CN111411242A - Method for dechlorinating high-chlorine tin-containing material - Google Patents

Method for dechlorinating high-chlorine tin-containing material Download PDF

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CN111411242A
CN111411242A CN202010370815.4A CN202010370815A CN111411242A CN 111411242 A CN111411242 A CN 111411242A CN 202010370815 A CN202010370815 A CN 202010370815A CN 111411242 A CN111411242 A CN 111411242A
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tin
chlorine
containing material
water
leaching
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李周华
王红彬
陈云
李月娟
刘庆东
谢云华
马松立
高超
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Smelting Branch Yunnan Tin Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/02—Obtaining tin by dry processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a method for dechlorinating a high-chlorine tin-containing material, which belongs to the technical field of tin smelting and mainly comprises four steps of water size mixing, leaching of a leaching solution, stirring of the material and solid-liquid separation, wherein the leached and separated tin material is sent to smelting, and the leaching solution is circularly concentrated; according to the invention, chlorine in the tin material is effectively removed to be below 1.5%, and part of impurities are also effectively removed, so that the grade of the tin material is improved, and the influence of chlorine on the tin smelting process is effectively reduced.

Description

Method for dechlorinating high-chlorine tin-containing material
Technical Field
The invention belongs to the technical field of tin smelting, and particularly relates to a method for dechlorinating a high-chlorine tin-containing material.
Background
Along with the complication of the structure of the tin resource material, the secondary tin resource material is enlarged and put into smelting production, and the content of impurity chlorine and the like in the tin-containing material is higher and higher, thereby bringing a plurality of problems to the pyrometallurgy of tin. The main sources of impurity chlorine of the tin-containing materials are tin resource secondary materials, tin slag produced by chlorine-containing organic additives and high-chlorine smoke dust produced by enrichment of a metallurgical furnace, wherein the chlorine content of the tin resource secondary materials is about 1-12%, the tin-containing materials such as an electroplating plate, an electronic component, a welding flux and the like are mainly treated by a wet method (acid leaching), then sludge is dried and treated by a rotary kiln to produce, the other type of the impurity chlorine is mainly tin slag produced by alkaline refining detinning of crude lead, and the additives are mostly NaOH and NaNO3NaCl, etc., basic. The chlorine content of the tin slag produced by the chlorine-containing organic additive is about 8-20%, and the tin slag produced by adding a dehurizing agent such as ammonium chloride and the like in the tin refining process is mainly used.
In the pyrometallurgical high-temperature furnace kiln reduction smelting process, chloride ions are combined with tin and mainly volatilize into smoke in the form of stannous chloride, so that the smoke rate in the tin reduction smelting process is increased, the direct tin yield is reduced, and the production operation cost is increased. The increase of the chlorine content in the tin material can lead to the increase of the stannous chloride content in the smoke dust, thereby not only causing the loss of tin, but also increasing the smelting cost of the tin. According to statistics, a certain large-scale tin smelting plant in China adopts an Ausmelt furnace to process a tin material with the chlorine content of 0.15-1%, and the smoke dust rate is about 18-25%. According to rough statistics of the factory, in the tin smelting process, the smoke dust rate rises by one percentage point every time, and the annual operation cost rises by about 387.75 ten thousand yuan.
Meanwhile, along with the increase of the chloride content in the smelting flue gas, the corrosivity to related matched industrial equipment is also increased rapidly, and the effective starting rate of the metallurgical furnace kiln is reduced. At present, high-chlorine tin-containing materials are mainly treated by a pyrogenic process, the high-chlorine tin-containing materials enter smoke dust enrichment by virtue of chlorination volatilization, and are repeatedly put into a metallurgical furnace for proportioning and then are subjected to chlorination volatilization again, so that most of chlorine in tin smelting is not effectively opened, and the vicious cycle is continuously realized in a smelting process. At present, the method for removing chloride ions in tin materials mainly comprises a silver sulfate precipitation method, a copper-cadmium slag dechlorination method and an ion exchange method, wherein the dechlorination effect by using silver sulfate is better, but silver salt is expensive, and the regeneration recovery rate of silver is low. The chlorine removal method by using the copper-cadmium slag can remove partial chlorine, but has high purification cost and brings some impurities back to the system. The ion exchange dechlorination method also has the problems of high cost, large investment and unsuitability for large-scale production. No effective method for dechlorinating tin materials is found at present
