Method for synergistically treating high-sulfur copper-containing hazardous waste and copper-containing solid waste

Abstract

The application provides a method for cooperatively treating high-sulfur copper-containing hazardous waste and copper-containing solid waste, comprising the following steps: step 1, mixing alkali copper carbonate waste and high-sulfur copper-containing hazardous waste to obtain mixed material one; step 2, pre-dehydrating the mixed material one by using a rotary dryer to obtain mixed material two; step 3, mixing the mixed material two and copper-containing solid waste to obtain mixed material three; step 4, mixing cement and soot to obtain mixed material four; step 5, adding water to the mixed material four and mixing to obtain mixed material five; step 6, mixing the mixed material three and the mixed material five to obtain mixed material six; and step 7, using a brick making machine to make the mixed material six into bricks, naturally drying the bricks, and then performing fire treatment. The application solves the problem that in the prior art, the low desulfurization rate of the fire treatment of high-sulfur copper-containing hazardous waste leads to a high content of copper matte, which is not conducive to the enrichment of heavy metals.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of harmless treatment of hazardous waste and solid waste, and particularly relates to a method for cooperatively treating high-sulfur copper-containing hazardous waste and copper-containing solid waste. BACKGROUND

[0002] A large amount of heavy metal sludge is generated in the wastewater treatment process of metal surface treatment, printed circuit board industry, electroplating industry and wire and cable industry. Most of the heavy metal sludge is hazardous waste and needs to be harmlessly treated. The metal value of such hazardous waste is good, and it contains a large amount of high-value precious metals such as gold, silver, platinum and palladium, and also contains a high content of sulfur (i.e. high-sulfur copper-containing hazardous waste). The copper-containing solid waste is generally leftover materials of non-ferrous industry and copper-containing waste materials from electronic industry, especially the copper-containing waste materials from electronic industry, which have high copper grade and good recycling value.

[0003] The high-sulfur copper-containing hazardous waste is generally obtained by sulfidation precipitation or hydroxide precipitation. Due to different front-end processes of electronic industry, the composition of the hazardous waste is relatively complex, and it contains hazardous substances. At present, the harmless treatment process of hazardous waste mainly relies on fire method. However, in the process of fire method, the desulfurization rate of the material is low, so that the output of the fire method treatment contains a large amount of copper matte, which is not conducive to the enrichment of heavy metals. SUMMARY

[0004] In view of the deficiencies in the prior art, the present application provides a method for cooperatively treating high-sulfur copper-containing hazardous waste and copper-containing solid waste, which solves the problem that the high-sulfur copper-containing hazardous waste is treated by fire method, and the low desulfurization rate leads to a large amount of copper matte, which is not conducive to the enrichment of heavy metals.

[0005] According to an embodiment of the present application, a method for cooperatively treating high-sulfur copper-containing hazardous waste and copper-containing solid waste comprises the following steps:

[0006] Step 1: mixing alkali copper carbonate waste and high-sulfur copper-containing hazardous waste material in a weight ratio of 1-1.2:4-6 to obtain mixed material one;

[0007] Step 2: pre-dehydrating the mixed material one by using a rotary dryer to obtain mixed material two;

[0008] Step 3: mixing the mixed material two and copper-containing solid waste material in a weight ratio of 3-4:1-1.5 to obtain mixed material three;

[0009] Step 4: mixing cement and soot in a weight ratio of 1:1-1.5 to obtain mixed material four;

[0010] Step 5: adding water accounting for 20-25% of the weight of the mixed material four to obtain mixed material five;

[0011] Step 6: Mix the mixture material three and the mixture material five in a weight ratio of 5-7:1-1.5 to obtain a mixture material six;

[0012] Step 7: After the mixture material six is processed by a brick machine and naturally air-dried, the brick material is obtained, and then the air-dried brick material, quartz stone and waste copper-plated steel wire are processed by a fire method in a weight ratio of 8-10:10-12:0.5-1.

[0013] Further, the soot includes coarse particle dust collected in the process of the fire method.

[0014] Further, 1-5% of calcium oxide is sprayed in the process of natural air-drying.

[0015] Further, the high-sulfur copper-containing hazardous waste material has a sulfur content of 40-50%.

[0016] Further, the high-sulfur copper-containing hazardous waste material includes sulfidation precipitation of electroplating wastewater.

[0017] Further, the copper-containing solid waste material includes waste circuit boards, waste cables and corner waste materials generated in copper processing.

