A process for tin removal from blister copper

Abstract

The application relates to the technical field of non-ferrous metal smelting, and discloses a method for removing tin from crude copper, which comprises the following steps: S1, component detection, collecting crude copper as raw material, and performing preliminary detection and analysis on the crude copper to determine the component proportion of gold, silver, copper, iron and tin in the crude copper; S2, surface pretreatment, soaking the crude copper in an alkaline solution of hydroxide; S3, tin removal by fire, melting the crude copper at 1100-1300 DEG C after surface cleaning, adding silica with 2-4 times the content of iron in the molten copper liquid, adding 5%-15% of a slagging agent of caustic soda, 1%-5% of sodium nitrate and sodium chloride by weight of the crude copper after primary stirring, and performing secondary stirring after the addition; and S4, oxidation separation, heating the molten copper liquid to 1200-1500 DEG C. Through the sectional flotation process, tin impurities in the molten copper liquid can be efficiently removed, and other metal impurities such as gold, silver and platinum in the crude copper can be synchronously removed, so that the utilization rate of other metals is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of non-ferrous metal smelting, in particular to a method for removing tin from crude copper. BACKGROUND

[0002] Copper is an indispensable important industrial raw material, and has a wide application field and high industrial correlation. Crude copper generally contains various impurities such as iron, zinc, nickel, silver, gold and tin. The main purpose of removing tin from crude copper is to improve the purity and properties of copper to meet the requirements of industrial production and manufacturing. High-purity copper is crucial to the electronic industry, construction industry and other fields. Traditional methods for removing tin from crude copper mainly include pyrometallurgical method and electrolytic method.

[0003] According to the search, the patent CN103243223B discloses a method for removing tin from crude copper. The crude copper is heated and melted, and silicon dioxide with a weight twice that of iron is added. After slagging by blowing compressed air, the oxidized dross is separated. The molten crude copper is cooled to 1100-1150 DEG C, and 5-10% of the weight of the crude copper of the slagging agent caustic soda is added. After stirring, 2-6% of the weight of the crude copper of the oxidizing agent sodium nitrate or potassium nitrate is added, and the stirring time is 10-30 minutes. The temperature is raised to 1130-1200 DEG C, and 10-20% of the weight of the crude copper of the slagging agent caustic soda, 2-5% of the weight of the crude copper of the oxidizing agent sodium nitrate or potassium nitrate and 2-3% of the weight of the crude copper of the additive are added. After stirring for 20-60 minutes, the mixture is allowed to stand for 30-180 minutes, and then cooled to 900-1080 DEG C. The upper alkali dross is removed. After removing the alkali dross, the molten copper is heated again, and 2-15% of the weight of the crude copper of the reducing agent carbon powder or pulverized coal is added. After stirring and heat preservation, the tin-removed copper is obtained.

[0004] The present application can not separate and recover other metals such as gold and silver during the removal of tin, which reduces the utilization rate of metals. Therefore, the present application provides a method for removing tin from crude copper to solve the above problems. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a method for removing tin from crude copper, which solves the problem that other metals such as gold and silver cannot be separated and recovered during the removal of tin.

[0006] To achieve the above object, the present application is realized by the following technical scheme: a method for removing tin from crude copper, comprising the following steps:

[0007] S1, component detection, collecting crude copper as raw material, and determining the component proportion of gold, silver, copper, iron and tin in the crude copper by preliminary detection and analysis;

[0008] S2, surface pretreatment, soaking the crude copper in an alkaline solution of hydroxide;

[0009] S3, tin removal, after surface cleaning of the crude copper, the crude copper is melted at 1100-1300 °C, and 2-4 times the amount of iron in the form of silicon dioxide is added to the molten copper, after primary stirring, 5-15% of a slag forming agent, caustic soda, 1-5% of sodium nitrate and sodium chloride are added to the crude copper, and after the addition, secondary stirring is performed;

[0010] S4, oxidation separation, the molten copper is heated to 1200-1500 °C, 15-20% of a slag forming agent, caustic soda, 2-5% of sodium nitrate and 2-3% of sodium chloride are added to the crude copper, and three times of stirring is performed;

