CN112391533A - Method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method - Google Patents
Method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method Download PDFInfo
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- CN112391533A CN112391533A CN202011343861.1A CN202011343861A CN112391533A CN 112391533 A CN112391533 A CN 112391533A CN 202011343861 A CN202011343861 A CN 202011343861A CN 112391533 A CN112391533 A CN 112391533A
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
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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
- C22B25/02—Obtaining tin by dry processes
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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
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- 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
Abstract
The invention discloses a method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method, which comprises the steps of mixing stanniferous electronic waste and an additive consisting of calcium sulfide and silicon dioxide uniformly, agglomerating, placing the mixture in a reducing atmosphere to perform reduction roasting at 750-900 ℃, and placing roasted volatile matter in a weak reducing atmosphere to perform reduction roasting at 450-700 ℃ to obtain nano stannous sulfide powder. The method takes the stanniferous electronic waste as the raw material to efficiently recover stannum and prepare the high-purity nano stannous sulfide powder material, not only realizes waste utilization and high economic added value, but also has simple operation, low production cost and environmental protection, and meets the requirement of industrial production.
Description
Technical Field
The invention relates to a preparation method of nano stannous sulfide, in particular to a method for separating tin in tin-containing electronic waste and recovering tin in the form of high-purity nano zinc oxide by taking the tin-containing electronic waste as a tin source, belonging to the technical field of electronic waste recovery.
Background
Electronic waste in urban mines contains abundant rare metal and precious metal resources, and is the key point of extracting metallurgy in the future. Unlike natural ore, most of the metal elements in the electronic waste exist in the form of simple metal and alloy, so the extraction metallurgical process cannot be completely similar to the traditional metallurgical process. Meanwhile, the electronic waste has various types and high content of metal elements, and if the electronic waste is completely put into the traditional pyrometallurgical and hydrometallurgical process, the loss rate of the metal elements is high, and particularly, in the pyrometallurgical process, precious metals such as gold and silver are easily dispersed in slag and are difficult to further enrich, separate and recover.
Most of the existing comprehensive extraction processes of tin in electronic waste use copper as a main target element, copper products are obtained through processes of blast furnace blowing, matte making, electrolytic refining and the like, in the process, a large amount of tin enters smoke dust or is dispersed into smelting slag, and subsequent separation and recovery are difficult. The hydrometallurgy technology generally adopts an oxidant and an acid system to carry out oxidation leaching on metal elements in the circuit board, and then selective separation and recovery are realized through the difference of precipitation intervals of various metal ions, but the tin element is dissolved with elements such as lead, zinc, antimony and the like, the coincidence degree of the precipitation intervals is high, and thorough separation is difficult to realize; the purity of the precipitate is limited, and the precipitate can only be used as one of raw materials of tin pyrometallurgy, so that the product value is further reduced.
The stannous sulfide has wide application and can be applied to a plurality of fields such as photoelectric conversion, organic catalysis, solid lubrication, battery cathode materials and the like. The existing preparation process of stannous sulfide mainly comprises a gas phase method, a precipitation method, a hydrothermal synthesis method, a solution gel method and the like. Most of the existing methods have the problems of low yield, harsh preparation conditions, difficulty in realizing large-scale production and the like. The stannous sulfide prepared by the traditional gas phase method has low purity, contains a large amount of impurities such as stannic oxide, stannic sulfide and the like, and the prepared products have the size of more than 100 microns, are coarse in granularity and have low economic added value.
Disclosure of Invention
Aiming at the problems of low comprehensive recovery rate and low economic added value of tin in tin-containing electronic waste in the prior art, the invention aims to provide the method for efficiently recovering tin and preparing high-purity nano stannous sulfide by using the tin-containing electronic waste as a tin source through a one-step method.
In order to achieve the technical purpose, the invention provides a method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method, which comprises the steps of mixing stanniferous electronic waste and additives uniformly, agglomerating, placing in a reducing atmosphere to perform reduction roasting at 750-900 ℃, and placing roasted volatile matter in a weak reducing atmosphere to perform reduction roasting at 450-700 ℃ to obtain nano stannous sulfide powder; the additive is a mixture of calcium sulfide and silica.
