CN110980794A - By using SiO2Method for preparing high-purity copper chloride dihydrate by regulating and controlling copper-containing sludge - Google Patents
By using SiO2Method for preparing high-purity copper chloride dihydrate by regulating and controlling copper-containing sludge Download PDFInfo
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- CN110980794A CN110980794A CN201911189660.8A CN201911189660A CN110980794A CN 110980794 A CN110980794 A CN 110980794A CN 201911189660 A CN201911189660 A CN 201911189660A CN 110980794 A CN110980794 A CN 110980794A
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Abstract
The invention belongs to the technical field of solid waste treatment and discloses a method for utilizing SiO2A method for preparing high-purity copper chloride dihydrate by regulating and controlling copper-containing sludge. Drying, grinding and sieving the copper-containing sludge, adding SiO into the copper-containing sludge according to a certain proportion2And hydrochloric acid, and stirring uniformly; roasting the obtained mixture in a flowing air atmosphere at the temperature of 700-1200 ℃, volatilizing the product and condensing to obtain CuCl2·2H2And O. By using the method, 95-97% of copper in the copper-containing sludge can be recovered, and the purity of the prepared product is about 95%. The method has simple process, little secondary pollution and high product application value, is a great breakthrough in the technical field of heavy metal waste residue recycling, overcomes the problems of complex process, high cost, great secondary pollution and the like of the copper extraction technology of the copper-containing sludge, and is the copper chloride dihydrateThe preparation and the recovery of heavy metals from other heavy metal waste residues provide a new idea, and the environmental and economic benefits are obvious.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for treating solid waste by using SiO2Regulating and controlling copper-containing sludge preparation heightA method for purifying copper chloride dihydrate.
Background
The copper-containing sludge is listed in national hazardous waste records (HW22) due to high heavy metal content, the average copper content is generally 3-7%, and some copper content is even more than 15%, and the copper-containing sludge is essentially electroplating sludge with high copper content. The method for recovering the copper in the copper-containing sludge has great significance from the viewpoint of environmental protection and sustainable development.
Chinese patent "an energy-saving and environment-friendly smelting method of copper-containing sludge" (CN201910688422.5) is to mix and granulate copper-containing sludge, lime and anthracite, add limestone coke and the like after sintering for reduction smelting, and finally obtain black copper or matte products. The method needs to carry out multi-step pretreatment on the copper-containing sludge, also needs to use a large amount of coke for high-temperature smelting, and has a complex treatment process. In the Chinese patent "method for producing electroplating-grade copper sulfate from copper-containing sludge" (CN201810780164.9), a large amount of acid liquor is used for leaching the copper-containing sludge, and copper sulfate is finally prepared through the steps of precipitation for impurity removal, extraction, back extraction, evaporation and concentration, and the method inevitably brings about the discharge of a large amount of acidic wastewater.
The application group is inspired by the application of the chloridizing roasting process to slag metallurgy research, develops a technology for extracting heavy metal by chloridizing roasting of electroplating sludge, and discloses a technology for recovering copper and nickel in sludge in a roasting and water-adding soaking mode under a reducing atmosphere in a patent of 'a method for selectively recovering heavy metal in electroplating sludge by using chloridizing roasting method' (CN 201811442392.1). However, one of the main phases of electroplating sludge is calcium carbonate, and the chlorination process generates intermediate CaCl2The utilization rate of chloride ions is reduced, so that the extraction efficiency of copper is influenced; and the partial dissolution of calcium chloride in the process affects the purity of the product. In addition, the copper recovery needs to be carried out in the solution, and an additional step of dissolving metal ions is also needed to obtain a metal mixed solution of copper and nickel, which is also a difficult problem for the separation of copper and nickel and the treatment of the wastewater after the recovery.
Disclosure of Invention
In order to overcome the defects of high energy consumption and high energy consumption in the prior artThe invention aims to provide a method for utilizing SiO to solve the problems of insufficient secondary pollution and the like and low purity of copper chloride product2A method for preparing high-purity copper chloride dihydrate by regulating and controlling copper-containing sludge. The method for treating the copper-containing sludge can realize short-flow and high-efficiency copper recovery, has lower energy consumption than that of a common pyrogenic process treatment method, realizes resource utilization of the sludge, and simultaneously provides a new idea for preparation of copper chloride hydrate and recovery of heavy metals from other heavy metal waste residues. In addition, the copper chloride has wide application and high economic value, and can greatly reduce the treatment of hazardous waste and the production cost by directly recycling the copper chloride in the electroplating process.
