A method for recovering copper from a silicone spent catalyst

Abstract

The application provides a method for recovering copper from silicone waste catalysts, comprising the following steps: step 1, mixing silicone waste catalysts with a binder and water, and making granular waste catalysts; step 2, mixing the granular waste catalysts with fuel materials, and then adding the mixture into a rotary kiln to perform calcination to obtain kiln residues after calcination; step 3, mixing the kiln residues, quicklime and waste copper with water, and making bricks; step 4, stacking the bricks, coke and copper-clad steel in a smelting furnace in sequence to perform rough smelting to obtain black copper; and step 5, placing the black copper into a refining furnace, introducing light fuel oil and liquid oxygen into the refining furnace, adding quartz sand after the black copper is completely melted to perform oxidation slagging, performing deslagging treatment on the surface of the copper liquid, adding a reducing agent to the copper liquid after the deslagging is completed, and obtaining crude copper after the reduction is completed, wherein the method has high copper recovery rate and is environment-friendly.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of solid waste resource recycling, and particularly relates to a method for recovering copper from organic silicon waste catalyst. BACKGROUND

[0002] The organic silicon waste catalyst (one kind of industrial waste residue) usually contains a large amount of silicon and copper, wherein the silicon content is about 65-75 wt%, the copper content is about 10-20 wt%, and in addition, it also contains a small amount of carbon (1-10 wt%) and zinc (0.2-2 wt%). With the continuous expansion of the production scale of organic silicon materials, the increasing amount of discharged organic silicon waste catalyst has brought serious pollution to the surrounding environment. In addition, since the organic silicon waste catalyst is fine dust, it is easy to catch fire in the air, so it also has a certain safety hazard. At present, the hazardous waste disposal company generally disposes the organic silicon waste catalyst by solidification landfill or cement kiln coordination, which causes waste of copper resources. At present, the copper in the organic silicon waste catalyst is mostly recovered by wet smelting. For example, the document No. CN116024431A "A method for extracting copper from organic silicon waste catalyst" discloses that after the organic silicon waste catalyst is slurried and inactivated, and then acid washed, an oxidizing agent is used for oxidation to prepare a copper-containing solution, and then a reducing agent is used to reduce the copper. This method needs to consume a large amount of acid for leaching, and also needs an oxidizing agent and a reducing agent for oxidation and reduction to obtain copper, which is easy to produce polluting liquid and cause serious environmental pollution. The method disclosed in the document No. CN114990334A "A method for recovering copper from organic silicon waste catalyst" also faces the same shortcomings. The method pretreats the organic silicon waste catalyst by water immersion, then performs acid leaching, and adds an oxidizing agent for reaction. After adjusting the acidity, electro-deposition is performed. Although the water washing reduces the amount of the oxidizing agent, the consumption of water resources, a large amount of acid and the use of the oxidizing agent still make the production cost not low, and polluting liquid is also produced. The method disclosed in the document No. CN112251608A "A method for resource utilization of organic silicon slurry residue and waste catalyst" uses hydrochloric acid for acid leaching, and adds iron powder for reduction to obtain sponge copper. This method has a low recovery rate of copper, and the copper content in the product is low, so the product has low value. The method disclosed in the document No. CN102795653B "A method for recovering copper oxide and zinc oxide from organic silicon waste catalyst" uses a combination of leaching and calcination to recover copper and zinc in the organic silicon waste catalyst. However, the process has a limited extraction rate, the zinc and copper cannot be completely separated in the precipitation process, and the copper and zinc are prone to co-precipitation. SUMMARY

[0003] In order to solve the above technical problems, the purpose of the present application is to provide a method for recovering copper from organic silicon waste catalyst, which does not need to use acid and alkali liquid, does not produce waste liquid, and has a high recovery rate of copper.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows: A method for recovering copper from waste organosilicon catalysts, comprising the following steps:

[0005] Step 1: Mix the organosilicon waste catalyst and adhesive with water to form granular waste catalyst;

[0006] Step 2: Mix the granular waste catalyst with the fuel and then add it to the rotary kiln for calcination to obtain the kiln slag remaining after calcination;

[0007] Step 3: Mix kiln slag, quicklime, and scrap copper with water and form into bricks;

[0008] Step 4: Stack bricks, coke, and copper-clad steel in a smelting furnace in sequence for rough refining to obtain black copper;

[0009] Step 5: Place the black copper in a refining furnace, and introduce light fuel oil and liquid oxygen into the refining furnace. After the black copper is completely melted, add quartz sand to oxidize and slag, and remove the slag from the surface of the copper liquid. After the slag removal is completed, add a reducing agent to reduce the copper liquid. After the reduction is completed, crude copper is obtained.