[0011] S4, precipitation separation, after standing for 30-180 min, the upper layer of alkali slag is removed;

[0012] S5, copper metal reduction, 5-20% of a reducing agent is added to the molten copper from which the alkali slag is removed, stirring and standing for 2-5 h to obtain the copper after tin removal;

[0013] S6, metal leaching, the alkali slag is ground using a ball mill, sulfuric acid is added to the alkali slag for leaching, and then the leaching solution is separated into leaching slag and leaching solution;

[0014] S7, metal flotation, the leaching slag is subjected to stepwise flotation;

[0015] S8, metal displacement, a reducing powder is added to the leaching solution for displacement of copper;

[0016] S9, refining, the metals obtained in the above steps are further refined respectively;

[0017] S10, the content of each metal component in the molten copper is detected, and the physicochemical properties of the obtained crude copper are detected.

[0018] Preferably, in the S2 step, the alkali solution of hydroxide is a sodium hydroxide solution with a concentration of 5-10%.

[0019] Preferably, in the S3 step, the slag forming agent is composed of the following substances in mass percentage: 20-45% of sodium chloride, 30-45% of potassium chloride, 3-9% of calcium fluoride, 1-7% of aluminum trichloride and 2-5% of Na3AlF.

[0020] Preferably, in the S5 step, the reducing agent is formic acid.

[0021] Preferably, in the S6 step, the concentration of sulfuric acid is 2.7-3.2 mol / L, and the mass of the added sulfuric acid is 3-6 times the mass of the leaching slag.

[0022] Preferably, in the S7 step, the stepwise flotation includes the following steps:

[0023] S701, raw material ball milling, using a ball mill to mill the leaching residue;

[0024] S702, stirring and aeration, relying on the stirring and aeration of the flotation machine to perform stirring and inhale air, so that the leaching residue particles are in a suspended state;

[0025] S703, bubble scraping, the bubbles in a foamy state are scraped and collected.

[0026] Preferably, in the S701 step, the leaching residue is milled to particles of 0.075-0.15 mm.

[0027] Preferably, in the S8 step, the reducing powder specifically comprises elemental iron, and the mass of the reducing agent is 2%-10% of the mass of the crude copper.

[0028] Preferably, in the S9 step, the refining comprises the following steps: first, high-temperature smelting each metal respectively to obtain the corresponding metal, and then removing the impurities in the metal by electrolysis.

[0029] Preferably, in the S10 step, the performance detection of the crude copper includes a bending resistance experiment, a tensile experiment, an electrical conductivity, and stability.

[0030] The present application provides a method for removing tin from crude copper.

[0031] 1. In the process of removing tin from crude copper, the present application can efficiently remove tin impurities from molten copper liquid, and can simultaneously remove other metal impurities such as gold, silver, and platinum from the crude copper, thereby improving the physical and chemical properties of the crude copper after the removal of tin, and enhancing the bending resistance, electrical conductivity, tensile property, and stability of the crude copper.

[0032] 2. The present application maintains a low temperature in the entire slagging process of the molten copper liquid through the comparison of the embodiments, thereby reducing the energy consumption and improving the energy-saving and emission-reducing level in the process of removing tin from crude copper.

[0033] 3. The present application removes impurities from other metals through electrolytic refining, thereby ensuring the quality and reusability of the extracted metals. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The flowchart of the method for removing tin from crude copper in the present application. DETAILED DESCRIPTION

[0035] With reference to the drawings of the embodiments of the present application, the technical solutions in the embodiments of the present application will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0036] Embodiment one:

[0037] Please refer to the drawings Figure 1 The embodiment of the present application provides a method for removing tin from crude copper, comprising the following steps:

[0038] S1, component detection, collecting crude copper as raw material, and performing preliminary detection and analysis on the crude copper to determine the component proportion of gold, silver, copper, iron and tin in the crude copper;

[0039] S2, surface pretreatment, soaking the crude copper in an alkaline solution of hydroxide, and the alkaline solution of hydroxide is a sodium hydroxide solution with a concentration of 7%;

