Complete non-cyanogens wet process for green recycling of waste printed circuit board

Abstract

The invention related to the recycling field of waste printed circuit boards (WPCB), and especially involved a complete non-cyanogens wet process for green recycling of WPCB, which belonged to the field of recycle economy. In the invention, the process included that WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification, the mixed copper powders were smelted and casted to get copper anode plates, the copper was purified by electrolytion, the valuable metals (such as copper, gold, silver, platinum and palladium, lead and tin) were recycled from the copper anode slime, and the waste water was recycled. The recovery ratio of all-metal was above 98%. The purity of the cathode copper was up to 4N level. The ratio of de-coppering was above 96%. The recovery ratio of gold was above 98.

Claims

1. A method of recycling a waste printed circuit board (WPCB) comprising: 1) breaking the WPCB to obtain a powder mixture, separating a copper powder from the powder mixture by a gravity separation, and casting copper anode plates by smelting the copper powder; 2) electrolyzing the copper anode plates in an electrolytic bath comprising CuSO.sub.4 and H.sub.2SO.sub.4 to obtain a cathode copper and a copper anode slime; 3) performing a de-coppering process that comprises mixing the copper anode slime with a de-coppering solution containing H.sub.2SO.sub.4 and NaCl; adding MnO.sub.2 into the de-coppering solution; separating a first slag from the de-coppering solution by filtration; and returning a first filtrate after separating the first slag to the electrolytic bath; 4) performing a de-golding process that comprises putting the first slag in a de-golding solution comprising NaCl, H.sub.2SO.sub.4 and NaClO.sub.3; separating a second slag from the de-golding solution by filtration; reducing a second filtrate after separating the second slag by Na.sub.2SO.sub.3 to obtain rough gold powders, wherein a residual solution of the second filtrate after removing rough gold powders is a first remanent reduction liquid; 5) performing a process of obtaining a platinum and palladium concentrate that comprises adjusting a pH value of the first remanent reduction liquid to 0-2; adding a metathesis metal into the first remanent reduction liquid until the pH value thereof reaches 2.5-3, wherein the metathesis metal is zinc, iron, or a mixture thereof; 6) performing a de-silvering process that comprises: putting the second slag in a de-silvering solution comprising Na.sub.2SO.sub.3; separating a third slag from the de-silvering solution by filtration, and reducing a third filtrate after separating the third slag to obtain rough silver powders; 7) performing a de-leading process that comprises heating the third slag in a de-leading solution comprising HCl, NaCl and CaCl.sub.2; separating a fourth slag from the de-leading solution by filtration; cooling a fourth filtrate to precipitate out PbCl.sub.2; separating the PbCl.sub.2 solids from the fourth filtrate to obtain a second remanent reduction liquid and returning the second remanent reduction liquid to the de-leading solution; and 8) performing a de-tinning process that comprises mixing the fourth slag and NaOH to obtain a mixture; roasting the mixture; quenching the roasted mixture by water to obtain a de-tinning solution; separating a fifth slag from the de-tinning solution by filtration; and evaporating a fifth filtrate after separating the fifth slag to obtain Na.sub.2SnO.sub.3.

2. The method of claim 1, wherein the electrolytic bath has a H.sub.2SO.sub.4 concentration of 0.5-2 mol/L, a CuSO.sub.4 concentration of 0.2-1.5 mol/L, a gelatin concentration of 50-300 mg/L, a thiourea concentration of 50-300 mg/L, a current density of 100-500 A/m.sup.2, and an electrolytic temperature of 30-80 C.

3. The method of claim 2, wherein the electrolytic bath has the H.sub.2SO.sub.4 concentration of 1-2 mol/L, the CuSO.sub.4 concentration of 0.5-1 mol/L, the gelatin concentration of 50-100 mg/L, and the thiourea concentration of 100-150 mg/L.

4. The method of claim 1, wherein the de-coppering solution has a H.sub.2SO.sub.4 concentration of 0.5-5 mol/L, a NaCl concentration of 0.1-5 mol/L, an amount of MnO.sub.2 at 2-40% of a weight of the anode slime, a solid-to-liquid ratio of 1:4-1:20, wherein the de-coppering process has a reaction temperature of 30-90 C., and a reaction time of 0.5-5 h.