[0010] In the above technical solution, the adhesive in step 1 is quicklime, and the amount of adhesive added is 0.5-2wt% of the amount of organosilicon waste catalyst added. The amount of water added in step 1 is 1-2wt% of the total amount of organosilicon waste catalyst and adhesive added.

[0011] The particle size of the granular waste catalyst in step 1 of the above technical solution is 10-15 mm.

[0012] In step 2 of the above technical solution, the fuel material includes waste resin and / or waste oil, and the calorific value of the fuel material is 3000-5000 kcal / kg.

[0013] The amount of fuel added in the above technical solution is 2-3.5 times the total copper content in the organosilicon waste catalyst.

[0014] In step 2 of the above technical solution, the temperature of the rotary kiln reaction zone is 900-1100℃; the excess air coefficient is 1.1-1.4; and the residence time of the granular waste catalyst in the rotary kiln is 30-60 minutes.

[0015] In step 3 of the above technical solution, the amount of quicklime added is 11-13 wt% of the total amount of kiln slag and scrap copper; the moisture content of the bricks is 10-15 wt%; and the copper content of the bricks is 15-25 wt%.

[0016] The waste copper mentioned in the above technical solution is at least one of waste copper powder, waste copper slag, and waste copper blocks.

[0017] In step 4 of the above technical solution, the amount of coke added is 0.4-0.8 times the total amount of black copper obtained, and the amount of copper-clad steel added is 0.012-0.018 times the total amount of black copper obtained.

[0018] In the above technical solution, the amount of light fuel oil added in step 5 is 0.03-0.05 times the total amount of crude copper obtained, the amount of liquid oxygen added is 0.08-0.12 times the total amount of crude copper obtained, and the amount of quartz sand added is 0.02-0.05 times the total amount of crude copper obtained; the reducing agent is carbon concentrate, and the amount of reducing agent added is 0.01-0.02 times the total amount of crude copper obtained.

[0019] The beneficial effects of this invention are as follows: This embodiment uses a resource-based approach to recover metallic copper from waste organosilicon catalysts, avoiding the direct incineration of the waste organosilicon catalysts in rotary kilns and cement kilns at high temperatures, which wastes copper resources. Furthermore, this embodiment can obtain higher purity crude copper products (copper content as high as 97wt%), improving the recovery rate of metallic copper from waste organosilicon catalysts. In the roughing stage, during the feeding process, the furnace body is semi-enclosed by the material, while maintaining a slight negative pressure inside the furnace. The enclosed furnace body reduces heat loss and the emission of feed exhaust gas, reduces the amount of carbon concentrate to be disposed of, and increases the smelting capacity per unit furnace bed. The impurities in the kiln slag are mainly silicon, iron, and calcium. To effectively remove these impurities, a certain amount is added during the brick-making process. Quicklime is used to form slag and react with iron oxides to generate high-melting-point complexes, preventing deoxidation and reduction reactions at smelting temperatures. This more effectively removes impurities and improves the purity of the crude copper product. In the refining process, the small amount of impurities in black copper mainly exists in the form of Cu2S. Towards the end of the oxidation stage, it reacts with cuprous oxide and releases SO2 gas. At the end of the oxidation stage, although the impurity content in the melt decreases, the oxygen content increases, requiring reduction. During the reduction operation, fuel supply is stopped, but combustion air continues to be supplied. A reducing agent (carbon concentrate) is added to maintain the reducing atmosphere in the furnace and remove oxygen from the copper. The final oxygen content after reduction is generally controlled at 0.1-0.2 wt%, and the copper content in the final crude copper product is as high as 97 wt% or more.

[0020] (2) In this embodiment, pyrometallurgical smelting is used to recover metallic copper from organosilicon waste catalyst. Compared with acid-base method and recovery method combining pyrometallurgical calcination and acid leaching, this embodiment does not require the use of acid or base substances and does not produce any polluting liquids. The flue gas discharged during rotary kiln combustion is treated to render it harmless before being discharged. Detailed Implementation

[0021] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0022] The present application provides a method for recovering copper from silicone waste cathode, comprising the following steps:

[0023] Step 1: mixing silicone waste cathode with adhesive and water to make granular waste cathode;

[0024] Step 2: mixing the granular waste cathode with fuel and then adding it into a rotary kiln to burn to obtain kiln residue after burning;

[0025] Step 3: mixing the kiln residue, quicklime and waste copper with water to make bricks;

[0026] Step 4: stacking the bricks, coke and copper-clad steel in the smelting furnace in turn to obtain black copper by rough smelting;

[0027] Step 5: placing the black copper in a refining furnace, introducing light fuel oil and liquid oxygen into the refining furnace, adding quartz sand (as a metallurgical flux) after the black copper is completely melted to oxidize and form slag, removing the slag on the surface of the copper liquid, adding a reducing agent to reduce the copper liquid after the slag removal is completed, and obtaining crude copper after the reduction is completed.

