Electronic-grade high-purity phosphor copper ball refining preparation process based on scrap copper

Abstract

The invention relates to an electronic-grade high-purity phosphor copper ball refining preparation process based on scrap copper, and belongs to the technical field of non-ferrous metal refining. The scrap copper is sorted and then put into a sodium hydroxide solution to be cleaned; adding the pretreated scrap copper into a medium-frequency induction furnace for melting; a composite refining agent is added into the molten copper for refining; after refining is finished, phosphorus-copper alloy is added into the copper liquid, and the phosphorus content is adjusted; the copper liquid added with phosphorus is subjected to heat preservation and standing; casting the copper liquid subjected to heat preservation and standing into a specific mold to obtain a phosphor copper ball blank; the phosphor copper ball blank is cooled, polished, cleaned and dried through the modified silicone oil cooling dispersion liquid, and the electronic-grade high-purity phosphor copper ball is obtained; the copper purity of the prepared phosphor copper ball reaches up to 99.99%, the total content of harmful impurities is lower than 0.025%, and the requirement of the electronic industry for the high-purity phosphor copper ball is completely met.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of non-ferrous metal refining, and particularly relates to an electronic-grade high-purity phosphor copper ball refining preparation process based on waste copper. BACKGROUND

[0002] With the rapid development of the electronic industry, the demand for electronic-grade high-purity phosphor copper balls is increasing. As a key anode material in the electroplating industry, the purity and performance of the phosphor copper ball directly affect the quality of the electroplated layer and the performance of electronic products. Traditionally, high-purity electrolytic copper is used as raw material to prepare the phosphor copper ball, but the electrolytic copper is high in cost, and with the increasing shortage of copper resources, it is urgent to find a low-cost and efficient raw material replacement solution.

[0003] Waste copper is widely sourced from electronic waste, waste wire and cable, copper processing waste and the like. If the waste copper can be effectively recycled and utilized to prepare high-purity phosphor copper balls meeting the requirements of the electronic industry, the production cost can be significantly reduced, the pressure of copper resource shortage can be alleviated, and the application has important economic and environmental significance. However, the waste copper is complex in composition and contains a large amount of impurity elements such as iron, zinc, lead, tin, nickel and the like, and surface pollutants such as oil stains and oxides, which brings great challenges to refining and purification.

[0004] Chinese patent CN108220620A discloses a waste copper refining process, which comprises the following steps: S1, waste copper with a copper content of greater than 95% is subjected to alkali washing, dried, and then heated to 1100-1150 DEG C to melt the copper; S2, the temperature of the copper liquid in S1 is controlled at 1150-1170 DEG C, low-sulfur coke is added to the copper liquid for the first refining, then slag is removed, then quartz, phosphor copper or boron oxide is added to the copper liquid for the second refining, then slag is removed, and finally lime and soda are added to the copper liquid for the third refining, and then slag is removed; S3, reduction gas is introduced into the copper liquid in S2, the temperature of the copper liquid is maintained at 1180-1200 DEG C for reduction refining, and the reduction time is 1-2 h; S4, under stirring, a refining agent is added to the copper liquid in S3, and the copper liquid is refined at a temperature of 1150-1200 DEG C for 0.5-1 h, and then the copper liquid is statically placed, slag is removed, and high-purity oxygen-free copper water is obtained.

[0005] Chinese patent CN104611574A: discloses a kind of waste copper refining method, the method of treating anode slime by medium temperature chlorination method is through charging melting→ oxidizing deslagging→ reduction deoxidation→ casting copper plate, compared with prior art, the waste copper refining method, waste copper is added to the charging port at the top of shaft furnace from vertical furnace feeding device, while natural gas is introduced from the nozzle around the bottom of shaft furnace, copper is melted near the bottom, the upper furnace charge is preheated using flue gas, and the column in the furnace moves downward to form a continuous molten metal stream;Anode refining is divided into two stages, oxidation period and reduction period, oxidation is compressed air, and reduction is nitrogen-containing natural gas.