The key point of the method for preparing the nano stannous sulfide by using the stanniferous electronic waste is to promote the stannum in the stanniferous electronic waste to be vulcanized and volatilized by cooperatively controlling the atmosphere and the temperature so as to obtain the high-purity nano stannous sulfide powder. The tin-containing electronic waste enters a first-stage roasting area, the roasting is carried out under the control of higher temperature and strong reducing atmosphere, the metal tin with higher boiling point can be selectively sulfurized into stannous sulfide with low boiling point to volatilize under the condition, the stannous sulfide enters a second-stage roasting area, the second-stage roasting area is regulated under the conditions of lower temperature and weaker reducing atmosphere, the chemical stability of the stannous sulfide in the gas phase transmission process can be ensured under the condition, meanwhile, the crystal growth process of the stannous sulfide can be controlled, the stannous sulfide is separated out from the gas phase to crystallize, and nanoparticles with uniform grain sizes are formed. According to the invention, the high-temperature volatilization, selective separation, vulcanization conversion and homogeneous nucleation of tin can be realized by cooperatively controlling the two-stage roasting atmosphere and temperature conditions, so that the nano stannous oxide powder with high crystallinity is obtained.
The additive consists of calcium sulfide and silicon dioxide, wherein the calcium sulfide is a vulcanizing agent and has the structural stability effect with the silicon dioxide, and the silicon dioxide has the effects of improving the melting point of a system and improving the strength of a briquette.
As a preferable scheme, the tin-containing electronic waste is pretreated by a vacuum pyrolysis method or a mechanical crushing separation method, wherein the mass percent of tin is higher than 8.0%, and the mass percent of organic matters is lower than 1.0%. The organic content of the tin-containing electronic waste can be reduced by pretreating the tin-containing electronic waste through a vacuum pyrolysis method or a mechanical crushing and separating method, so that toxic organic gas generated in the roasting process is reduced, and the influence on the volatilization process of tin is reduced.
As a preferred scheme, the additive and the tin-containing electronic waste are mixed in a ratio that: Ca/Si is 2 to 2.2, and Sn/S is 1.5 to 2.0. The additive in the technical scheme of the invention plays a role in vulcanizing and improving the melting point and the briquetting strength of the mixed material, and ensures the high-selectivity separation of tin.
As a preferred scheme, the reaction is carried out under a reducing atmosphereIn the process of reduction roasting, the reducing atmosphere is controlled to be CO and CO2A mixed atmosphere, wherein the volume percentage of carbon monoxide satisfies: CO/(CO + CO)2) 3-10%, and the gas flow rate is 0.1-0.3 m/s. The strong reducing atmosphere can stabilize the composite additive and promote the vulcanization of tin, converting tin into stannous sulfide.
As a preferable scheme, in the process of carrying out reduction roasting under the weak reducing atmosphere, the weak reducing atmosphere is controlled to be CO and CO2A mixed atmosphere, wherein the volume percentage of carbon monoxide satisfies: CO/(CO + CO)2) 1-5%, and the gas flow rate is 0.2-0.5 m/s. The weak reducing atmosphere ensures the chemical stability of the gas phase stannous sulfide in the gas phase transmission process.
The invention removes organic components from tin-containing electronic waste by pretreatment, and then mainly mixes metal powder, wherein the main metal elements comprise lead, tin, zinc, copper, gold, silver, indium and the like, and various metal elements exist in a simple substance or alloy phase form, in the simple substance component, the tin melting point is lowest, a liquid phase is easy to form to be bonded with other metals, under the action of a special additive and under a strong reduction roasting condition, the tin can be subjected to a selective vulcanization reaction to form volatile stannous sulfide, and the product is separated by air flow regulation and control to reduce the product partial pressure in the environment and promote the reaction to continue, so that the vulcanization reaction and volatilization efficiency of the tin are improved. The transformation process of tin is controlled by the cooperation of temperature and atmosphere, so that homogeneous nucleation and grain growth of stannous sulfide are realized, and finally, a nanoscale stannous sulfide product with uniform granularity and stable components is obtained.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the method takes the tin-containing electronic waste as the raw material, realizes the secondary utilization and sustainable development of tin resources, treats the solid waste in a green and high-efficiency manner, and obtains products with high added values.
2) The invention can efficiently and selectively separate tin in the electronic waste by controlling the atmosphere roasting conversion in two stages, and the recovery rate can reach more than 90%.
3) The stannous sulfide product obtained by the invention reaches the nanometer levelSpecific surface area 100m2More than g, has uniform particle size, and can be applied to a plurality of fields such as gas sensitivity, batteries, catalytic materials and the like.