Along with continuous exploitation of tin ore, the grade level of tin materials is continuously reduced, the content of impurities is continuously increased, the increase of chlorine content and the decrease of tin grade cause great troubles for tin smelting, the control of a production system is more complicated, the smelting cost is also continuously increased, the improvement of tin grade and the reduction of chlorine content in tin materials become technical problems which must be solved by the tin smelting industry.
Disclosure of Invention
In order to overcome the problems in the background art, the invention provides a method for dechlorinating a high-chlorine tin-containing material, which is particularly suitable for treating a secondary tin-containing material with higher chlorine content and has the characteristics of simple process, low cost and higher chlorine removal rate of the treated tin-containing material.
In order to realize the purpose, the invention is realized by the following technical scheme:
the method for dechlorinating the high-chlorine tin-containing material comprises the following steps:
(1) pulping the tin-containing material with water;
(2) leaching the material after size mixing with a leaching solution;
(3) stirring the materials;
(4) filtering the leached material;
(5) returning the filtrate to the step (2) for recycling; and drying the tin-containing material, and then sending the tin-containing material to a metallurgical furnace for smelting.
Further, in the step (1), water and the tin-containing material are mixed according to the proportion of 1-3: 1.
Further, the leaching solution in the step (2) is prepared by mixing sodium hydroxide, calcium hydroxide, sodium carbonate and water in a ratio of 0-15: 0-10: 1-10: 30-95 by mass ratio.
Further, in the step (2): for the high-chlorine tin-containing material with the pH value less than 7 after water is used for size mixing, the leaching solution is prepared by mixing sodium hydroxide, calcium hydroxide, sodium carbonate and water in a ratio of 0-5: 0-10: 5-10: 75-85, and controlling the pH value of the leaching solution to be 8-12; for the high-chlorine tin-containing material with the pH value larger than 7 after being slurried by water, the leaching solution is prepared by mixing sodium hydroxide, calcium hydroxide, sodium carbonate and water in a ratio of 1-10: 0-10%: 1-10: 30-97, and controlling the pH value of the leaching solution to be 8-10.
Further, in the step (3): stirring the high-chlorine tin-containing material with the pH value less than 7 for 5-15min after the high-chlorine tin-containing material is subjected to size mixing by water; stirring the high-chlorine tin-containing material with the pH value of more than 7 after the high-chlorine tin-containing material is subjected to size mixing by water for 0-5 min.
Further, in the step (1), for the mixed high-chlorine tin-containing material with the pH value of more than 7 and the pH value of less than 7 after being slurried by water, the weight ratio of water: high-chlorine tin-containing material 1: mixing the slurry according to the proportion of 0.5-1.5; step (2) taking the production water as a leaching solution for spraying and washing; the stirring time in the step (3) is 0-5 min.
Furthermore, after the high-chlorine tin-containing material is mixed with water to be slurry, the pH value of the high-chlorine tin-containing material is less than 7, the chlorine leaching rate is more than or equal to 80%, the chlorine content can be reduced to less than or equal to 2% (the chlorine content is reduced by 3-8%), the tin grade can be improved by 4-9%, and the direct yield of tin metal is more than or equal to 99%.
Furthermore, after the high-chlorine tin-containing material is subjected to size mixing by water, the pH value is more than 7, the chlorine leaching rate is more than or equal to 90 percent, the chlorine content can be reduced to less than or equal to 1 percent (reduced by 4-10 percent), the tin grade can be improved by 5-10 percent, and the direct yield of tin metal is more than or equal to 99 percent.
The invention has the beneficial effects that:
according to the invention, the secondary tin material is treated by the leaching solution, and the tin material is repulped and leached, so that chlorine in the tin-containing material is effectively removed, the removal rate reaches over 90 percent, and the tin grade is improved by 4-10 percent; in the leaching process, the tin is basically insoluble, the direct yield of the tin reaches more than 99%, the chlorine in the tin material is effectively removed to be less than 1.5%, and partial impurities are also effectively removed, so that the grade of the tin material is improved, and the influence of the chlorine on the tin smelting process is effectively reduced.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
Example 1
The leaching solution is prepared by sodium hydroxide, calcium hydroxide, sodium carbonate and process water.