[0006] Existing waste copper refining processes, such as pyrometallurgical refining and hydrometallurgical refining, can remove impurities to some extent, but have problems such as poor refining effect, complex process flow, high energy consumption, and serious environmental pollution, which cannot meet the strict requirements of electronic-grade high-purity phosphor copper balls on copper purity and impurity content. SUMMARY

[0007] To solve the above problems, the present application provides a kind of electronic-grade high-purity phosphor copper ball refining preparation process based on waste copper, and the operation steps are as follows:

[0008] S1 pretreatment: 20-30 parts by mass of waste copper are sorted to remove plastic, rubber and other non-copper impurities, then put into 70-100 parts by mass of 5-10% sodium hydroxide solution, clean for 10-20 minutes at 60-80℃ to remove oil stains and oxides;Take out and dry;

[0009] S2 melting: the pretreated waste copper is added to a medium-frequency induction furnace and melted at 1100-1200℃;

[0010] S3 refining: 0.5-1.5 parts by mass of composite refining agent is added to 70-100 parts by mass of copper liquid for refining to remove iron, zinc, lead and tin impurities in the copper liquid, so that the impurity content is greatly reduced;

[0011] S4 phosphorus addition: after refining, phosphor copper alloy is added to the copper liquid to adjust the phosphorus content to 0.03wt%-0.07wt%;When adding phosphor copper alloy, the temperature of the copper liquid is kept at 1180-1230℃ to ensure that the phosphor copper alloy melts quickly and disperses uniformly in the copper liquid;

[0012] S5 holding and standing: the copper liquid after adding phosphorus is held and stood at 1150-1200℃ for 15-30 minutes;During holding and standing, the inclusions and bubbles in the copper liquid have enough time to float out, making the copper liquid purer and the composition more uniform;

[0013] S6 Casting: The copper liquid after heat preservation and standing is cast into a specific mold to obtain a phosphor copper ball blank; during the casting process, the mold temperature is controlled at 200-300 DEG C;

[0014] S7 Post-processing: The phosphor copper ball blank is cooled, polished, washed, and dried by a modified silicone oil cooling dispersion liquid to obtain an electronic grade high purity phosphor copper ball.

[0015] Further, the melting temperature of S2 is 1100-1200 DEG C.

[0016] Further, the composite refining agent is quartz sand, sodium carbonate and fluorite, and the mass ratio is (3-5):(1-2):(0.5-1).

[0017] Further, the refining temperature of S3 is 1150-1220 DEG C, and the refining time is 30-60 minutes.

[0018] Further, during the casting process of S6, the mold temperature is 200-300 DEG C, and the cooling rate is 5-10 DEG C / min.

[0019] Further, the preparation method of the modified silicone oil cooling dispersion liquid is:

[0020] According to the mass fraction, 5-8 parts of polymethyl hydrogen siloxane, 3-5 parts of allyl polyoxyethylene ether, 0.2-2 parts of allyl diphenyl phosphine, 0.05-0.5 parts of phosphate acrylate, 30-60 parts of ethylene glycol butyl ether are added to the reaction kettle, heated to 80-90 DEG C, 0.1-0.3 parts of 0.1-0.5wt% chloroplatinic acid isopropyl alcohol solution is added, and the reaction is stirred for 4-6 hours. After the reaction is completed, the temperature is lowered to 30-40 DEG C, 0.1-0.4 parts of nano boron nitride and 150-220 parts of deionized water are added, and stirred and dispersed for 50-100 minutes to obtain a modified silicone oil cooling dispersion liquid.

[0021] Reaction mechanism:

[0022] The Si-H bond in polymethyl hydrogen siloxane and the C=C bond in allyl polyoxyethylene ether undergo a silicon hydrogen addition reaction under the catalysis of chloroplatinic acid isopropyl alcohol solution to form a modified silicone oil connected by Si-C bond.

[0023] The complex antioxidant (combination of hindered phenol and phosphite) is combined with the modified silicone oil by intermolecular force, and the active group is coordinated with the copper surface metal ion, and at the same time, the free radicals generated by oxidation are captured to block the oxidation process.

[0024] Technical effects

[0025] Compared with the prior art, the present application has the following remarkable effects:

[0026] 1. Efficient utilization of scrap copper: Through the process of the present application, complex scrap copper can be converted into high-purity phosphor copper balls, increasing the added value of scrap copper and achieving efficient recycling of resources.

[0027] 2. Modified silicone oil forms a lubricating protective film on the surface of copper, and the synergistic effect of the compounded antioxidant effectively delays copper rod oxidation, avoids the formation of black spots, and maintains the good performance of copper.