5. The method of claim 4, wherein the de-coppering solution has the H.sub.2SO.sub.4 concentration of 1-2 mol/L, the NaCl concentration of 0.5-2 mol/L, the amount of MnO.sub.2 at 10-20% of the weight of the anode slime, and the solid-to-liquid ratio of 1:5-1:10.

6. The method of claim 1, wherein the de-golding solution has a NaCl concentration of 20-100 g/L, a H.sub.2SO.sub.4 concentration of 50-300 g/L, a molar ratio of NaClO.sub.3 and NaCl of 1:5-3:5, a solid-to-liquid ratio of 1:4-1:20, wherein the de-golding process has a reaction temperature of 50-95 C., a reaction time of 0.5-5 h, a Na.sub.2SO.sub.3 concentration of 70-280 g/L, a reduction temperature of 10-50 C., and a reduction time of 5-60 min.

7. The method of claim 6, wherein the de-golding solution has a NaCl concentration of 20-100 g/L, the H.sub.2SO.sub.4 concentration of 100-200 g/L, the solid-to-liquid ratio of 1:5-1:10, and wherein the concentration of Na.sub.2SO.sub.3 used for reducing the second filtrate is 150-250 g/L.

8. The method of claim 1, wherein the de-silvering solution has a Na.sub.2SO.sub.3 concentration of 70-280 g/L, a solid-to-liquid ratio of 1:4-1:20, a pH value of 11-14, a reducing agent that is formaldehyde or oxalic acid at a mass ratio of the reducing agent to silver of 1:5-5:5, wherein the de-silvering process has a reaction temperature of 20-50 C. and a reaction time of 0.5-5 h.

9. The method of claim 8, wherein the de-silvering solution has the Na.sub.2SO.sub.3 concentration of 100-230 g/L and the solid-to-liquid ratio of 1:5-1:10.

10. The method of claim 1, wherein in the de-leading solution has a HCl concentration of 10-200 g/L, a NaCl concentration of 50-350 g/L, a CaCl.sub.2 concentration of 10-300 g/L, a total concentration of chloride ion of 3-6.5 mol/L, a solid-to-liquid ratio of 1:5-1:30, wherein the de-leading process has a reaction temperature is 70-110 C., and a reaction time is 0.5-5 h.

11. The method of claim 10, wherein in the de-leading solution has a HCl concentration of 50-150 g/L, the NaCl concentration of 200-300 g/L, the CaCl.sub.2 concentration of 10-100 g/L, and the solid-to-liquid ratio of 1:10-1:20.

12. The method of claim 1, further comprising adding CaCl.sub.2 to the second remanent reduction liquid of the de-leading process so that the CaCl.sub.2 concentration in the second remanent reduction liquid reaches 10-300 g/L.

13. The method of claim 12, wherein the CaCl.sub.2 concentration in the second remanent reduction liquid reaches 10-100 g/L.

14. The method of claim 1, employing no aqua regia or cyanide.

15. The method of claim 1, wherein the copper anode slime comprises PbSO.sub.4, SnO.sub.2, Ag.sub.2SO.sub.4, copper, and a noble metal that is gold, platinum, or palladium.

16. The method of claim 1, wherein in step 8), a mass ratio of the fourth slag and NaOH is 1:1-10:1, a roasting temperature is 300-600 C., and a roasting time is 0.5-5 h.

17. The method of claim 1, wherein the metathesis metal is zinc.

18. The method of claim 1, wherein the third filtrate is reduced using formaldehyde.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows the whole implementation process flow diagram of the complete non-cyanogens wet process for green recycling of WPCB in the invention.

(2) FIG. 2 shows the process flow diagram of recovering copper from anode slime in the invention.

(3) FIG. 3 shows the process flow diagram of recovering gold in the invention.

(4) FIG. 4 shows the process flow diagram of recovering platinum and palladium in the invention.

(5) FIG. 5 shows the process flow diagram of recovering silver in the invention.

(6) FIG. 6 shows the process flow diagram of recovering lead in the invention.

(7) FIG. 7 shows the process flow diagram of recovering tin in the invention.