[0040] S3, tin removal by calcination, after surface cleaning of the crude copper, melting at 1150°C, and adding silica with 4 times the content of iron in the molten copper liquid, after primary stirring, adding 12% of the weight of the crude copper of caustic soda as a slagging agent, 3% of sodium nitrate and sodium chloride, after adding, secondary stirring is performed, in the S3 step, the slagging agent is composed of the following substances with mass percentage: 35% sodium chloride, 40% potassium chloride, 6% calcium fluoride, 5% aluminum chloride and 3% Na3AlF;

[0041] S4, oxidation separation, heating the molten copper liquid to 1250°C, adding 17% of the weight of the crude copper of caustic soda as a slagging agent, 3% of sodium nitrate and 2% of sodium chloride, and stirring three times;

[0042] S4, precipitation separation, after standing for 120 min, removing the upper alkali residue;

[0043] S5, copper metal reduction, adding 10% of the weight of the copper of a reducing agent in the molten copper liquid after removing the alkali residue, stirring and standing for 3h to obtain the copper after removing tin, and the reducing agent is formic acid;

[0044] S6, metal leaching, using a ball mill to grind the leaching alkali residue, adding sulfuric acid in the alkali residue for leaching, and then separating the leaching solution into leaching residue and leaching liquid, the concentration of sulfuric acid is 2.9 mol / L, and the mass of added sulfuric acid is 3 times the mass of the leaching residue;

[0045] S7, metal flotation, segmenting the leaching residue for flotation;

[0046] S8, metal replacement, adding reducing powder in the leaching solution to replace copper, the specific composition of the reducing powder is elemental iron, and the mass of the reducing agent is 8% of the mass of the crude copper;

[0047] S9, refining, further refining the metals obtained in the above steps respectively, the refining comprising the following steps: firstly, high-temperature smelting each metal respectively to obtain an alloy, and then removing impurities in the metal by electrolysis;

[0048] S10, detecting the content of each metal component in the molten copper liquid, and detecting the physical and chemical properties of the obtained crude copper, the performance detection of the crude copper comprising a bending experiment, a tensile experiment, an electrical conductivity and stability.

[0049] In the S7 step, the staged flotation comprises the following steps:

[0050] S701, raw material ball milling, using a ball mill to mill the leaching slag, and the leaching slag is 0.10 mm after ball milling;

[0051] S702, stirring and aeration, relying on the stirring and aeration device of the flotation machine to perform stirring and inhale air, so that the leaching slag particles are in a suspended state;

[0052] S703, bubble scraping, the bubbles in the foam state are scraped and collected.

[0053] Example two:

[0054] The embodiment of the present application provides a method for removing tin from crude copper, comprising the following steps:

[0055] S1, component detection, collecting crude copper as raw material, and performing preliminary detection and analysis to determine the component proportion of gold, silver, copper, iron and tin inside;

[0056] S2, surface pretreatment, immersing the crude copper in an alkaline solution of a hydroxide, and the alkaline solution of the hydroxide is a sodium hydroxide solution with a concentration of 7%;

[0057] S3, tin removal by calcination, after surface cleaning of the crude copper, melting at 1150 DEG C, adding 4 times of silicon dioxide in terms of iron content in the molten copper liquid, adding 15% of a slagging agent caustic soda, 3% of sodium nitrate and sodium chloride in terms of the weight of the crude copper after first stirring, and performing second stirring after adding, in the S3 step, the slagging agent is composed of the following substances in mass percentage: 40% of sodium chloride, 40% of potassium chloride, 7% of calcium fluoride, 7% of aluminum trichloride and 5% of Na3Al F;

[0058] S4, oxidation separation, heating the molten copper liquid to 1250 DEG C, adding 17% of a slagging agent caustic soda, 3% of sodium nitrate and 2% of sodium chloride in terms of the weight of the crude copper, and performing three times of stirring;

[0059] S4, precipitate separation, remove the upper alkali residue after standing for 120 min;

[0060] S5, copper metal reduction, add 10% of the weight of the copper reducing agent to the molten copper liquid after removing the alkali residue, stir and stand for 3h to obtain the copper after removing tin, and the reducing agent is formic acid;