Crushing the tin dross, namely: and (3) mixing the production water in a ratio of 1:1-3, and after mixing, adjusting the pH value of the material to 4.2. A tin material contains 6.84% chlorine, and is prepared from the tin-contained material such as electroplated plate, electronic element and solder through wet (acid dipping) and drying in rotary kiln. Through phase analysis of the materials, the chlorine is mainly Na3Pb2(SO4)3Cl、NaCl、KClPbCl2Etc. with a tin oxide content of 50.40% and CuFeS2、ZnS、As2O3、SiO2、CaSO4·2H2O, and the like. During the process of mixing the slurry with the production water, part of the water-soluble impurities are dissolved.
Pumping the mixed materials into a leaching tower by a pump, carrying out spray leaching in the leaching tower according to the ratio of leaching liquid to tin slag slurry of 3-5:1, accelerating the leaching of chlorine in the presence of calcium hydroxide, stirring for 5-15min after the spray leaching is finished, conveying the materials in the leaching tower to a plate-and-frame filter press by the pump for solid-liquid separation, returning filtrate to the leaching tower for spray leaching of tin slag after second batch of mixing, recycling leaching waste liquid after 15-18 times, measuring that the main component of the leaching waste liquid is sodium chloride, the content of which is 40-60 g/L, and treating the leaching waste liquid by a concentration crystallization method.
In the leaching process under alkaline conditions, Na3Pb2(SO4)3Cl is dissociated to generate (PbCl)4)2-Complex ion, (PbCl)4)2-Further reacts with chloride ions to generate PbCl2During the reaction, the following reactions also occur:
2NaOH+PbCl2＝Pb(OH)2+2NaCl；
PbCl2+3OH-＝[Pb(OH)3]-+2Cl-
therefore, most of the chlorine and other impurities in the tin ore are dissolved in the water, and the chlorine in the tin ore is effectively removed.
And (4) sending the tin slag after the leaching solution is filtered out to a pyrometallurgical system.
The treatment results of different treatment processes are shown in the following table by using the same tin resource secondary material and the same method.
TABLE 1 statistical table of tin materials that are acidic after repulping under different treatment processes
Figure BDA0002478058010000051
The calcium hydroxide is not used, and the recycling frequency of the leaching solution is obviously reduced.
Example 2
The leaching solution is prepared by sodium hydroxide, calcium hydroxide, sodium carbonate and process water.
Crushing the tin dross, namely: and (3) mixing the production water with the proportion of 1 to 3, wherein the pH value of the material is 7.8 after mixing. The secondary material of the tin resource contains about 9.04 percent of chlorine, and is mainly tin slag produced by alkaline refining detinning of metals such as lead bullion and the like, and the tin slag is alkaline after being pulped. Through phase analysis of the materials, the chlorine is mainly NaCl and Pb5(AsO4)3Cl、FeCl3Etc. with tin oxide content of 62.48% and Pb content2SnSbO6.5、Pb5(AsO4)3Cl、PbSi2O5·1.6H2O、Na2CaSiO4And simple substance lead and other substances, and partial water-soluble substances are dissolved in the pulp mixing process.
Pumping the mixed materials into a leaching tower by a pump, and adding the mixed materials into the leaching tower according to the following leaching solution: spraying and leaching tin slag slurry at a ratio of 2-4:1, wherein chlorine leaching is accelerated by the presence of calcium hydroxide, stirring for 0-5min after spraying and leaching are finished, and conveying materials in a leaching tower to a plate by a pumpPerforming solid-liquid separation by using a frame filter press, returning filtrate to the leaching tower for spray leaching of the tin slag after the second batch of size mixing, recycling the leaching waste liquid after 18-22 times, measuring that the main component of the leaching waste liquid is sodium chloride with the content of 40-70 g/L, treating the leaching waste liquid by using a concentration crystallization method, and in the leaching process, Pb is removed5(AsO4)3Cl gradually releases chloride ions, ferric chloride reacts with hydroxyl to release chloride ions and Na2CaSiO4Reacts with hydroxyl to dissolve, so that most of chlorine and other impurities in the tin ore are dissolved in water, and the chlorine in the tin ore is effectively removed. And (4) sending the tin slag after the leaching solution is filtered out to a pyrometallurgical system.
TABLE 2 treatment results of alkaline tin materials after repulping under different treatment processes
Figure BDA0002478058010000061
The above preferred embodiments are only for illustrating the technical solutions of the present invention and are not limiting. From the above examples, it can be seen that in the case of no sodium hydroxide, the dechlorination effect is poor, and in the case of no calcium hydroxide, the cycle number of the leachate is significantly reduced, because in the process of chlorine leaching, calcium hydroxide participates in the reaction and accelerates the leaching of chlorine and other impurities, so that the chlorine leaching reaction continues, and the addition of calcium hydroxide in a proportion can also reduce the entry of a part of sodium ions, alleviate the saturated precipitation of sodium ions, thereby increasing the use number of the cycle liquid. On the other hand, the use of the calcium hydroxide in a proportioning manner can also reduce the use cost of the additive. While the invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