Drawings
FIG. 1 XRD analysis of the product of example 1 preparation
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Comparative example 1
The method comprises the following steps of (1) taking tin-containing electronic waste pyrolysis slag as a raw material (the tin content is 9.2%, the organic matter content is 0.5%), adding an additive (calcium sulfide) according to the dosage of Sn/S which is 2.0, mixing the additive uniformly, briquetting, and then placing the dried briquette into a two-section type controlled atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 10 vol.%, the calcination temperature is 900 ℃, and the gas flow rate is 0.3 m/s; the volatile product enters a second-stage roasting zone along with airflow, and the second-stage roasting weak reducing atmosphere comprises CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 5 vol.%, the calcination temperature is 700 ℃, and the gas flow rate is 0.5 m/s; the product can be separated and collected in the second section area, the recovery rate of tin is 62.6 percent, and the purity of the nano stannous sulfide is 72.4 percent. This comparative example is used to illustrate that without the additive complex, the system has a low melting point and an unstable structure, resulting in low tin conversion and low product purity.
Comparative example 2
The method comprises the following steps of (1) taking tin-containing electronic waste pyrolysis slag as a raw material (the tin content is 9.2%, the organic matter content is 0.5%), adding a composite additive (the composite additive is a mixture of calcium sulfide and silicon dioxide, and the proportion of Ca/Si is 2) according to the dosage of Sn/S being 1.7, fully mixing, briquetting, and placing the dried briquette into a one-stage controllable atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 10 vol.%, the calcination temperature is 900 ℃, and the gas flow rate is 0.3 m/s;the volatile products are condensed and separated out along with the temperature gradient, the products can be separated and collected in a section of area, the recovery rate of tin is 68.7 percent, and the purity of the nano stannous sulfide is 79.8 percent. The comparative example is used for illustrating that after the composite additive is added, the melting point of the system is improved, the material structure is stable, the components are uniform at high temperature, and the vulcanization of tin is promoted, but the one-section strong oxidizing atmosphere is controlled to directly convert most substances, so that the gas phase separation cannot be formed, the collected products are fewer, and the product purity is not high.
Example 1
The method comprises the following steps of (1) taking tin-containing electronic waste pyrolysis slag as a raw material (the tin content is 9.2%, the organic matter content is 0.5%), adding a composite additive (the composite additive is a mixture of calcium sulfide and silicon dioxide, and the proportion of Ca/Si is 2.2) according to the dosage of Sn/S being 2.0, fully mixing the composite additive and the silicon dioxide, briquetting, and placing the dried briquette into a two-stage controllable atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 10 vol.%, the calcination temperature is 900 ℃, and the gas flow rate is 0.3 m/s; the volatile product enters a second-stage roasting zone along with airflow, and the second-stage roasting weak reducing atmosphere comprises CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 5 vol.%, the calcination temperature is 700 ℃, and the gas flow rate is 0.5 m/s; the product can be separated and collected in the second-stage area, the recovery rate of tin is 95.3 percent, the purity of nano stannous sulfide is 98.8 percent, and the specific surface area of the stannous sulfide is 176m2(ii) in terms of/g. (XRD phase analysis of the synthesized product is shown in FIG. 1, the refined analysis grain size is 56nm, and the theoretical purity is 99.4%)
Example 2
The method comprises the following steps of taking tin-containing electronic waste pyrolysis slag as a raw material (the tin content is 9.2%, the organic matter content is 0.5%), adding a composite additive (the composite additive is a mixture of calcium sulfide and silicon dioxide, the proportion of the composite additive is Ca/Si is 2.0) according to the dosage of Sn/S being 1.5, mixing the composite additive fully, briquetting, and placing the dried briquette into a two-section type controlled atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2)＝10vol%, the roasting temperature is 850 ℃, and the gas flow rate is 0.3 m/s; the volatile product enters a second-stage roasting zone along with airflow, and the second-stage roasting weak reducing atmosphere comprises CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 3 vol.%, the calcination temperature 650 ℃, and the gas flow rate 0.4 m/s; the product can be separated and collected in a second-stage area, the recovery rate of tin is 93.4 percent, the purity of nano stannous sulfide is 97.3 percent, and the specific surface area of the stannous sulfide is 163m2/g。
Example 3