[0028] In step 1, the adhesive is quicklime, and the addition amount of the adhesive is 0.5-2wt% (which can be any value or a range between any two values of 0.5wt%, 1wt%, 1.5wt% and 2wt%, and preferably 1wt%) of the addition amount of the silicone waste cathode. The addition amount of water in step 1 is 1-2wt% (which can be any value or a range between any two values of 1wt%, 1.5wt% and 2wt%, and preferably 2wt%) of the total addition amount of the silicone waste cathode and the adhesive. The purpose of adding water in step 1 is mainly to make the quicklime form a slurry to mix with the silicone waste cathode to form a soft mud, which is then constrained by a ball making machine to form a granular waste cathode (spherical particles) with a diameter of 10-15mm (which can be any value or a range between any two values of 10mm, 13mm and 15mm, or as long as the particle size of the granular waste cathode falls within 10-15mm, or as long as the particle size of more than 80% of the granular waste cathode falls within 10-15mm).

[0029] The fuel material in step 2 includes waste resin (recycled waste resin such as waste ion exchange resin or waste Dow resin, but not limited thereto) and / or waste oil (waste lubricating oil or waste hydraulic oil, etc., but not limited thereto), and the heat value of the fuel material is 3000-5000 kcal / kg (any one value or a range between any two values of 3000 kcal / kg, 4000 kcal / kg and 5000 kcal / kg), and the addition amount of the fuel material is 2-3.5 times (any one value or a range between any two values of 2 times, 2.5 times, 3 times and 3.5 times) of the total copper content in the silicone waste contact mass (i.e., the weight of copper element in the added silicone waste contact mass).

[0030] In step 2, the temperature of the rotary kiln reaction zone is 900-1100°C (any one value or a range between any two values of 900°C, 1000°C and 1100°C); the air excess coefficient is 1.1-1.4 (any one value or a range between any two values of 1.1, 1.2, 1.3 and 1.4), and the residence time of the granular waste contact mass in the rotary kiln is 30-60 min (any one value or a range between any two values of 30 min, 40 min, 50 min and 60 min).

[0031] In step 3, the addition amount of quicklime is 11-13 wt% (any one value or a range between any two values of 11 wt%, 12 wt% and 13 wt%) of the total addition amount of kiln slag and waste copper; the water content of the brick is 10-15 wt% (any one value or a range between any two values of 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt%); and the copper content of the brick is 15-25 wt% (any one value or a range between any two values of 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt% and 25 wt%).

[0032] The waste copper (mainly recycled waste copper) is at least one of waste copper powder, waste copper slag and waste copper block.

[0033] In step 4, the addition amount of coke is 0.4-0.8 times (any one value or a range between any two values of 0.4 times, 0.5 times, 0.6 times, 0.7 times and 0.8 times) of the total amount of black copper, and the addition amount of copper-coated steel is 0.012-0.018 times (any one value or a range between any two values of 0.012 times, 0.014 times, 0.016 times and 0.018 times) of the total amount of black copper.

[0034] The light fuel oil (which can be one or mixture of gasoline, diesel and kerosene, but not limited to) in step 5 is added in an amount of 0.03-0.05 times (which can be any one of 0.03 times, 0.04 times and 0.05 times or a range between any two values) of the total amount of the obtained crude copper, the liquid oxygen is added in an amount of 0.08-0.12 times (which can be any one of 0.08 times, 0.1 times and 0.12 times or a range between any two values) of the total amount of the obtained crude copper, the quartz sand is added in an amount of 0.02-0.05 times (which can be any one of 0.02 times, 0.03 times, 0.04 times and 0.05 times or a range between any two values) of the total amount of the obtained crude copper; the reducing agent is carbon powder, and the reducing agent is added in an amount of 0.01-0.02 times (which can be any one of 0.01 times, 0.015 times and 0.02 times or a range between any two values) of the total amount of the obtained crude copper.

[0035] Due to the large difference in the composition of the organic silicon waste anode, the content of copper, silicon, zinc and carbon fluctuates within a certain range, so the addition amount of various materials in the above specific embodiments is mostly a range value. If the value is greater than the corresponding range value, it is easy to cause waste of materials and energy and increase production cost. If the value is less than the corresponding range value, it is easy to cause insufficient reaction of materials, decrease of copper extraction rate and decrease of copper purity in the product, etc.

