heating block 20 to the working position, and then the roasting can be continued. The structure and control method of the rotary cylinder can be realized by adopting the existing technology.

Referring to fig. 3, specifically, two ends of the condenser pipe 2 are respectively communicated with a condenser pipe inlet pipe 8 and a condenser pipe outlet pipe 13, two partition plates 9 which are radially distributed are further fixedly arranged in an inner cavity of the condenser pipe 2, a condensation cavity 11 for cooling gas is enclosed between the partition plates 9, a condensate outlet 7 and a condensate inlet 12 which are communicated with the condensation cavity 11 are fixedly arranged on the side wall of the condenser pipe 2, a plurality of vent pipes 10 are further communicated between the partition plates 9, and two ends of each vent pipe 10 are respectively communicated with the partition plates 9.

Referring to fig. 4, specifically, the tail gas treatment assembly 4 includes a plurality of filter screens 16 located in an inner cavity thereof, and an adsorbent 17 is filled between adjacent filter screens 16, the inlet end of the tail gas treatment assembly 4 is communicated with the outlet end of the condensation pipe 2, an end cover 14 is detachably installed at the other end of the tail gas treatment assembly 4, and an exhaust pipe 15 is communicated on the end cover 14. The condenser pipe 2 that this application set up has fine heat transfer effect.

In addition, a dust collecting box body 5 is further arranged between the tail gas processing assembly 4 and the condensation pipe 2, a dust collecting box air inlet pipe 18 and a dust collecting box air outlet pipe 3 which are communicated with the inner cavity of the dust collecting box body 5 are arranged on the dust collecting box body 5, the dust collecting box air inlet pipe 18 is communicated with the air outlet end of the condensation pipe 2, and the dust collecting box air outlet pipe 3 is communicated with the air inlet end of the tail gas processing assembly 4. The tail gas treatment component 4 that this application set up then has fine adsorption effect to the harmful substance in the gas after the cooling, and the filter screen 16 and the adsorbent 17 that set up still have the effect of filtering the dust, hold back the dust in collection dust box body 5, make things convenient for its centralized processing, in addition, can also open end cover 14 after tail gas treatment component 4 uses a period, then take out filter screen 16 and adsorbent 17 in the inner chamber clear up and change can, simple and convenient.

Example 1

The invention provides a high-yield environment-friendly tin recovery process for anode slime, which comprises the following steps:

s1: putting the anode mud into a calcining device for calcining;

s2: adding nitrobenzoic acid and hydrochloric acid into the calcined anode mud for oxidation leaching, and filtering and separating to obtain SnCl₂Leaching liquor;

s3: adding sponge lead powder into the leachate of S2, carrying out oxidation-reduction reaction, purifying the solution after the reaction by using a purifying agent after the reaction is finished, and filtering and separating out a purified solution;

s4: and (4) taking the solution in the S2 as an electrolyte, taking inert electrodes as a cathode and an anode, and depositing tin by electrolysis.

The calcining temperature in S1 is 350 ℃, and the time is 2 h.

In the S2, the mass-volume ratio of the anode mud to the nitrobenzoic acid to the hydrochloric acid is 1g:1ml:8 ml.

The purifying agent in the S3 is a mixed solution of sodium bicarbonate, calcium hydroxide and sulfuric acid according to the mass ratio of 1:0.5: 0.1; the reaction conditions for purification were: the temperature is 50 deg.C and the time is 30 min.

The tin recovery was calculated to be 96.4%.

Example 2

The invention provides a high-yield environment-friendly tin recovery process for anode slime, which comprises the following steps:

s1: putting the anode mud into a calcining device for calcining;

s2: adding nitrobenzoic acid and hydrochloric acid into the calcined anode mud for oxidation leaching, and filtering and separating to obtain SnCl₂Leaching liquor;

s3: adding sponge lead powder into the leachate of S2, carrying out oxidation-reduction reaction, purifying the solution after the reaction by using a purifying agent after the reaction is finished, and filtering and separating out a purified solution;

s4: and (4) taking the solution in the S2 as an electrolyte, taking inert electrodes as a cathode and an anode, and depositing tin by electrolysis.

The calcining temperature in S1 is 450 ℃, and the time is 3 h.

In the S2, the mass-volume ratio of the anode mud to the nitrobenzoic acid to the hydrochloric acid is 1g to 3ml to 12 ml.

The purifying agent in the S3 is a mixed solution of sodium bicarbonate, calcium hydroxide and sulfuric acid according to the mass ratio of 1:1: 0.5; the reaction conditions for purification were: the temperature is 100 ℃ and the time is 90 min.

The tin recovery was calculated to be 97.2%.

Example 3

The invention provides a high-yield environment-friendly tin recovery process for anode slime, which comprises the following steps:

s1: putting the anode mud into a calcining device for calcining;

s2: adding nitrobenzoic acid and hydrochloric acid into the calcined anode mud for oxidation leaching, and filtering and separating to obtain SnCl₂Leaching liquor;

s3: adding sponge lead powder into the leachate of S2, carrying out oxidation-reduction reaction, purifying the solution after the reaction by using a purifying agent after the reaction is finished, and filtering and separating out a purified solution;

s4: and (4) taking the solution in the S2 as an electrolyte, taking inert electrodes as a cathode and an anode, and depositing tin by electrolysis.

The calcining temperature in S1 is 400 ℃, and the time is 2.5 h.

In the S2, the mass volume ratio of the anode mud to the nitrobenzoic acid to the hydrochloric acid is 1g to 2ml to 10 ml.

The purifying agent in the S3 is a mixed solution of sodium bicarbonate, calcium hydroxide and sulfuric acid according to the mass ratio of 1:0.8: 0.3; the reaction conditions for purification were: the temperature is 75 ℃ and the time is 60 min.

The tin recovery was calculated to be 97.8%.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.