[0028] 3. Nanometer boron nitride and silicone oil synergistically enhance the heat dissipation effect, the cooling process is stable, the copper rod performance is uniform, and it meets the requirements of the copper rod cooling process.

[0029] 4. High-purity product: The prepared phosphor copper ball has a copper purity of 99.99%, fully meeting the requirements of the electronic industry for high-purity phosphor copper balls, and can significantly improve the quality of the electroplated layer and the performance of electronic products. DETAILED DESCRIPTION

[0030] To further illustrate the technical means and effects adopted by the present application to achieve the predetermined invention purpose, the following embodiments and comparative examples are described in detail:

[0031] 1. Copper purity: detected by inductively coupled plasma mass spectrometry (ICP-MS).

[0032] 2. Phosphorus content: determined by spectrophotometry.

[0033] 3. Harmful impurity content: inductively coupled plasma mass spectrometry (ICP-MS) is used to detect harmful impurity elements such as iron, zinc, lead, tin, and nickel in the phosphor copper ball, and the total content of harmful impurities is calculated according to the detection results.

[0034] Example 1

[0035] A kind of electronic grade high-purity phosphor copper ball refining preparation process based on scrap copper, its operation steps are:

[0036] S1 pretreatment: 20g of scrap copper is sorted to remove plastic, rubber non-copper impurities, then put into 70g of 5% mass percentage sodium hydroxide solution, clean for 10 minutes at 60℃ to remove oil stains and oxides; take out and dry;

[0037] S2 melting: the pretreated scrap copper is added to a medium-frequency induction furnace and melted at 1100℃;

[0038] S3 refining: 0.5g of composite refining agent is added to 70g of copper liquid for refining to remove iron, zinc, lead, tin impurity elements in the copper liquid, so that the impurity content is greatly reduced;

[0039] S4 phosphorus addition: after refining, phosphorus copper alloy is added to the copper liquid to adjust the phosphorus content to 0.03wt%; when the phosphorus copper alloy is added, the copper liquid temperature is kept at 1180℃, ensuring that the phosphorus copper alloy melts quickly and disperses uniformly in the copper liquid;

[0040] S5 holding and standing: the copper liquid after adding phosphorus is held and stood at 1150℃ for 15 minutes; during the holding and standing process, the inclusions and bubbles in the copper liquid have enough time to float out, making the copper liquid purer and the composition more uniform;

[0041] S6 casting and forming: the copper liquid after holding and standing is cast into a specific mold to obtain a phosphorus copper ball blank; during the casting process, the mold temperature is controlled at 200℃℃;

[0042] S7 post-treatment: the phosphorus copper ball blank is cooled, polished, washed, and dried by a modified silicone oil cooling dispersion liquid to obtain an electronic-grade high-purity phosphorus copper ball.

[0043] The melting temperature of S2 is 1100℃.

[0044] The composite refining agent is quartz sand, sodium carbonate, and fluorite, with a mass ratio of 3:1:0.5.

[0045] The refining temperature of S3 is 1150℃℃, and the refining time is 30 minutes.

[0046] During the casting process of S6, the mold temperature is 200℃℃, and the cooling rate is 5℃ / min.

[0047] The preparation method of the modified silicone oil cooling dispersion liquid is:

[0048] 5g of polymethylhydrogen siloxane HF2030-M400, 3g of allyl polyoxyethylene ether APEG-700, 0.2g of allyl diphenyl phosphine, 0.05g of phosphate acrylate, 30g of ethylene glycol butyl ether are added to a reaction kettle, heated to 80℃, 0.1g of 0.1wt% chloroplatinic acid isopropyl alcohol solution is added, and stirred for 4 hours. After the reaction is completed, the temperature is lowered to 30℃, 0.1g of nano boron nitride and 150g of deionized water are added, and stirred and dispersed for 50 minutes to obtain a modified silicone oil cooling dispersion liquid.