DETAILED DESCRIPTION

(8) With the illustration, the following was to explain the complete non-cyanogens wet process for green recycling of WPCB further by specific examples.

Example 1

(9) FIG. 1 was the whole implementation process flow diagram of the complete non-cyanogens wet process for green recycling of WPCB in the invention. As was shown in FIG. 1, WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification. The mixed copper powders were smelted and casted to get copper anode plates.

(10) The copper anode plates were put in the mixed solution of CuSO4 and H2SO4 to be electrolyzed and purified, and then to get cathode copper and copper anode slime. In the process of copper electrolyzation and purification, the concentration of H2SO4 was 0.5 mol/L, the concentration of CuSO4 was 1.5 mol/L, the concentration of gelatin was 100 mg/L, the concentration of thiourea was 120 mg/L, the current density is 130 A/m2, and electrolytic temperature was 60 C. The purity of the cathode copper was up to 4N level.

(11) FIG. 2 was the process flow diagram of recovering copper from anode slime in the invention. Mixing copper anode slime with the solution of H2SO4 and NaCl, MnO2 was added to recover copper. The solution and slag of de-coppering were got by filtering. The solution of de-coppering was returned to the process of copper electrolyzation and purification. In the process of de-coppering, the concentration of H2SO4 was 0.5 mol/L, the concentration of NaCl was 0.1 mol/L, the amount of MnO2 added was 2% of anode slime, the solid-to-liquid ratio was 1:8, the reaction temperature was 80 C., and the reaction time was 4 h. The ratio of de-coppering was 96.7%.

(12) FIG. 3 was the process flow diagram of recovering gold in the invention. The slag of de-coppering was put in the mixed solution of NaCl, H2SO4 and NaClO3 to recover gold. The solution and slag of de-golding were got by filtering. The solution of de-golding was reduced to rough gold powders by Na2SO3 and the residual solution was the remanent reduction liquid of de-golding. In the process of de-golding, the concentration of NaCl was 100 g/L, the concentration of H2SO4 was 50 g/L, the molar ratio of NaClO3 and NaCl was 2:5, the solid-to-liquid ratio was 1:10, the reaction temperature was 65 C., reaction time was 0.5 h. The concentration of Na2SO3 for gold reduced was 140 g/L, the reduction temperature was 20 C., and the reduction time was 10 min. The recovery ratio of gold was 98.5%.

(13) FIG. 4 was the process flow diagram of recovering platinum and palladium in the invention. Platinum and palladium concentrate was obtained by metathesis in the remanent reduction liquid of de-golding. The pH value of remanent reduction liquid was adjusted to 0, and the replacement reaction temperature was 20 C. Until the pH value of remanent reduction liquid was adjusted to 2.5, stop adding the metathesis metals, which were zinc powders. The recovery ratio of platinum and palladium was 96.2%.

(14) FIG. 5 was the process flow diagram of recovering silver in the invention. The slag of de-golding was put in the solution of Na2SO3 to recover silver. The solution and slag of de-silvering were got by filtering. The solution of de-silvering was reduced to rough silver powders. The concentration of Na2SO3 was 140 g/L, the solid-to-liquid ratio was 1:10, the reaction temperature was 20 C., the reaction time was 5 h, and the pH value of de-silvering solution was 14. The reducing agent was formaldehyde. The quality ratio of the reducing agent and silver was 1:4. The recovery ratio of silver was 97%.

(15) FIG. 6 was shows the process flow diagram of recovering lead in the invention. The slag of de-silvering was heated in the mixed solution of HCl, NaCl and CaCl2 to recover lead. The solution and slag of de-leading were got by filtering. The solution of de-leading was cooled to dissolve out PbCl2, and the residual solution was the remanent reduction liquid of de-leading, which was returned to the process of de-leading. In the process of de-leading, the concentration of HCl was 10 g/L, the concentration of NaCl was 350 g/L, the concentration of CaCl2 was 20 g/L, the total concentration of chloride ion was 6.4 mol/L, the solid-to-liquid ratio was 1:20, the reaction temperature was 110 C., and the reaction time was 2 h. The regeneration process for remanent reduction liquid of de-leading was that adding CaCl2 to make the concentration to 20 g/L. The recovery ratio of lead was 97%.