The method comprises the following steps of (1) taking tin-containing electronic waste pyrolysis slag as a raw material (the tin content is 9.2%, the organic matter content is 0.5%), adding a composite additive (the composite additive is a mixture of calcium sulfide and silicon dioxide, and the proportion of Ca/Si is 2.1) according to the dosage of Sn/S which is 1.8, fully mixing, briquetting, and placing the dried briquette into a two-stage controllable atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 8 vol.%, the calcination temperature is 800 ℃, and the gas flow rate is 0.2 m/s; the volatile product enters a second-stage roasting zone along with airflow, and the second-stage roasting weak reducing atmosphere comprises CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 2 vol.%, the calcination temperature is 550 ℃, and the gas flow rate is 0.2 m/s; the product can be separated and collected in a second-stage area, the recovery rate of tin is 91.7 percent, the purity of nano stannous sulfide is 95.5 percent, and the specific surface area of the stannous sulfide is 116m2/g。
Example 4
The method comprises the steps of taking a metal mixture obtained by a mechanical crushing separation method of tin-containing electronic waste as a raw material (the tin content is 8.4%, the organic matter content is 0.8%), adding a composite additive (the composite additive is a mixture of calcium sulfide and silicon dioxide, the proportion of the composite additive is Ca/Si is 2.0) according to the dosage of Sn/S which is 1.6, fully mixing, agglomerating, and then placing the dried agglomerated masses into a two-section type controlled atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 6 vol.%, the calcination temperature is 850 ℃, and the gas flow rate is 0.3 m/s; the volatile products enter the second stage baking along with the airflowIn the burning zone, the second-stage roasting is carried out in the weak reducing atmosphere of CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 2 vol.%, the calcination temperature is 650 ℃, and the gas flow rate is 0.5 m/s; the product can be separated and collected in the second-stage area, the recovery rate of tin is 95.3 percent, the purity of nano stannous sulfide is 96.1 percent, and the specific surface area of the stannous sulfide is 127m2/g。
Example 5
The method comprises the steps of taking a metal mixture obtained by a mechanical crushing separation method of tin-containing electronic waste as a raw material (the tin content is 8.4%, the organic matter content is 0.8%), adding a composite additive (the composite additive is a mixture of calcium sulfide and silicon dioxide, the proportion of the composite additive is Ca/Si is 2.0) according to the dosage of Sn/S, mixing the composite additive and the silicon dioxide fully, agglomerating the mixture, and then placing the dried agglomerated masses into a two-section type controlled atmosphere roasting furnace for controlled atmosphere roasting; the material is placed in a first-stage roasting area, and the first-stage roasting strong reducing atmosphere is CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 8 vol.%, the calcination temperature is 800 ℃, and the gas flow rate is 0.2 m/s; the volatile product enters a second-stage roasting zone along with airflow, and the second-stage roasting weak reducing atmosphere comprises CO and CO2Mixed atmosphere with concentration of CO/(CO + CO)2) 1 vol.%, the calcination temperature is 550 ℃, and the gas flow rate is 0.3 m/s; the product can be separated and collected in a second-stage area, the recovery rate of tin is 91.3 percent, the purity of nano stannous sulfide is 97.2 percent, and the specific surface area of the stannous sulfide is 132m2/g。
Claims (5)
1. A method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method is characterized by comprising the following steps: uniformly mixing tin-containing electronic waste and an additive, agglomerating, placing in a reducing atmosphere, carrying out reduction roasting at 750-900 ℃, and placing roasted volatile matter in a weak reducing atmosphere, and carrying out reduction roasting at 450-700 ℃ to obtain nano stannous sulfide powder; the additive is a mixture of calcium sulfide and silica.
2. The method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method according to claim 1, wherein the method comprises the following steps: the tin-containing electronic waste is pretreated by a vacuum pyrolysis method or a mechanical crushing and separating method, the mass percent of tin is higher than 8.0%, and the mass percent of organic matters is lower than 1.0%.
3. The method for preparing nano stannous sulfide from stanniferous electronic waste by one-step method according to claim 1, which is characterized in that: the mixing proportion of the additive and the tin-containing electronic waste meets the following requirements: Ca/Si is 2 to 2.2, and Sn/S is 1.5 to 2.0.
4. The method for synchronously preparing nano tin dioxide by selectively separating tin from electronic waste according to claim 1, which is characterized in that: in the process of reducing roasting in reducing atmosphere, the reducing atmosphere is controlled to be CO and CO2A mixed atmosphere, wherein the volume percentage of carbon monoxide satisfies: CO/(CO + CO)2) 3-10%, and the gas flow rate is 0.1-0.3 m/s.
5. The method for synchronously preparing nano tin dioxide by selectively separating tin from electronic waste according to claim 1, which is characterized in that: in the process of carrying out reduction roasting in the weak reducing atmosphere, the weak reducing atmosphere is controlled to be CO and CO2A mixed atmosphere, wherein the volume percentage of carbon monoxide satisfies: CO/(CO + CO)2) 1-5%, and the gas flow rate is 0.2-0.5 m/s.
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| CN103589870A (en) * | 2013-11-08 | 2014-02-19 | 昆明理工大学 | Method for processing tin refining sulfur slag |
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