[0049] Example 2

[0050] An electronic-grade high-purity phosphorus copper ball refining preparation process based on waste scrap copper, the operation steps are:

[0051] S1 pretreatment: 23 g of waste copper is sorted to remove plastic, rubber and other non-copper impurities, then placed in 80 g of 6% by mass sodium hydroxide solution, cleaned at 65℃ for 15 minutes to remove oil and oxides; take out and dry;

[0052] S2 melting: the pretreated waste copper is added to a medium-frequency induction furnace and melted at 1140℃;

[0053] S3 refining: 0.8 g of composite refining agent is added to 80 g of copper liquid for refining to remove iron, zinc, lead and tin impurities in the copper liquid, so that the impurity content is greatly reduced;

[0054] S4 phosphorus addition: after refining, phosphorus copper alloy is added to the copper liquid to adjust the phosphorus content to 0.04wt%; when the phosphorus copper alloy is added, the copper liquid temperature is kept at 1190℃ to ensure that the phosphorus copper alloy melts quickly and disperses uniformly in the copper liquid;

[0055] S5 holding and standing: the copper liquid after adding phosphorus is held and stood at 1160℃ for 20 minutes; during the holding and standing process, the inclusions and bubbles in the copper liquid have enough time to float out, making the copper liquid purer and the composition more uniform;

[0056] S6 casting: the copper liquid after holding and standing is cast into a specific mold to obtain a phosphorus copper ball blank; during casting, the mold temperature is controlled at 240℃;

[0057] S7 post-treatment: the phosphorus copper ball blank is cooled, polished, washed and dried by modified silicone oil cooling dispersion liquid to obtain electronic-grade high-purity phosphorus copper ball.

[0058] The melting temperature of S2 is 1140℃.

[0059] The composite refining agent is quartz sand, sodium carbonate and fluorite, and the mass ratio is 4:1.5:0.6.

[0060] The refining temperature of S3 is 1170℃, and the refining time is 40 minutes.

[0061] During the casting of S6, the mold temperature is 240℃, and the cooling rate is 6℃ / min.

[0062] The preparation method of the modified silicone oil cooling dispersion liquid is:

[0063] 6g polymethylhydrogen siloxane HF2030-M400, 4g allyl polyoxyethylene ether APEG-700, 1g allyl diphenyl phosphine, 0.2g phosphate acrylate, 40g ethylene glycol butyl ether are added into a reaction kettle, the temperature is raised to 85℃, 0.2g 0.2wt% chloroplatinic acid isopropanol solution is added, stirring reaction for 5 hours, after the reaction is completed, the temperature is lowered to 35℃, 0.2g nano boron nitride, 170g deionized water are added, stirring and dispersing for 60 minutes, a modified silicone oil cooling dispersion is obtained.

[0064] Example 3

[0065] A process for refining electronic-grade high-purity phosphor copper balls based on waste copper scraps, the operation steps are:

[0066] S1 Pretreatment: 28g of waste copper scraps are sorted to remove plastic, rubber and other non-copper impurities, then put into 90g of 8wt% sodium hydroxide solution, washed at 75℃ for 15 minutes to remove oil stains and oxides, and then taken out for drying;

[0067] S2 Melting: the pretreated waste copper scraps are added into a medium-frequency induction furnace and melted at 1180℃;

[0068] S3 Refining: 1.3g of a composite refining agent is added into 90g of copper liquid for refining to remove iron, zinc, lead and tin impurities in the copper liquid, so that the content of impurities is greatly reduced;

[0069] S4 Phosphorus addition: after the refining is completed, phosphor copper alloy is added into the copper liquid to adjust the phosphorus content to 0.06wt%; when the phosphor copper alloy is added, the temperature of the copper liquid is kept at 1210℃ to ensure that the phosphor copper alloy is quickly melted and uniformly dispersed in the copper liquid;

[0070] S5 Holding and standing: the copper liquid after adding phosphorus is held and stood at 1180℃ for 25 minutes; during the holding and standing, the inclusions and bubbles in the copper liquid have enough time to float out, so that the copper liquid is more pure and the composition is more uniform;

[0071] S6 Casting and forming: the copper liquid after holding and standing is cast into a specific mold to obtain a phosphor copper ball blank; during the casting, the temperature of the mold is controlled at 280℃;

[0072] S7 Post-treatment: the phosphor copper ball blank is cooled, polished, washed and dried by using a modified silicone oil cooling dispersion to obtain electronic-grade high-purity phosphor copper balls.

[0073] The melting temperature of S2 is 1180℃.