(16) FIG. 7 was the process flow diagram of recovering tin in the invention. The slag of de-leading and NaOH were mixed, which were roasted to recover tin. The solution and slag of de-tinning were got by calcined sands water quenching and filtering. To get Na2SnO3, the solution of de-tinning was evaporated and crystallized. The quality ratio of the de-leading slag and NaOH was 2:1, the roasting temperature was 350 C., and the roasting time was 2 h. The recovery ratio of tin was 94.2%.

Example 2

(17) Firstly, WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification. The mixed copper powders were smelted and casted to get copper anode plates.

(18) The copper anode plates were put in the mixed solution of CuSO4 and H2SO4 to be electrolyzed and purified, and then to get cathode copper and copper anode slime. In the process of copper electrolyzation and purification, the concentration of H2SO4 was 2 mol/L, the concentration of CuSO4 was 1 mol/L, the concentration of gelatin was 50 mg/L, the concentration of thiourea was 100 mg/L, the current density is 100 A/m2, and electrolytic temperature was 40 C. The purity of the cathode copper was up to 4N level.

(19) Mixing copper anode slime with the solution of H2SO4 and NaCl, MnO2 was added to recover copper. The solution and slag of de-coppering were got by filtering. The solution of de-coppering was returned to the process of copper electrolyzation and purification. In the process of de-coppering, the concentration of H2SO4 was 2 mol/L, the concentration of NaCl was 3 mol/L, the amount of MnO2 added was 8% of anode slime, the solid-to-liquid ratio was 1:15, the reaction temperature was 70 C., and the reaction time was 1 h. The ratio of de-coppering was 97.1%.

(20) The slag of de-coppering was put in the mixed solution of NaCl, H2SO4 and NaClO3 to recover gold. The solution and slag of de-golding were got by filtering. The solution of de-golding was reduced to rough gold powders by Na2SO3 and the residual solution was the remanent reduction liquid of de-golding. In the process of de-golding, the concentration of NaCl was 40 g/L, the concentration of H2SO4 was 150 g/L, the molar ratio of NaClO3 and NaCl was 1:5, the solid-to-liquid ratio was 1:20, the reaction temperature was 80 C., reaction time was 4 h. The concentration of Na2SO3 for gold reduced was 70 g/L, the reduction temperature was 50 C., and the reduction time was 10 min. The recovery ratio of gold was 98.7%.

(21) Platinum and palladium concentrate was obtained by metathesis in the remanent reduction liquid of de-golding. The pH value of remanent reduction liquid was adjusted to 1, and the replacement reaction temperature was 10 C. Until the pH value of remanent reduction liquid was adjusted to 2.7, stop adding the metathesis metals, which were iron powders. The recovery ratio of platinum and palladium was 96.8%.

(22) The slag of de-golding was put in the solution of Na2SO3 to recover silver. The solution and slag of de-silvering were got by filtering. The solution of de-silvering was reduced to rough silver powders. The concentration of Na2SO3 was 70 g/L, the solid-to-liquid ratio was 1:20, the reaction temperature was 40 C., the reaction time was 0.5 h, and the pH value of de-silvering solution was 14. The reducing agent was oxalic acid. The quality ratio of the reducing agent and silver was 1:2. The recovery ratio of silver was 96.9%.

(23) The slag of de-silvering was heated in the mixed solution of HCl, NaCl and CaCl2 to recover lead. The solution and slag of de-leading were got by filtering. The solution of de-leading was cooled to dissolve out PbCl2, and the residual solution was the remanent reduction liquid of de-leading, which was returned to the process of de-leading. In the process of de-leading, the concentration of HCl was 50 g/L, the concentration of NaCl was 200 g/L, the concentration of CaCl2 was 50 g/L, the total concentration of chloride ion was 5.2 mol/L, the solid-to-liquid ratio was 1:5, the reaction temperature was 90 C., and the reaction time was 3 h. The regeneration process for remanent reduction liquid of de-leading was that adding CaCl2 to make the concentration to 50 g/L. The recovery ratio of lead was 96.2%.