[0061] S6, metal leaching, use a ball mill to grind the leaching alkali residue, add sulfuric acid to the alkali residue for leaching, and then separate the leaching solution into leaching residue and leaching liquid, the concentration of sulfuric acid is 2.9mol / L, and the mass of added sulfuric acid is 3 times the mass of the leaching residue;

[0062] S7, metal flotation, the leaching residue is subjected to step-by-step flotation;

[0063] S8, metal replacement, add reducing powder to the leaching liquid for copper replacement, and the specific composition of the reducing powder is elemental iron, and the mass of the reducing agent is 8% of the mass of the copper;

[0064] S9, refining, the metals obtained in the above steps are further refined, and the refining includes the following steps: first, high-temperature smelting is carried out on each metal respectively to obtain phase metal, and then impurities in the metal are removed by electrolysis;

[0065] S10, detecting the content of each metal component in the molten copper liquid, and detecting the physical and chemical properties of the obtained copper, and the performance detection of the copper includes bending experiment, tensile test, electrical conductivity and stability.

[0066] In step S7, the step-by-step flotation includes the following steps:

[0067] S701, raw material ball milling, the leaching residue is ball milled using a ball mill, and the ball milled leaching residue is 0.10mm particles;

[0068] S702, stirring and aeration, the stirring and aeration of the flotation machine are relied on to stir and inhale air, so that the leaching residue particles are in a suspended state;

[0069] S703, bubble scraping, the bubbles in the foam state are scraped and collected.

[0070] Example three:

[0071] The embodiment of the application provides a method for removing tin from copper, which comprises the following steps:

[0072] S1, component detection, collecting copper as raw material, and detecting and analyzing the internal gold, silver, copper, iron and tin component ratio;

[0073] S2, surface pretreatment, soaking the copper in an alkali solution of hydroxide, and the alkali solution of hydroxide is a sodium hydroxide solution with a concentration of 7%.

[0074] S3, tin removal, after surface cleaning of the crude copper, the crude copper is melted at 1150℃, and 4 times the amount of iron of silicon dioxide is added to the molten copper liquid, after one stirring, 12% of the weight of the crude copper of the slag forming agent caustic soda, 3% of sodium nitrate and sodium chloride are added, after the addition, secondary stirring is carried out, in the S3 step, the slag forming agent is composed of the following mass percentage of substances: 35% sodium chloride, 40% potassium chloride, 6% calcium fluoride, 5% aluminum chloride and 3% Na3AlF;

[0075] S4, oxidation separation, the temperature of the molten copper liquid is raised to 1250℃, 17% of the weight of the crude copper of the slag forming agent caustic soda, 3% of sodium nitrate and 2% of sodium chloride are added, and three times of stirring is carried out;

[0076] S4, precipitation separation, after standing for 120 min, the upper alkali slag is removed;

[0077] S5, copper metal reduction, 10% of the weight of the copper of the reducing agent is added to the molten copper liquid after removing the alkali slag, after stirring and standing for 3h, the copper after tin removal is obtained, the reducing agent is formic acid;

[0078] S6, metal leaching, the leaching alkali slag is ground by using a ball mill, sulfuric acid is added to the alkali slag for leaching, and then the leaching solution is separated into leaching slag and leaching liquid, the concentration of the sulfuric acid is 2.9 mol / L, and the mass of the added sulfuric acid is 3 times the mass of the leaching slag;

[0079] S7, metal flotation, the leaching slag is subjected to staged flotation;

[0080] S8, metal displacement, the reducing powder is added to the leaching liquid for displacement to remove copper, the specific composition of the reducing powder is elemental iron, and the mass of the reducing agent is 8% of the mass of the crude copper;

[0081] S9, refining, the metals obtained in the above steps are further refined, the refining includes the following steps: first, the metals are subjected to high-temperature smelting respectively to obtain phase metals, and then the impurities in the metals are removed by electrolysis;

[0082] S10, the content of each metal component in the molten copper liquid is detected, and the physicochemical performance of the obtained crude copper is detected, the performance detection of the crude copper includes bending resistance experiment, tensile experiment, electrical conductivity and stability.