[0074] The composite refining agent is quartz sand, sodium carbonate and fluorite, and the mass ratio is 4:1.5:0.8.

[0075] The refining temperature of S3 is 120 DEG C, and the refining time is 50 minutes.

[0076] During the casting process of S6, the mold temperature is 280 DEG C, and the cooling rate is 8 DEG C / min.

[0077] The preparation method of the modified silicone oil cooling dispersion liquid is as follows:

[0078] 7g of polymethylhydrogen siloxane HF2030-M400, 4g of allyl polyoxyethylene ether APEG-700, 1.5g of allyl diphenyl phosphine, 0.4g of phosphate acrylate, 50g of ethylene glycol butyl ether are added into a reaction kettle, heated to 85 DEG C, 0.2g of 0.4wt% chloroplatinic acid isopropyl alcohol solution is added, and stirring reaction is carried out for 5 hours, after the reaction is completed, the temperature is lowered to 35 DEG C, 0.3g of nano boron nitride and 200g of deionized water are added, and stirring and dispersion are carried out for 90 minutes to obtain a modified silicone oil cooling dispersion liquid.

[0079] Example 4

[0080] An electronic-grade high-purity phosphor copper ball refining preparation process based on waste copper, the operation steps are as follows:

[0081] S1 pretreatment: 30g of waste copper is sorted to remove plastic, rubber and other non-copper impurities, then put into 100g of 10wt% sodium hydroxide solution, clean for 20 minutes at 80 DEG C to remove oil stains and oxides, and then take out and dry;

[0082] S2 melting: the pretreated waste copper is added into a medium-frequency induction furnace and melted at 1200 DEG C;

[0083] S3 refining: 1.5g of composite refining agent is added into 100g of copper liquid for refining to remove iron, zinc, lead and tin impurities in the copper liquid, so that the impurity content is greatly reduced;

[0084] S4 phosphorus addition: after the refining is completed, phosphor copper alloy is added into the copper liquid to adjust the phosphorus content to 0.07wt%; when the phosphor copper alloy is added, the temperature of the copper liquid is kept at 1230 DEG C to ensure that the phosphor copper alloy is quickly melted and uniformly dispersed in the copper liquid;

[0085] S5 holding and standing: the copper liquid after adding phosphorus is held and stood at 1200 DEG C for 30 minutes; during the holding and standing process, the inclusions and bubbles in the copper liquid have enough time to float out, so that the copper liquid is more pure and the composition is more uniform;

[0086] S6 casting: the copper liquid after holding and standing is cast into a specific mold to obtain a phosphor copper ball blank; during the casting process, the mold temperature is controlled at 300 DEG C;

[0087] S7 post-processing: the phosphor copper ball blank is cooled, polished, washed, and dried by the modified silicone oil cooling dispersion liquid to obtain the electronic grade high purity phosphor copper ball.

[0088] The melting temperature of S2 is 1200℃.

[0089] The composite refining agent is quartz sand, sodium carbonate, and fluorite, and the mass ratio is 5:2:1.

[0090] The refining temperature of S3 is 1220℃, and the refining time is 60 minutes.

[0091] During the S6 casting process, the mold temperature is 300℃, and the cooling rate is 10℃ / min.

[0092] The preparation method of the modified silicone oil cooling dispersion liquid is:

[0093] 8g of polymethylhydrogen siloxane HF2030-M400, 5g of allyl polyoxyethylene ether APEG-700, 2g of allyl diphenyl phosphine, 0.5g of phosphate acrylate, 60g of ethylene glycol butyl ether are added into a reaction kettle, heated to 90℃, 0.3g of 0.5wt% chloroplatinic acid isopropyl alcohol solution is added, and stirred for 6 hours. After the reaction is completed, the temperature is lowered to 40℃, 0.4g of nano boron nitride and 220g of deionized water are added, and stirred and dispersed for 100 minutes to obtain a modified silicone oil cooling dispersion liquid.

[0094] Comparative Example 1

[0095] An electronic grade high purity phosphor copper ball refining preparation process based on waste copper, the operation steps are:

[0096] S1 pretreatment: 20g of waste copper is sorted to remove plastic, rubber and other non-copper impurities, then put into 70g of 5wt% sodium hydroxide solution, clean for 10 minutes at 60℃ to remove oil stains and oxides; take out and dry;

[0097] S2 melting: the pretreated waste copper is added into a medium frequency induction furnace and melted at 1100℃.