The purpose of the invention is realized by the following technical scheme:
a method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge comprises the following steps:
(1) drying, grinding and sieving the copper-containing sludge, adding SiO into the copper-containing sludge according to a certain proportion2And hydrochloric acid, and stirring uniformly;
(2) roasting the mixture obtained in the step (1) in a flowing air atmosphere at the temperature of 700-1200 ℃, volatilizing the product and condensing to obtain CuCl2·2H2O。
Further, the drying, grinding and sieving in the step (1) means drying at 105 ℃ for 10-12 hours, and grinding and sieving with a 100-mesh sieve.
Further, the copper-containing sludge in the step (1) refers to copper-containing sludge with the copper content of not less than 3% by mass.
Further, the hydrochloric acid in the step (1) refers to concentrated hydrochloric acid with the mass fraction of 36%.
Further, the sludge containing copper and SiO in the step (1)2The mass ratio of (A) to (B) is 1: 0.1-0.5.
Preferably, the copper-containing sludge in the step (1) is mixed with SiO2The mass ratio of (A) to (B) is 1: 0.1.
Further, the mass ratio of the copper-containing sludge to the hydrochloric acid in the step (1) is 1 (1-2).
Further, the roasting treatment in the step (2) is carried out in a roasting system comprising an air inlet and an air outlet; the roasting system comprises a central heating zone and a low-temperature condensation zone.
Furthermore, the roasting system is a tube furnace with a built-in quartz tube, an air inlet and an air outlet are respectively connected to two ends of the quartz tube, and the air outlet is connected with a gas washing bottle for tail gas absorption; the middle part of the quartz tube is a heating area, and the two ends are low-temperature condensation areas; the flow velocity of the air atmosphere flowing in the roasting treatment process in the quartz tube is 5-10 m/min.
Further, the temperature rise rate of the roasting treatment in the step (2) is 5-10 ℃/min.
Further, the roasting temperature in the step (2) is 800-1000 ℃, and the roasting time is 60-120 min.
The principle of the invention is as follows: the copper-containing sludge contains metal impurities such as nickel, iron and the like, and calcium carbonate and calcium chromate in phases, besides copper. The solid-liquid reaction is more thorough than the solid-solid reaction, and the CuCl is favorably reduced under the condition of moisture2The volatile chemical reaction activation energy, concentrated hydrochloric acid is selected as the chlorinating agent for the reaction instead of the chloride salt in the previous application. Hydrochloric acid can react with copper-containing phases Cu (OH)2The reaction generates target products, and the crystal phase structures of calcium carbonate and calcium chromate are destroyed to release the entrapped copper ions, so that the copper ions are chlorinated. Chromium is volatilized at low temperature below 400 ℃ namely chlorination, and under the action of high temperature (generally above 700 ℃ and 800 ℃) and flowing air, the target product copper chloride is volatilized and condensed in a low-temperature region of the tube furnace. Oxygen in the air can promote the conversion of iron chloride to oxide ferroferric oxide, so that the influence on the purity of the product is avoided. The greater gas velocity (at least 5m/min) has a pumping action which advantageously reduces the partial pressure of the gaseous phase of the copper chloride volatiles, thereby promoting their volatilization and rapidly carrying the copper chloride away from the heated zone for early cooling. Added SiO2Has main regulation and control effect on the transformation of calcium-containing phase and can promote the chlorinated intermediate product CaCl2To more stable CaSiO3Converting and releasing chloride ions, thereby improving the utilization efficiency of the chloride ions, and simultaneously SiO2Also has the effect of reducing the activation energy of the chlorination reaction, and SiO2Without bringing new cations to contaminate the chlorinated product. In addition, studies have shown thatThe more main factor influencing the purity of copper chloride and the recovery rate of copper is the heating temperature, the high purity degree of about 95 percent is required, and the reaction temperature is at least above 800 ℃. Certainly, the reaction temperature cannot be too high, the recovery rate of copper is not obviously improved to exceed a certain degree, but energy is wasted, the economic benefit is comprehensively considered, the reaction temperature is limited below 1200 ℃, and the optimal reaction temperature is between 800 ℃ and 1000 ℃.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the method has short flow and easy operation, and the SiO is used2The regulation and control function can save the usage amount of the chlorinating agent; and SiO introduced2No new cationic pollution is brought.
(2) The method can shorten the flow of the traditional pyrogenic process sludge copper extraction technology, only needs roasting and cooling, does not need additional steps such as dissolution and the like, saves a large amount of reaction raw materials, and reduces energy consumption.
(3) The method is carried out in a relatively closed system, so that the secondary pollution of the flue gas is reduced to the maximum extent.