(24) The slag of de-leading and NaOH were mixed, which were roasted to recover tin. The solution and slag of de-tinning were got by calcined sands water quenching and filtering. To get Na2SnO3, the solution of de-tinning was evaporated and crystallized. The quality ratio of the de-leading slag and NaOH was 1:1, the roasting temperature was 300 C., and the roasting time was 4 h. The recovery ratio of tin was 91.8%.

Example 3

(25) Firstly, WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification. The mixed copper powders were smelted and casted to get copper anode plates.

(26) The copper anode plates were put in the mixed solution of CuSO4 and H2SO4 to be electrolyzed and purified, and then to get cathode copper and copper anode slime. In the process of copper electrolyzation and purification, the concentration of H2SO4 was 1 mol/L, the concentration of CuSO4 was 0.5 mol/L, the concentration of gelatin was 300 mg/L, the concentration of thiourea was 300 mg/L, the current density is 250 A/m2, and electrolytic temperature was 80 C. The purity of the cathode copper was up to 4N level.

(27) Mixing copper anode slime with the solution of H2SO4 and NaCl, MnO2 was added to recover copper. The solution and slag of de-coppering were got by filtering. The solution of de-coppering was returned to the process of copper electrolyzation and purification. In the process of de-coppering, the concentration of H2SO4 was 1 mol/L, the concentration of NaCl was 4 mol/L, the amount of MnO2 added was 15% of anode slime, the solid-to-liquid ratio was 1:12, the reaction temperature was 90 C., and the reaction time was 0.5 h. The ratio of de-coppering was 97.4%.

(28) The slag of de-coppering was put in the mixed solution of NaCl, H2SO4 and NaClO3 to recover gold. The solution and slag of de-golding were got by filtering. The solution of de-golding was reduced to rough gold powders by Na2SO3 and the residual solution was the remanent reduction liquid of de-golding. In the process of de-golding, the concentration of NaCl was 30 g/L, the concentration of H2SO4 was 200 g/L, the molar ratio of NaClO3 and NaCl was 3:5, the solid-to-liquid ratio was 1:10, the reaction temperature was 70 C., reaction time was 5 h. The concentration of Na2SO3 for gold reduced was 200 g/L, the reduction temperature was 25 C., and the reduction time was 10 min. The recovery ratio of gold was 98.9%.

(29) Platinum and palladium concentrate was obtained by metathesis in the remanent reduction liquid of de-golding. The pH value of remanent reduction liquid was adjusted to 2, and the replacement reaction temperature was 25 C. Until the pH value of remanent reduction liquid was adjusted to 3, stop adding the metathesis metals, which were mixed with zinc powders and iron powders by the quality ratio 1:1. The recovery ratio of platinum and palladium was 97.6%.

(30) The slag of de-golding was put in the solution of Na2SO3 to recover silver. The solution and slag of de-silvering were got by filtering. The solution of de-silvering was reduced to rough silver powders. The concentration of Na2SO3 was 200 g/L, the solid-to-liquid ratio was 1:10, the reaction temperature was 20 C., the reaction time was 2 h, and the pH value of de-silvering solution was 12.5. The reducing agent was formaldehyde. The quality ratio of the reducing agent and silver was 1:5. The recovery ratio of silver was 95.7%.

(31) The slag of de-silvering was heated in the mixed solution of HCl, NaCl and CaCl2 to recover lead. The solution and slag of de-leading were got by filtering. The solution of de-leading was cooled to dissolve out PbCl2, and the residual solution was the remanent reduction liquid of de-leading, which was returned to the process of de-leading. In the process of de-leading, the concentration of HCl was 10 g/L, the concentration of NaCl was 200 g/L, the concentration of CaCl2 was 100 g/L, the total concentration of chloride ion was 4.6 mol/L, the solid-to-liquid ratio was 1:15, the reaction temperature was 70 C., and the reaction time was 1 h. The regeneration process for remanent reduction liquid of de-leading was that adding CaCl2 to make the concentration to 100 g/L. The recovery ratio of lead was 95.3%.

(32) The slag of de-leading and NaOH were mixed, which were roasted to recover tin. The solution and slag of de-tinning were got by calcined sands water quenching and filtering. To get Na2SnO3, the solution of de-tinning was evaporated and crystallized. The quality ratio of the de-leading slag and NaOH was 5:1, the roasting temperature was 500 C., and the roasting time was 0.5 h. The recovery ratio of tin was above 92.1%.