[0098] S3 refining: 0.5g of composite refining agent is added into 70g of copper liquid for refining to remove iron, zinc, lead, tin and other impurity elements in the copper liquid, so that the impurity content is greatly reduced.

[0099] S4 phosphorus addition: after refining, phosphor copper alloy is added into the copper liquid to adjust the phosphorus content to 0.03wt%; when the phosphor copper alloy is added, the copper liquid temperature is kept at 1180℃ to ensure that the phosphor copper alloy is quickly melted and uniformly dispersed in the copper liquid.

[0100] S5: holding and standing: the copper liquid after adding phosphorus is held and stood at 1150℃ for 15 minutes; during the holding and standing process, the inclusions and bubbles in the copper liquid have enough time to float out, so that the copper liquid is more pure and the composition is more uniform;

[0101] S6: casting: the copper liquid after holding and standing is cast into a specific mold to obtain a phosphor copper ball blank; during the casting process, the mold temperature is controlled at 200℃;

[0102] S7: post-treatment: the phosphor copper ball blank is cooled, polished, washed, and dried by a cooling dispersion liquid to obtain an electronic-grade high-purity phosphor copper ball.

[0103] The melting temperature of S2 is 1100℃.

[0104] The composite refining agent is quartz sand, sodium carbonate, and fluorite, and the mass ratio is 3:1:0.5.

[0105] The refining temperature of S3 is 1150℃, and the refining time is 30 minutes.

[0106] During the casting process of S6, the mold temperature is 200℃, and the cooling rate is 5℃ / min.

[0107] The preparation method of the cooling dispersion liquid is:

[0108] 5g polymethylhydrogen siloxane HF2030-M400, 3g allyl polyoxyethylene ether APEG-700, 30g ethylene glycol butyl ether are added to a reaction kettle, heated to 80℃, 0.1g 0.1wt% chloroplatinic acid isopropyl alcohol solution is added, and stirred for 4 hours. After the reaction is completed, the temperature is lowered to 30℃, 0.1g nano boron nitride and 150g deionized water are added, and stirred and dispersed for 50 minutes to obtain a cooling dispersion liquid.

[0109] Comparative example 2

[0110] An electronic-grade high-purity phosphor copper ball refining preparation process based on scrap copper, the operation steps are:

[0111] S1: pretreatment: 20g of scrap copper is sorted to remove plastic, rubber and other non-copper impurities, then put into 70g of 5wt% sodium hydroxide solution, clean for 10 minutes at 60℃ to remove oil stains and oxides; take out and dry;

[0112] S2: melting: the pretreated scrap copper is added to a medium-frequency induction furnace and melted at 1100℃;

[0113] S3: refining: 0.5g of composite refining agent is added to 70g of copper liquid for refining to remove iron, zinc, lead, tin and other impurity elements in the copper liquid, so that the impurity content is greatly reduced;

[0114] S4 phosphorus addition: after refining, phosphorus copper alloy is added to the copper liquid to adjust the phosphorus content to 0.03wt%; when the phosphorus copper alloy is added, the temperature of the copper liquid is kept at 1180℃, ensuring that the phosphorus copper alloy melts quickly and disperses uniformly in the copper liquid;

[0115] S5 holding and standing: the copper liquid after adding phosphorus is kept at 1150℃ for 15 minutes; during the holding and standing process, the inclusions and bubbles in the copper liquid have enough time to float out, making the copper liquid purer and the composition more uniform;

[0116] S6 casting: the copper liquid after holding and standing is cast into a specific mold to obtain a phosphorus copper ball blank; during the casting process, the mold temperature is controlled at 200℃.

[0117] S7 post-processing: the phosphorus copper ball blank is cooled, polished, washed, and dried by a cooling dispersion liquid to obtain an electronic-grade high-purity phosphorus copper ball.

[0118] The melting temperature of S2 is 1100℃.

[0119] The composite refining agent is quartz sand, sodium carbonate, and fluorite, with a mass ratio of 3:1:0.5.

[0120] The refining temperature of S3 is 1150℃, and the refining time is 30 minutes.