[0083] In the S7 step, the staged flotation includes the following steps:

[0084] S701, raw material ball milling, the leaching slag is ball milled by using a ball mill, and the particle size of the ball milled leaching slag is 0.10 mm;

[0085] S702, stirring and aeration: relying on the stirring and aeration device of the flotation machine to stir and draw in air, so that the leaching residue particles are in a suspended state.

[0086] S703. Scrape out the bubbles: scrape out and collect the foamy bubbles.

[0087] Example 4:

[0088] This invention provides a method for removing tin from crude copper, comprising the following steps:

[0089] S1. Composition analysis: Collect crude copper as raw material, conduct preliminary analysis and determination of the proportions of gold, silver, copper, iron and tin in its composition.

[0090] S2. Surface pretreatment: Immerse crude copper in an alkaline solution of hydroxide, which is a 7% sodium hydroxide solution.

[0091] S3. Detinning: After cleaning the surface of crude copper, melt it at 1150℃. Add silicon dioxide with an iron content of 4 times to the molten copper. After stirring once, add 12% of the crude copper weight of slag-forming agent caustic soda, 3% sodium nitrate and sodium chloride. Stir a second time after adding. In step S3, the slag-forming agent consists of the following substances by mass percentage: 35% sodium chloride, 40% potassium chloride, 6% calcium fluoride, 5% aluminum trichloride and 3% Na3AlF.

[0092] S4. Oxidation separation: Heat the molten copper liquid to 1250℃, add 17% of the slag-forming agent caustic soda, 3% of sodium nitrate and 2% of sodium chloride by weight of crude copper, and stir three times.

[0093] S4. Sedimentation and separation: After standing for 120 minutes, remove the upper layer of alkaline residue.

[0094] S5. Copper metal reduction: Add 10% of the copper weight of the reducing agent to the molten copper liquid after removing the alkaline slag, stir and let stand for 3 hours to obtain copper after removing tin. The reducing agent is formic acid.

[0095] S6. Metal leaching: The leaching alkaline residue is ground using a ball mill. Sulfuric acid is added to the alkaline residue for leaching. The leaching solution is then separated into leaching residue and leaching liquid. The concentration of sulfuric acid is 3.2 mol / L, and the mass of sulfuric acid added is 6 times the mass of the leaching residue.

[0096] S7. Metal flotation: staged flotation of leaching residue;

[0097] S8. Metal replacement: copper is removed by adding reducing powder to the leachate. The reducing powder is composed of elemental iron, and the mass of the added reducing agent is 8% of the mass of crude copper.

[0098] S9, refining, the metal obtained in the above steps is further refined respectively, and the refining comprises the following steps: firstly, high-temperature smelting is performed on each metal respectively to obtain a phase metal, and then impurities in the metal are removed by electrolysis;

[0099] S10, detecting the content of each metal component in the molten copper liquid, and detecting the physical and chemical properties of the obtained crude copper, and the performance detection of the crude copper comprises a bending experiment, a tensile experiment, an electrical conductivity and stability.

[0100] In S7, the step of staged flotation comprises the following steps:

[0101] S701, raw material ball milling, using a ball mill to mill the leaching slag, and the leaching slag is 0.10mm after ball milling;

[0102] S702, stirring and aeration, relying on the stirring and aeration device of the flotation machine to perform stirring and inhale air, so that the leaching slag particles are in a suspended state;

[0103] S703, bubble scraping, the bubbles in the foam state are scraped and collected.

[0104] Example five:

[0105] The embodiment of the present application provides a method for removing tin from crude copper, comprising the following steps:

[0106] S1, component detection, collecting crude copper as raw material, and performing preliminary detection and analysis to determine the component proportion of gold, silver, copper, iron and tin inside;

[0107] S2, surface pretreatment, soaking the crude copper in an alkaline solution of a hydroxide, and the alkaline solution of the hydroxide is a sodium hydroxide solution with a concentration of 7%;

[0108] S3, tin removal by calcination, after surface cleaning of the crude copper, melting at 1150 DEG C, adding 4 times of silica in terms of iron content in the molten copper liquid, adding 12% of a slagging agent caustic soda, 3% of sodium nitrate and sodium chloride by weight of the crude copper after first stirring, and performing secondary stirring after adding, in S3, the slagging agent is composed of the following mass percentage of substances: 35% sodium chloride, 40% potassium chloride, 6% calcium fluoride, 5% aluminum trichloride and 3% Na3Al F;