Example 4

(33) Firstly, WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification. The mixed copper powders were smelted and casted to get copper anode plates.

(34) The copper anode plates were put in the mixed solution of CuSO4 and H2SO4 to be electrolyzed and purified, and then to get cathode copper and copper anode slime. In the process of copper electrolyzation and purification, the concentration of H2SO4 was 1.5 mol/L, the concentration of CuSO4 was 0.2 mol/L, the concentration of gelatin was 100 mg/L, the concentration of thiourea was 70 mg/L, the current density is 500 A/m2, and electrolytic temperature was 40 C. The purity of the cathode copper was up to 4N level.

(35) Mixing copper anode slime with the solution of H2SO4 and NaCl, MnO2 was added to recover copper. The solution and slag of de-coppering were got by filtering. The solution of de-coppering was returned to the process of copper electrolyzation and purification. In the process of de-coppering, the concentration of H2SO4 was 5 mol/L, the concentration of NaCl was 0.2 mol/L, the amount of MnO2 added was 30% of anode slime, the solid-to-liquid ratio was 1:20, the reaction temperature was 30 C., and the reaction time was 4 h. The ratio of de-coppering was 98.3%.

(36) The slag of de-coppering was put in the mixed solution of NaCl, H2SO4 and NaClO3 to recover gold. The solution and slag of de-golding were got by filtering. The solution of de-golding was reduced to rough gold powders by Na2SO3 and the residual solution was the remanent reduction liquid of de-golding. In the process of de-golding, the concentration of NaCl was 20 g/L, the concentration of H2SO4 was 150 g/L, the molar ratio of NaClO3 and NaCl was 1:2, the solid-to-liquid ratio was 1:5, the reaction temperature was 95 C., reaction time was 2 h. The concentration of Na2SO3 for gold reduced was 280 g/L, the reduction temperature was 20 C., and the reduction time was 30 min. The recovery ratio of gold was 98.8%.

(37) Platinum and palladium concentrate was obtained by metathesis in the remanent reduction liquid of de-golding. The pH value of remanent reduction liquid was adjusted to 1.5, and the replacement reaction temperature was 50 C. Until the pH value of remanent reduction liquid was adjusted to 3, stop adding the metathesis metals, which were mixed with zinc powders and iron powders by the quality ratio 2:1. The recovery ratio of platinum and palladium was 97.1%.

(38) The slag of de-golding was put in the solution of Na2SO3 to recover silver. The solution and slag of de-silvering were got by filtering. The solution of de-silvering was reduced to rough silver powders. The concentration of Na2SO3 was 280 g/L, the solid-to-liquid ratio was 1:8, the reaction temperature was 50 C., the reaction time was 4 h, and the pH value of de-silvering solution was 12. The reducing agent was oxalic acid. The quality ratio of the reducing agent and silver was 1:1. The recovery ratio of silver was 97.4%.

(39) The slag of de-silvering was heated in the mixed solution of HCl, NaCl and CaCl2 to recover lead. The solution and slag of de-leading were got by filtering. The solution of de-leading was cooled to dissolve out PbCl2, and the residual solution was the remanent reduction liquid of de-leading, which was returned to the process of de-leading. In the process of de-leading, the concentration of HCl was 200 g/L, the concentration of NaCl was 50 g/L, the concentration of CaCl2 was 10 g/L, the total concentration of chloride ion was 6.4 mol/L, the solid-to-liquid ratio was 1:30, the reaction temperature was 80 C., and the reaction time was 5 h. The regeneration process for remanent reduction liquid of de-leading was that adding CaCl2 to make the concentration to 10 g/L. The recovery ratio of lead was 95.2%.

(40) The slag of de-leading and NaOH were mixed, which were roasted to recover tin. The solution and slag of de-tinning were got by calcined sands water quenching and filtering. To get Na2SnO3, the solution of de-tinning was evaporated and crystallized. The quality ratio of the de-leading slag and NaOH was 10:1, the roasting temperature was 600 C., and the roasting time was 5 h. The recovery ratio of tin was 90.2%.