[0121] During the casting process of S6, the mold temperature is 200℃, and the cooling rate is 5℃ / min.

[0122] The preparation method of the cooling dispersion liquid is:

[0123] 5g polymethylhydrogen siloxane HF2030-M400, 3g allyl polyoxyethylene ether APEG-700, 0.05g phosphate acrylate, 30g ethylene glycol butyl ether are added to a reaction kettle, heated to 80℃, 0.1g 0.1wt% chloroplatinic acid isopropyl alcohol solution is added, stirred for 4 hours, after the reaction is completed, the temperature is lowered to 30℃, 0.1g nano boron nitride and 150g deionized water are added, and stirred and dispersed for 50 minutes to obtain a cooling dispersion liquid.

[0124] Comparative Example 3

[0125] An electronic-grade high-purity phosphorus copper ball refining preparation process based on scrap copper, the operation steps are:

[0126] S1 pretreatment: 20g of scrap copper is sorted to remove plastic, rubber and other non-copper impurities, then placed in a 70g mass percentage of 5% sodium hydroxide solution, washed at 60℃ for 10 minutes to remove oil and oxides; take out and dry;

[0127] S2 melting: the pretreated scrap copper is added to a medium-frequency induction furnace and melted at 1100℃;

[0128] S3 refining: 0.5g of the composite refining agent is added to 70g of copper liquid for refining, so as to remove iron, zinc, lead, tin and other impurity elements in the copper liquid and greatly reduce the content of impurities;

[0129] S4 phosphorus addition: after the refining is completed, phosphorus copper alloy is added to the copper liquid to adjust the phosphorus content to 0.03wt%; when the phosphorus copper alloy is added, the temperature of the copper liquid is kept at 1180℃, so as to ensure that the phosphorus copper alloy is quickly melted and uniformly dispersed in the copper liquid;

[0130] S5 holding and standing: the copper liquid after the addition of phosphorus is held and stood at 1150℃ for 15 minutes; during the holding and standing, the inclusions and bubbles in the copper liquid have enough time to float out, so that the copper liquid is more pure and the composition is more uniform;

[0131] S6 casting and forming: the copper liquid after the holding and standing is cast into a specific mold to obtain a phosphorus copper ball blank; during the casting, the temperature of the mold is controlled at 200℃.

[0132] S7 post-treatment: the phosphorus copper ball blank is cooled, polished, washed, and dried by a cooling dispersion liquid to obtain an electronic-grade high-purity phosphorus copper ball.

[0133] The melting temperature of S2 is 1100℃.

[0134] The composite refining agent is quartz sand, sodium carbonate, and fluorite, and the mass ratio is 3:1:0.5.

[0135] The refining temperature of S3 is 1150℃, and the refining time is 30 minutes.

[0136] During the casting of S6, the temperature of the mold is 200℃, and the cooling rate is 5℃ / min.

[0137] The preparation method of the cooling dispersion liquid is as follows:

[0138] 5g of polymethylhydrogen siloxane HF2030-M400, 3g of allyl polyoxyethylene ether APEG-700, 0.2g of allyl diphenyl phosphine, 30g of ethylene glycol butyl ether are added to a reaction kettle, heated to 80℃, 0.1g of 0.1wt% chloroplatinic acid isopropyl alcohol solution is added, and stirred for 4 hours. After the reaction is completed, the temperature is lowered to 30℃, 0.1g of nano boron nitride and 150g of deionized water are added, and stirred and dispersed for 50 minutes to obtain a cooling dispersion liquid.

[0139] Table 1: test results of examples and comparative examples

[0140] Copper purity (%) Phosphorus content (%) Total content of harmful impurities (%) Example 1 99.95 0.03 0.025 Example 2 99.96 0.04 0.024 Example 3 99.98 0.06 0.022 Example 4 99.99 0.07 0.021 Comparative Example 1 85.64 0.0007 18.34 Comparative Example 2 95.85 0.03 0.92 Comparative Example 3 96.37 0.03 0.73

[0141] Through data analysis of the above examples and comparative examples, the phosphor copper ball prepared by the application has a purity of up to 99.99%, and the total content of harmful impurities is less than 0.025%, which fully meets the requirements of the electronic industry for high-purity phosphor copper balls.