[0109] S4, oxidation separation, heating the molten copper liquid to 1250 DEG C, adding 17% of a slagging agent caustic soda, 3% of sodium nitrate and 2% of sodium chloride by weight of the crude copper, and stirring three times;

[0110] S4, precipitation separation, after standing for 120 min, removing the upper alkali slag;

[0111] S5, copper metal reduction, adding a reducing agent of 10% of the weight of copper in the molten copper liquid from which the alkali residue is removed, stirring and standing for 3h to obtain copper after tin removal, and the reducing agent is formic acid;

[0112] S6, metal leaching, grinding the leaching alkali residue using a ball mill, adding sulfuric acid in the alkali residue for leaching, and then separating the leaching solution into leaching residue and leaching liquid, the concentration of sulfuric acid is 2.9 mol / L, and the mass of added sulfuric acid is 4 times the mass of the leaching residue;

[0113] S7, metal flotation, the leaching residue is subjected to staged flotation;

[0114] S8, metal displacement, adding a reducing powder in the leaching liquid for displacement to remove copper, and the specific component of the reducing powder is elemental carbon, and the mass of the reducing agent is 8% of the mass of the crude copper;

[0115] S9, refining, further refining the metals obtained in the above steps, and the refining includes the following steps: first, high-temperature smelting each metal to obtain a phase metal, and then removing impurities in the metal by electrolysis;

[0116] S10, detecting the content of each metal component in the molten copper liquid, and detecting the physical and chemical properties of the obtained crude copper, and the performance detection of the crude copper includes bending resistance experiment, tensile test, electrical conductivity and stability.

[0117] In the S7 step, the staged flotation includes the following steps:

[0118] S701, raw material ball milling, the leaching residue is ball milled using a ball mill, and the ball milled leaching residue is a particle of 0.10mm;

[0119] S702, stirring and aeration, relying on the stirring and aeration device of the flotation machine to perform stirring and inhale air, so that the leaching residue particles are in a suspended state;

[0120] S703, bubble scraping, the bubbles in the foam state are scraped and collected.

[0121] Comparative Example One:

[0122] The present application provides a method for removing tin from crude copper, which includes the following steps:

[0123] S11, heating and melting the crude copper, according to the pre-determined content of other metals, adding an oxidizing agent of 5% of the corresponding mass and a slagging agent of 10% of the mass, and then stirring;

[0124] S12, standing for 2h and cooling, and removing the upper alkali residue;

[0125] S13, adding reducing carbon powder in the molten copper liquid, stirring and standing to obtain copper after tin removal

[0126] Comparative Example Two:

[0127] The present application comparative example provides a method for removing tin from crude copper, comprising the following steps:

[0128] S21, melting the crude copper, 10% of the mass of the crude copper of the reducing agent, and 15% of the mass of the crude copper of the slagging agent together;

[0129] S22, separating the reduction slag and the reduction metal;

[0130] S23, oxidizing the metal with 2L / kg of air;

[0131] S24, adding 4 times the mass of sodium hydroxide to the oxidized crude copper, and melting in the air oxidation environment of 2L / kg to complete the removal of tin from the crude copper.

[0132] Comparative Example Three:

[0133] The present application comparative example provides a method for removing tin from crude copper, comprising the following steps:

[0134] S31, melting the crude copper;

[0135] S32, spraying the slagging agent and the oxidizing agent into the molten copper liquid to complete the oxidation and slagging;

[0136] S33, removing the slag body to complete the removal of tin from the crude copper.

[0137] Physicochemical properties of tin-removed crude copper:

[0138] Through the above-mentioned example one to example five and comparative example one to comparative example three in the process of removing tin from the crude copper, the bending resistance, tensile property, electrical conductivity and stability of the crude copper are tested and evaluated, and the purity composition of the other metal is detected, the best conditions for removing tin and other metals from the crude copper under the condition of changing the processing temperature of the molten copper liquid and the component ratio of the slagging agent are determined, and the type of reducing agent is set as a measurement index in the single factor influence experiment, and the observation phenomenon is shown in the following table 1:

[0139] Table 1: Physicochemical property data table of crude copper provided by example one to example five and comparative example.