[0018] Further, the waste copper-plated steel wire includes a grounding wire or a pin wire of an electronic component.

[0019] Further, the material has a water content of 15-20% after the pre-dehydration treatment.

[0020] Further, the natural air-drying time is 3-5 days.

[0021] Compared with the prior art, the present application has the following beneficial effects:

[0022] 1) By adding basic copper carbonate, the interaction between copper sulfide and cuprous oxide is increased, which is beneficial to the formation of crude copper, increases the desulfurization rate, and helps to improve the enrichment rate of high-value precious metals such as gold, silver, platinum and palladium in the sulfur-containing hazardous waste;

[0023] 2) By adding calcium oxide powder, it is beneficial to remove free water in the brick material, reduce the curing time of the brick material, and at the same time, by adding a small amount of calcium oxide, it helps to reduce the melting point of the slag and improve the fluidity of the slag in the process of the fire method, which helps to improve the enrichment rate of high-value precious metals such as gold, silver, platinum and palladium in the sulfur-containing hazardous waste;

[0024] 3) By adding copper-plated steel wire, not only iron is added, but also the copper plating layer on the surface is recovered, and in addition, the addition of iron is also beneficial to the formation of slag, thereby helping to improve the enrichment rate of high-value precious metals such as gold, silver, platinum and palladium in the sulfur-containing hazardous waste;

[0025] 4) By adding copper-containing solid waste, it is beneficial to the formation of blister copper, so that high-value precious metals such as gold, silver, platinum, and palladium in hazardous waste can be enriched in blister copper by 99%, increasing the added value of blister copper. DETAILED DESCRIPTION

[0026] The technical solutions in the present application are further described below in combination with examples.

[0027] Example 1

[0028] Step 1: Put 10t of basic copper carbonate waste and 40t of sulfurized sediment (sulfur content 40%) of electroplating wastewater into a mixing device (i.e. a disperser, the same below), and use a rotary dryer to pre-dehydrate the mixture to 15% to obtain mixture two;

[0029] Step 2: Add 15t of discarded circuit boards, discarded cables, and corner waste generated during copper processing to 40t of mixture two to obtain mixture three, wherein the copper grade is 95%;

[0030] Step 3: Mix cement and soot in a ratio of 4t of cement and 6t of soot (soot includes coarse particle dust collected during the pyroprocessing process) to obtain mixture four;

[0031] Step 4: Mix mixture four with water in a ratio of 25% of mixture four to obtain mixture five;

[0032] Step 5: Mix mixture three and five to obtain mixture six;

[0033] Step 6: Use a brick making machine to make bricks from mixture six, and then naturally air dry for 5 days, and spray 1% of calcium oxide during the natural air drying process;

[0034] Brick material main components: 39.10% Cu, 6.37% Fe, 8.11% CaO, 5.96% SiO2, 14.35% S;

[0035] Step 7: Put the dried brick material, quartz stone, and discarded copper-plated steel wire into an oxygen-enriched side-blown furnace for pyroprocessing in a ratio of 12t of quartz stone and 0.5t of discarded copper-plated steel wire, wherein the quartz stone grade SiO2 is 90%;

[0036] Product: 20.7t of blister copper is recovered, with a grade of 90%, 28.5t of matte is recovered, with a grade of 50%, and the slag contains 0.82% of copper; the precious metals are enriched in the blister copper, with a recovery rate of 99%.

[0037] Example 2

[0038] The embodiment provides a method for cooperatively treating high-sulfur copper-containing hazardous waste and copper-containing solid waste, which comprises the following steps.

[0039] Step 1: 11t of copper carbonate waste is mixed with 50t of sulfurized precipitation of electroplating wastewater (sulfur content 45%), and the mixture is pre-dehydrated to 18% by using a rotary dryer to obtain mixture two;

[0040] Step 2: 13t of discarded circuit boards, discarded cables and corner waste generated in copper processing are added into 35t of the mixture two to obtain mixture three with a grade of 92%;

[0041] Step 3: cement and flue ash are mixed in a proportion of 5t of cement and 5t of flue ash to obtain mixture four;

[0042] Step 4: mixture four is mixed with water in a proportion of 23% of the mixture four to obtain mixture five;

[0043] Step 5: mixture three and five are mixed to obtain mixture six;

[0044] Step 6: the mixture six is dried naturally for 4 days by using a brick making machine, and 3% of calcium oxide is sprayed in the process of natural drying;