[0036] Example 1

[0037] The embodiment provides a method for recovering copper from a silicone waste catalyst, step 1: 1 t of the silicone waste catalyst (the copper content is about 16 wt%) is uniformly mixed with 10 kg of quicklime, after mixing, 20 kg of water is added and stirring is continued until uniform, and then the granular waste catalyst with a diameter of 10-15 mm is constrained by a ball making machine; step 2: the obtained granular waste catalyst is mixed with 300 kg of fuel material (including waste resin and waste oil) and then added into a rotary kiln, under the condition that the reaction zone is 900-1100 DEG C, the carbon and zinc in the material enter the flue gas and move to the kiln tail, the copper compound in the material is oxidized into copper oxide, the silicon powder is oxidized into silicon dioxide, and the kiln slag moves to the kiln head (the kiln slag can be discharged at the kiln head and cooled by water, or can be naturally cooled), and the residence time of the granular waste catalyst in the rotary kiln can be set to 40 min; step 3: the kiln slag is mixed with 130 kg of quicklime and 200 kg of waste copper (waste copper powder, waste copper slag or waste copper powder), and then sent into a stirrer for stirring, in the stirring process, 150 kg of water is added to facilitate subsequent brick making, after the stirring is completed, the mixture is sent to a brick making machine through a closed belt conveyor, and 24 cm*12 cm*6 cm brick blocks are made by the brick making machine; step 4: the copper-containing material after brick making, 250 kg of coke and 6.0 kg of copper-coated steel are sequentially stacked into a smelting furnace, the furnace body is ignited, and smelting is performed, the rough smelting furnace is continuously produced, and it takes about 2 hours from feeding to the outflow of black copper; step 5: after the rough smelting is completed, the copper in the smelting furnace mainly exists in the form of molten liquid metal at the bottom, a discharge port is arranged at the bottom of the smelting furnace, the black copper with a grade of about 70 wt% is intermittently discharged into a copper ladle through a chute, and the black copper blocks are cooled and then added into a refining furnace for further refining; the cooled black copper is transferred into the refining furnace through a material car, 14 kg of light fuel oil and 36 kg of liquid oxygen are introduced, the melting time is about 8 h, part of impurities starts to oxidize and volatilize in the melting process, and slag is generated on the surface of the melt, after the copper is completely melted and the slag is removed, compressed air is introduced into the molten copper through a bent air pipe to oxidize and form slag, 15 kg of quartz sand is added during the slag forming, and the oxidation time is about 7 h, after the oxidation and slag forming are completed, the slag on the surface of the copper liquid is removed, after the slag is completely removed, 5 kg of a reducing agent (carbon powder) is sent into the copper liquid through the bent air pipe for reduction, after the reduction is completed, casting is performed, and finally, coarse copper blocks are obtained, the copper content of the product coarse copper blocks is measured according to the method specified in YS / T 521.1-2009 “Chemical Analysis Method of Coarse Copper Determination of Copper Content”, and through detection and calculation, the copper content in the product is 98.1 wt%.

[0038] Embodiment 2

[0039] The difference between the example 1 is that the copper content of the silicone waste anode is about 19.5wt%, the adding amount of fuel material in step 1 is 450kg, the residence time of the silicone waste anode in the rotary kiln in step 2 is 60min, the adding amount of quicklime in step 3 is 140kg, the adding amount of waste copper scrap is 250kg, the adding amount of water in the stirring is 200kg, the adding amount of coke in step 4 is 300kg, the adding amount of copper clad steel is 7.0kg, the adding amount of light fuel oil in step 5 is 20kg, the adding amount of liquid oxygen is 40kg, the adding amount of quartz sand is 18kg, and the adding amount of reducing agent is 7.5kg. The copper content of the product blister copper block is determined according to the method specified in YS / T 521.1-2009 "Determination of Copper Content in Blister Copper Chemical Analysis Method", and the copper content in the product is 98.5wt% after detection and calculation.

[0040] Example 3

[0041] The difference between the example 1 is that the copper content of the silicone waste anode is about 19.5wt%, the adding amount of fuel material in step 1 is 450kg, the residence time of the silicone waste anode in the rotary kiln in step 2 is 60min, the adding amount of quicklime in step 3 is 140kg, the adding amount of waste copper scrap is 250kg, the adding amount of water in the stirring is 200kg, the adding amount of coke in step 4 is 300kg, the adding amount of copper clad steel is 7.0kg, the adding amount of light fuel oil in step 5 is 20kg, the adding amount of liquid oxygen is 40kg, the adding amount of quartz sand is 18kg, and the adding amount of reducing agent is 7.5kg. The copper content of the product blister copper block is determined according to the method specified in YS / T 521.1-2009 "Determination of Copper Content in Blister Copper Chemical Analysis Method", and the copper content in the product is 98.5wt% after detection and calculation.