[0142] The above is only the preferred embodiment of the application, and does not limit the application in any form. Although the application has been disclosed as above with the preferred embodiment, it is not intended to limit the application. Any person skilled in the art can make some changes or modifications to the equivalent embodiments with the disclosed technical content without departing from the scope of the technical solution of the application. Any modification, equivalent change and modification of the above examples made according to the technical essence of the application still belong to the scope of the technical solution of the application.

Claims

1. A process for the preparation of electronic grade high purity phosphorous copper spheres based on scrap copper, characterized in that: The operation steps are: ​ S1 pretreatment: 20-30 parts by mass of waste copper scraps are sorted to remove plastic, rubber and non-copper impurities, and then put into 70-100 parts by mass of a sodium hydroxide solution with a mass percentage of 5-10%, cleaned at 60-80℃ for 10-20 minutes to remove oil stains and oxides; and then taken out and dried; S2 melting: the pretreated waste copper scraps are added into a medium-frequency induction furnace and melted at 1100-1200℃; S3 refining: 0.5-1.5 parts by mass of a composite refining agent is added into 70-100 parts by mass of copper liquid for refining to remove iron, zinc, lead and tin impurities in the copper liquid, so that the impurity content is greatly reduced; S4 phosphorus addition: after the refining is completed, a phosphor copper alloy is added into the copper liquid to adjust the phosphorus content to 0.03wt%-0.07wt%; when the phosphor copper alloy is added, the temperature of the copper liquid is kept at 1180-1230℃ to ensure that the phosphor copper alloy is quickly melted and uniformly dispersed in the copper liquid; S5 holding and standing: the copper liquid after the addition of phosphorus is held and stood at 1150-1200℃ for 15-30 minutes; during the holding and standing, the inclusions and bubbles in the copper liquid have enough time to float out, so that the copper liquid is more pure and the composition is more uniform; S6 casting and forming: the copper liquid after the holding and standing is cast into a specific mold to obtain a phosphor copper ball blank; during the casting, the mold temperature is controlled at 200-300℃; S7 post-treatment: the phosphor copper ball blank is cooled, polished, washed and dried by a modified silicone oil cooling dispersion liquid to obtain an electronic-grade high-purity phosphor copper ball. The modified silicone oil cooling dispersion liquid is prepared by reacting polymethylhydrogen siloxane, allyl polyoxyethylene ether, allyl diphenyl phosphine, phosphate acrylate, ethylene glycol butyl ether, chloroplatinic acid isopropanol solution and nano boron nitride.

2. The refining and preparation process of electronic-grade high-purity phosphorus copper balls based on scrap copper according to claim 1, characterized in that: The melting temperature of S2 is 1100-1200℃.

3. The refining and preparation process of electronic-grade high-purity phosphorus copper balls based on waste copper according to claim 1, characterized in that: The composite refining agent is quartz sand, sodium carbonate and fluorite, and the mass ratio is (3-5):(1-2):(0.5-1).

4. The refining and preparation process of electronic-grade high-purity phosphorus copper balls based on waste copper according to claim 1, characterized in that: The refining temperature of S3 is 1150-1220℃, and the refining time is 30-60 minutes.

5. The refining and preparation process of electronic-grade high-purity phosphorus copper balls based on scrap copper according to claim 1, characterized in that: During the casting of S6, the mold temperature is 200-300℃, and the cooling rate is 5-10℃ / min.

6. The refining and preparation process of electronic-grade high-purity phosphorus copper balls based on waste copper according to claim 1, characterized in that: The preparation method of the modified silicone oil cooling dispersion liquid is: According to the mass fraction, 5-8 parts of polymethylhydrogen siloxane, 3-5 parts of allyl polyoxyethylene ether, 0.2-2 parts of allyl diphenyl phosphine, 0.05-0.5 parts of phosphate acrylate, 30-60 parts of ethylene glycol butyl ether are added into a reaction kettle, heated to 80-90℃, 0.1-0.3 parts of 0.1-0.5wt% chloroplatinic acid isopropanol solution is added, stirred for 4-6 hours, after the reaction is completed, the temperature is lowered to 30-40℃, 0.1-0.4 parts of nano boron nitride and 150-220 parts of deionized water are added, and stirred and dispersed for 50-100 minutes to obtain the modified silicone oil cooling dispersion liquid.