[0140]

[0141]

[0142] Summary: the invention can remove tin impurities in molten copper liquid efficiently in the process of removing tin from crude copper, and can remove other metal impurities such as gold, silver and platinum in crude copper simultaneously, improve the physical and chemical properties of crude copper after removing tin, and enhance the bending resistance, conductivity, tensile property and stability of crude copper. Through comparison of examples, the whole slagging process of molten copper liquid is kept at low temperature, which is below the threshold of processing environment temperature, the energy consumption is reduced while tin impurities in copper are removed efficiently, and the energy saving and emission reduction level in the process of removing tin from crude copper is improved. In addition, through electrolytic refining, the removal of other metal impurities is completed, and the quality and reusability of other extracted metals are ensured.

[0143] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A process for tin removal from crude copper, characterized by, The method comprises the following steps: S1, component detection, collecting crude copper as raw material, and performing preliminary detection and analysis on the crude copper to determine the component proportion of gold, silver, copper, iron and tin in the crude copper; S2, surface pretreatment, soaking the crude copper in an alkaline solution of hydroxide; S3, tin removal by fire, melting the crude copper at 1100-1300 DEG C after surface cleaning, adding silica with 2-4 times the content of iron in the molten copper liquid, adding 5%-15% of a slag forming agent, caustic soda, 1%-5% of sodium nitrate and sodium chloride by weight of the crude copper after primary stirring, and performing secondary stirring after adding the slag forming agent, the slag forming agent being composed of the following components in mass percentage: 20%-45% of sodium chloride, 30%-45% of potassium chloride, 3%-9% of calcium fluoride, 1%-7% of aluminum trichloride and 2%-5% of Na3AlF; S4, oxidation separation, heating the molten copper liquid to 1200-1500 DEG C, adding 15%-20% of a slag forming agent, caustic soda, 2%-5% of sodium nitrate and 2%-3% of sodium chloride by weight of the crude copper, and performing three times of stirring, and then performing sedimentation separation, and removing the upper alkali slag after standing for 30-180 min; S5, copper metal reduction, adding 5%-20% of a reducing agent by weight of copper in the molten copper liquid after removing the alkali slag, and standing for 2-5 h to obtain copper after removing tin; S6, metal leaching, grinding the leaching alkali slag by using a ball mill, adding sulfuric acid in the alkali slag for leaching, and then separating the leaching solution into leaching residue and leaching liquid; S7, metal flotation, performing segmented flotation on the leaching residue, the segmented flotation comprising the following steps: S701, raw material ball milling, ball milling the leaching residue by using a ball mill; S702, stirring and aeration, performing stirring action by relying on a stirring aerator of a flotation machine and inhaling air to make the leaching residue particles in a suspended state; S703, bubble scraping, scraping and collecting bubbles in a foamy state; S8, metal displacement, adding a reducing powder in the leaching liquid for displacement and copper removal; S9, refining, further refining the metals obtained in the above steps respectively; S10, detecting the content of each metal component in the molten copper liquid, and detecting the physical and chemical properties of the obtained crude copper.

2. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S2 step, the alkali solution of hydroxide is a sodium hydroxide solution with a concentration of 5%-10%.

3. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S5 step, the reducing agent is formic acid.

4. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S6 step, the concentration of sulfuric acid is 2.7-3.2 mol / L, and the added mass of sulfuric acid is 3-6 times the mass of the leaching residue.

5. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S701 step, the leaching residue after ball milling is a particle with a size of 0.075-0.15 mm.

6. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S8 step, the specific component of the reducing powder is elemental iron, and the added mass of the reducing agent is 2%-10% of the mass of the crude copper.

7. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S9 step, the refining comprises the following steps: first, high-temperature smelting each metal to obtain phase metal, and then removing impurities in the metal by electrolysis.

8. A process for tin removal from crude copper as claimed in claim 1 wherein, In the S10 step, the physical and chemical property detection of the crude copper comprises a bending resistance experiment, a tensile experiment, an electrical conductivity and stability.

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