[0045] Main components of the brick material: 42% Cu, 4.37% Fe, 9.02% CaO, 6.96% SiO2 and 10.35% S;

[0046] Step 7: the dried brick material, quartz stone and discarded copper-plated steel wire are put into an oxygen-enriched side-blown furnace for fire treatment in a proportion of 11t of quartz stone and 0.8t of discarded copper-plated steel wire, wherein the grade of SiO2 of the quartz stone is 85%;

[0047] Product: 21.4t of copper is recovered with a grade of 90%, 23.1t of matte is recovered with a grade of 54%, and the copper content of the slag is 0.7%; the noble metal is enriched in the copper, and the recovery rate is 99%.

[0048] Embodiment 3

[0049] Step 1: 12t of copper carbonate waste is mixed with 60t of sulfurized precipitation of electroplating wastewater (sulfur content 50%), and the mixture one is pre-dehydrated to 20% by using a rotary dryer to obtain mixture two;

[0050] Step 2: 10t of discarded circuit boards, discarded cables and corner waste generated in copper processing are added into 30t of the mixture two to obtain mixture three with a copper grade of 88%;

[0051] Step 3: cement and soot are mixed in a ratio of 4t cement and 4t soot (soot includes coarse particle dust collected in the process of fire treatment of flue gas), to obtain mixed material four;

[0052] Step 4: mixed material four is mixed with water in a ratio of 20% of mixed material four, to obtain mixed material five;

[0053] Step 5: mixed material three and five are mixed, to obtain mixed material six;

[0054] Step 6: mixed material six is made into bricks by a brick making machine, and then naturally air dried for 3 days, and 5% calcium oxide is sprayed in the process of natural air drying;

[0055] Main components of the brick material: 38.00% Cu, 10.31% Fe, 10.04% CaO, 7.15% SiO2, 17.12% S;

[0056] Step 7: the dried brick material, quartz stone and waste copper-plated steel wire are put into the oxygen-enriched side-blown furnace for fire treatment in a ratio of 10t quartz stone and 1t waste copper-plated steel wire, wherein the quartz stone has a grade of SiO2: 80%;

[0057] Product: 19.95t of crude copper is recovered with a grade of 90%, 22.6t of matte is recovered with a grade of 52%, and the slag contains 0.61% copper; noble metals are enriched in the crude copper, and the recovery rate is 99%.

[0058] Finally, it should be pointed out that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the purpose and scope of the present application, and all should be covered in the scope of the claims of the present application.

Claims

1. A method for the co-treatment of high-sulfur copper-containing hazardous waste and copper-containing solid waste, characterized in that, Includes the following steps: Step 1: Mix the basic copper carbonate waste and the high-sulfur copper-containing hazardous waste at a weight ratio of 1-1.2:4-6 to obtain mixture one; Step 2: Pre-dehydrate mixture one using a rotary dryer to obtain mixture two; Step 3: Mix mixture two and copper-containing solid waste material at a weight ratio of 3-4:1-1.5 to obtain mixture three; Step 4: Mix cement and soot at a weight ratio of 1:1-1.5 to obtain mixture four; Step 5: Add water (20-25% by weight) to mixture four and mix well to obtain mixture five; Step 6: Mix mixture three and mixture five in a weight ratio of 5-7:1-1.5 to obtain mixture six; Step 7: After the mixture of materials 6 is processed by a brick-making machine, it is naturally air-dried to obtain brick material. Then, the air-dried brick material, quartz stone and waste copper-plated steel strands are subjected to fire treatment in a weight ratio of 8-10:10-12:0.5-1.

2. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, Soot includes coarse particulate dust collected from flue gas during pyrometallurgical processes.

3. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, Spray 1-5% calcium oxide during the natural air drying process.

4. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, The sulfur content in high-sulfur copper-containing hazardous waste is 40-50%.

5. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, High-sulfur copper-containing hazardous waste materials include sulfide precipitation from electroplating wastewater.

6. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, Copper-containing solid waste includes discarded circuit boards, discarded cables, and scraps generated from copper processing.

7. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, Discarded copper-plated steel stranded wires include stranded grounding wires or lead wires of electronic components.

8. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 1, characterized in that, The moisture content of the material after pre-dehydration treatment is 15-20%.

9. The method for co-processing high-sulfur copper-containing hazardous waste and copper-containing solid waste as described in claim 3, characterized in that, Natural air drying time is 3-5 days.