Example 5

(41) Firstly, WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification. The mixed copper powders were smelted and casted to get copper anode plates.

(42) The copper anode plates were put in the mixed solution of CuSO4 and H2SO4 to be electrolyzed and purified, and then to get cathode copper and copper anode slime. In the process of copper electrolyzation and purification, the concentration of H2SO4 was 2 mol/L, the concentration of CuSO4 was 0.5 mol/L, the concentration of gelatin was 70 mg/L, the concentration of thiourea was 50 mg/L, the current density is 300 A/m2, and electrolytic temperature was 30 C. The purity of the cathode copper was up to 4N level.

(43) Mixing copper anode slime with the solution of H2SO4 and NaCl, MnO2 was added to recover copper. The solution and slag of de-coppering were got by filtering. The solution of de-coppering was returned to the process of copper electrolyzation and purification. In the process of de-coppering, the concentration of H2SO4 was 2.5 mol/L, the concentration of NaCl was 5 mol/L, the amount of MnO2 added was 40% of anode slime, the solid-to-liquid ratio was 1:4, the reaction temperature was 60 C., and the reaction time was 6 h. The ratio of de-coppering was 98.2%.

(44) The slag of de-coppering was put in the mixed solution of NaCl, H2SO4 and NaClO3 to recover gold. The solution and slag of de-golding were got by filtering. The solution of de-golding was reduced to rough gold powders by Na2SO3 and the residual solution was the remanent reduction liquid of de-golding. In the process of de-golding, the concentration of NaCl was 70 g/L, the concentration of H2SO4 was 300 g/L, the molar ratio of NaClO3 and NaCl was 3:5, the solid-to-liquid ratio was 1:4, the reaction temperature was 60 C., reaction time was 1 h. The concentration of Na2SO3 for gold reduced was 100 g/L, the reduction temperature was 40 C., and the reduction time was 5 min. The recovery ratio of gold was 98.7%.

(45) Platinum and palladium concentrate was obtained by metathesis in the remanent reduction liquid of de-golding. The pH value of remanent reduction liquid was adjusted to 1, and the replacement reaction temperature was 50 C. Until the pH value of remanent reduction liquid was adjusted to 2.5, stop adding the metathesis metals, which were zinc powders. The recovery ratio of platinum and palladium was 96.6%.

(46) The slag of de-golding was put in the solution of Na2SO3 to recover silver. The solution and slag of de-silvering were got by filtering. The solution of de-silvering was reduced to rough silver powders. The concentration of Na2SO3 was 110 g/L, the solid-to-liquid ratio was 1:4, the reaction temperature was 40 C., the reaction time was 4 h, and the pH value of de-silvering solution was 12. The reducing agent was formaldehyde. The quality ratio of the reducing agent and silver was 2:3. The recovery ratio of silver was 96.4%.

(47) The slag of de-silvering was heated in the mixed solution of HCl, NaCl and CaCl2 to recover lead. The solution and slag of de-leading were got by filtering. The solution of de-leading was cooled to dissolve out PbCl2, and the residual solution was the remanent reduction liquid of de-leading, which was returned to the process of de-leading. In the process of de-leading, the concentration of HCl was 25 g/L, the concentration of NaCl was 100 g/L, the concentration of CaCl2 was 80 g/L, the total concentration of chloride ion was 3.1 mol/L, the solid-to-liquid ratio was 1:20, the reaction temperature was 95 C., and the reaction time was 0.5 h. The regeneration process for remanent reduction liquid of de-leading was that adding CaCl2 to make the concentration to 80 g/L. The recovery ratio of lead was 95.7%.

(48) The slag of de-leading and NaOH were mixed, which were roasted to recover tin. The solution and slag of de-tinning were got by calcined sands water quenching and filtering. To get Na2SnO3, the solution of de-tinning was evaporated and crystallized. The quality ratio of the de-leading slag and NaOH was 4:1, the roasting temperature was 550 C., and the roasting time was 0.5 h. The recovery ratio of tin was 92.3%.

Example 6

(49) Firstly, WPCB were broken by the jaw crusher, and then mixed copper powders and nonmetallic powders were separated by the method of air classification. The mixed copper powders were smelted and casted to get copper anode plates.