Claims (5)

1. A method for dechlorinating a high-chlorine tin-containing material is characterized by comprising the following steps: the method for dechlorinating the high-chlorine tin-containing material comprises the following steps:
(1) pulping the tin-containing material with water;
(2) leaching the material after size mixing with a leaching solution;
(3) stirring the materials;
(4) filtering the leached material;
(5) returning the filtrate to the step (2) for recycling; and drying the tin-containing material, and then sending the tin-containing material to a metallurgical furnace for smelting.
2. The method for dechlorinating the high-chlorine tin-containing material according to the claim 1, which is characterized by comprising the following steps: and (2) mixing the water and the tin-containing material in the step (1) according to the ratio of 1-3: 1.
3. A process according to claim 1 or 2 for dechlorinating a high chlorine tin-containing material, characterized in that: the leaching solution in the step (2) is prepared by mixing sodium hydroxide, calcium hydroxide, sodium carbonate and water in a ratio of 0-15: 0-10: 1-10: 30-95 mass ratio.
4. A process for dechlorinating a high chlorine tin-containing material according to any one of claims 1 to 3, characterized in that: in the step (2):
for the high-chlorine tin-containing material with the pH value less than 7 after water size mixing, the mixture ratio of the used leaching solution is as follows: sodium hydroxide: calcium hydroxide: sodium carbonate, water = 0-5: 0-10: 5-10: 75-85, and controlling the pH value of the leaching solution to be 8-12;
for the high-chlorine tin-containing material with the pH value larger than 7 after water size mixing, the mixture ratio of the used leaching solution is as follows: sodium hydroxide: calcium hydroxide: sodium carbonate: water = 1-10: 0-10%: 1-10: 30-97, and controlling the pH value of the leaching solution to be 8-9.
5. A process for dechlorinating a high chlorine tin-containing material according to any one of claims 1 to 3, characterized in that: in the step (3):
stirring the high-chlorine tin-containing material with the pH value less than 7 for 5-15min after the high-chlorine tin-containing material is subjected to size mixing by water;
stirring the high-chlorine tin-containing material with the pH value of more than 7 after the high-chlorine tin-containing material is subjected to size mixing by water for 0-5 min.
CN202010370815.4A 2020-05-06 2020-05-06 Method for dechlorinating high-chlorine tin-containing material Pending CN111411242A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307385A (en) * 2008-06-23 2008-11-19 云南锡业集团（控股）有限责任公司 Method for treating indium stannum smoke raw material
CN105366713A (en) * 2015-12-10 2016-03-02 柳州华锡铟锡材料有限公司 Method for producing high-purity sodium stannate by utilization of tin slag
CN110872649A (en) * 2019-12-27 2020-03-10 华中科技大学 Method for recovering tin from tin-containing lead slag

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307385A (en) * 2008-06-23 2008-11-19 云南锡业集团（控股）有限责任公司 Method for treating indium stannum smoke raw material
CN105366713A (en) * 2015-12-10 2016-03-02 柳州华锡铟锡材料有限公司 Method for producing high-purity sodium stannate by utilization of tin slag
CN110872649A (en) * 2019-12-27 2020-03-10 华中科技大学 Method for recovering tin from tin-containing lead slag

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
石玉霞: "碱式氯化亚锡渣生产氧化亚锡", 《有色冶炼》 *

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