[0042] The flue gas of the rotary kiln, the flue gas of the rough smelting furnace and the flue gas of the fine smelting furnace in each of the above examples can be subjected to environmental protection treatment. For example, the flue gas of the rotary kiln can be sequentially subjected to waste heat boiler (waste heat recovery), surface cooling, bag dust removal and desulfurization system before being discharged. The flue gas of the rough smelting furnace and the flue gas of the fine smelting furnace can be subjected to bag dust removal and flue gas desulfurization treatment before being discharged (the flue gas treatment method belongs to the prior art in the art, and will not be described here).

[0043] The above embodiments of the present application are described in detail, and the principles and implementation modes of the present application are described by applying specific examples. The above embodiment description is only used to help understand the method of the present application and its core idea; meanwhile, for those skilled in the art, the specific implementation mode and application range can be changed according to the idea of the present application. In summary, the content of the specification should not be understood as a limitation of the present application.

Claims

1. A method for recovering copper from a spent organosilicon catalyst, characterized by, The method comprises the following steps: Step 1: mixing the silicone waste catalyst with the binder and water, and making granular waste catalyst; Step 2: mixing the granular waste catalyst with fuel materials, and feeding into a rotary kiln for incineration to obtain kiln residue after incineration; Step 3: mixing the kiln residue, quicklime and waste copper with water, and making bricks; Step 4: stacking the bricks, coke and copper-clad steel in the smelting furnace in sequence to obtain black copper after rough smelting; Step 5: placing the black copper in a refining furnace, feeding light fuel oil and liquid oxygen into the refining furnace, adding quartz sand after the black copper is completely melted to oxidize and form slag, removing the slag on the surface of the copper liquid, adding a reducing agent to reduce the copper liquid, and obtaining crude copper after reduction.

2. The method of recovering copper from a silicone spent catalyst according to claim 1, wherein In step 1, the binder is quicklime, and the addition amount of the binder is 0.5-2wt% of the addition amount of the silicone waste catalyst; in step 1, the addition amount of water is 1-2wt% of the total addition amount of the silicone waste catalyst and the binder.

3. The method of recovering copper from a silicone spent catalyst according to claim 1, wherein In step 1, the particle size of the granular waste catalyst is 10-15mm.

4. The method of recovering copper from a silicone spent catalyst according to claim 1, wherein In step 2, the fuel materials include waste resin and / or waste oil, and the calorific value of the fuel materials is 3000-5000kcal / kg.

5. The method of recovering copper from a silicone spent catalyst according to claim 4, wherein The addition amount of the fuel materials is 2-3.5 times of the total copper content in the silicone waste catalyst.

6. The method of recovering copper from a silicone spent catalyst according to claim 4, wherein In step 2, the temperature of the rotary kiln reaction zone is 900-1100℃, the air excess coefficient is 1.1-1.4, and the residence time of the granular waste catalyst in the rotary kiln is 30-60min.

7. The method of recovering copper from a silicone spent catalyst according to claim 1, wherein In step 3, the addition amount of quicklime is 11-13wt% of the total addition amount of the kiln residue and the waste copper; the water content of the bricks is 10-15wt%; and the copper content of the bricks is 15-25wt%.

8. The method of recovering copper from a silicone spent catalyst according to claim 7, wherein The waste copper is at least one of waste copper powder, waste copper slag and waste copper block.

9. The method of recovering copper from a silicone spent catalyst according to claim 1, wherein In step 4, the addition amount of coke is 0.4-0.8 times of the total amount of the obtained black copper, and the addition amount of copper-clad steel is 0.012-0.018 times of the total amount of the obtained black copper.

10. The method of recovering copper from a silicone spent catalyst according to claim 1, wherein In step 5, the addition amount of light fuel oil is 0.03-0.05 times of the total amount of the obtained crude copper, the addition amount of the liquid oxygen is 0.08-0.12 times of the total amount of the obtained crude copper, and the addition amount of the quartz sand is 0.02-0.05 times of the total amount of the obtained crude copper; the reducing agent is carbon powder, and the addition amount of the reducing agent is 0.01-0.02 times of the total amount of the obtained crude copper.