(50) The copper anode plates were put in the mixed solution of CuSO4 and H2SO4 to be electrolyzed and purified, and then to get cathode copper and copper anode slime. In the process of copper electrolyzation and purification, the concentration of H2SO4 was 1 mol/L, the concentration of CuSO4 was 1 mol/L, the concentration of gelatin was 100 mg/L, the concentration of thiourea was 120 mg/L, the current density is 180 A/m2, and electrolytic temperature was 30 C. The purity of the cathode copper was up to 4N level.

(51) Mixing copper anode slime with the solution of H2SO4 and NaCl, MnO2 was added to recover copper. The solution and slag of de-coppering were got by filtering. The solution of de-coppering was returned to the process of copper electrolyzation and purification. In the process of de-coppering, the concentration of H2SO4 was 2 mol/L, the concentration of NaCl was 1 mol/L, the amount of MnO2 added was 10% of anode slime, the solid-to-liquid ratio was 1:15, the reaction temperature was 45 C., and the reaction time was 6 h. The ratio of de-coppering was 97.6%.

(52) The slag of de-coppering was put in the mixed solution of NaCl, H2SO4 and NaClO3 to recover gold. The solution and slag of de-golding were got by filtering. The solution of de-golding was reduced to rough gold powders by Na2SO3 and the residual solution was the remanent reduction liquid of de-golding. In the process of de-golding, the concentration of NaCl was 60 g/L, the concentration of H2SO4 was 150 g/L, the molar ratio of NaClO3 and NaCl was 1:3, the solid-to-liquid ratio was 1:15, the reaction temperature was 50 C., reaction time was 1.5 h. The concentration of Na2SO3 for gold reduced was 150 g/L, the reduction temperature was 10 C., and the reduction time was 30 min. The recovery ratio of gold was 98.4%.

(53) Platinum and palladium concentrate was obtained by metathesis in the remanent reduction liquid of de-golding. The pH value of remanent reduction liquid was adjusted to 0, and the replacement reaction temperature was 25 C. Until the pH value of remanent reduction liquid was adjusted to 2.5, stop adding the metathesis metals, which were iron powders. The recovery ratio of platinum and palladium was 96.5%.

(54) The slag of de-golding was put in the solution of Na2SO3 to recover silver. The solution and slag of de-silvering were got by filtering. The solution of de-silvering was reduced to rough silver powders. The concentration of Na2SO3 was 180 g/L, the solid-to-liquid ratio was 1:10, the reaction temperature was 25 C., the reaction time was 2 h, and the pH value of de-silvering solution was 11. The reducing agent was oxalic acid. The quality ratio of the reducing agent and silver was 1:3. The recovery ratio of silver was 96.9%.

(55) The slag of de-silvering was heated in the mixed solution of HCl, NaCl and CaCl2 to recover lead. The solution and slag of de-leading were got by filtering. The solution of de-leading was cooled to dissolve out PbCl2, and the residual solution was the remanent reduction liquid of de-leading, which was returned to the process of de-leading. In the process of de-leading, the concentration of HCl was 50 g/L, the concentration of NaCl was 100 g/L, the concentration of CaCl2 was 300 g/L, the total concentration of chloride ion was 5.8 mol/L, the solid-to-liquid ratio was 1:15, the reaction temperature was 75 C., and the reaction time was 2 h. The regeneration process for remanent reduction liquid of de-leading was that adding CaCl2 to make the concentration to 300 g/L. The recovery ratio of lead was 96.3%.

(56) The slag of de-leading and NaOH were mixed, which were roasted to recover tin. The solution and slag of de-tinning were got by calcined sands water quenching and filtering. To get Na2SnO3, the solution of de-tinning was evaporated and crystallized. The quality ratio of the de-leading slag and NaOH was 7:1, the roasting temperature was 450 C., and the roasting time was 3 h. The recovery ratio of tin was 90.4%.

(57) There were detailed illustration by the examples above of the invention, but only for the better examples of the invention, which can't be limited scope of the invention. All the equalization change and improvement according to the range applied in the invention, shall be still belongs to the range of this invention patent.