Drawings
FIG. 1 is an SEM photograph of copper chloride dihydrate obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) The copper-containing sludge is placed in an oven, dried for 12 hours at 105 ℃, ground and sieved by a 100-mesh sieve. 2g of dried sludge containing copper are taken and added with 3.0ml of 36 wt.% concentrated hydrochloric acid and 0.2g of SiO2Fully and uniformly stirring.
(2) Placing the uniformly stirred mixture in a tube furnace (quartz tube is arranged in the tube furnace, an air inlet and an air outlet are respectively connected with two ends of the quartz tube, the middle part of the quartz tube is a heating region, two ends are low-temperature condensation regions, the air outlet is connected with a gas washing bottle for tail gas absorption), and then, introducing air with the flow speed of 6m/minHeating to 700 ℃ at a heating rate of 10 ℃/min in the atmosphere, roasting for 120min, cooling, and recovering the product CuCl in a low-temperature condensation zone of a tubular furnace2·2H2O, calculated copper recovery efficiency was 86.62%.
Example 2
(1) The copper-containing sludge is placed in an oven, dried for 10 hours at 105 ℃, ground and sieved by a 100-mesh sieve. 2g of dried sludge containing copper are taken and added with 3.0ml of 36 wt.% concentrated hydrochloric acid and 0.2g of SiO2Fully and uniformly stirring.
(2) Placing the uniformly stirred mixture in a tube furnace (a quartz tube is arranged in the tube furnace, an air inlet and an air outlet are respectively connected with two ends of the quartz tube, the middle part of the quartz tube is a heating region, two ends of the quartz tube are low-temperature condensation regions, an air outlet is connected with a gas washing bottle for tail gas absorption), heating to 800 ℃ at a heating rate of 10 ℃/min under an air atmosphere with a flow rate of 5m/min, roasting for 60min, cooling, and recovering a product CuCl in the low-temperature condensation region of the tube furnace2·2H2O, calculated copper recovery efficiency 96.80%, purity 95.61% as measured by indirect sodium thiosulfate titration.
The SEM image of the copper chloride dihydrate product obtained in this example is shown in FIG. 1. The crystal appearance is a columnar structure. An XRD spectrum shows that the main phase of the product prepared by the method is CuCl with two crystal waters2EDS spectra further demonstrate that the atomic ratio of copper to chlorine matches a 1:2 ratio.
Example 3
(1) The copper-containing sludge is placed in an oven, dried for 10 hours at 105 ℃, ground and sieved by a 100-mesh sieve. 4g of dried sludge containing copper are taken and added with 4.0ml of 36 wt.% concentrated hydrochloric acid and 0.4g of SiO2Fully and uniformly stirring.
(2) Placing the uniformly stirred mixture into a tube furnace (a quartz tube is arranged in the tube furnace, an air inlet and an air outlet are respectively connected with two ends of the quartz tube, the middle part of the quartz tube is a heating area, two ends of the quartz tube are low-temperature condensation areas, an air outlet is connected with a gas washing bottle for tail gas absorption), heating to 800 ℃ at a heating rate of 10 ℃/min under an air atmosphere with a flow rate of 6m/min, roasting for 120min, and recovering a product CuCl in the low-temperature condensation area of the tube furnace after cooling2·2H2O, calculated copper recovery efficiency 95.20%, 94.65% purity as measured by sodium thiosulfate indirect titration.
Example 4
(1) The copper-containing sludge is placed in an oven, dried for 12 hours at 105 ℃, ground and sieved by a 100-mesh sieve. 2g of dried sludge containing copper are taken and added with 3.5ml of 36 wt.% concentrated hydrochloric acid and 0.2g of SiO2Fully and uniformly stirring.
(2) Placing the uniformly stirred mixture in a tube furnace (a quartz tube is arranged in the tube furnace, an air inlet and an air outlet are respectively connected with two ends of the quartz tube, the middle part of the quartz tube is a heating region, two ends of the quartz tube are low-temperature condensation regions, an air outlet is connected with a gas washing bottle for tail gas absorption), heating to 900 ℃ at a heating rate of 10 ℃/min under an air atmosphere with a flow rate of 6m/min, roasting for 60min, cooling, and recovering a product CuCl in the low-temperature region of the tube furnace2·2H2O, calculated copper recovery efficiency 96.70%, 95.60% purity by indirect sodium thiosulfate titration.
Example 5
(1) The copper-containing sludge is placed in an oven, dried for 10 hours at 105 ℃, ground and sieved by a 100-mesh sieve. 2g of dried sludge containing copper are taken and added with 3.0ml of 36 wt.% concentrated hydrochloric acid and 0.2g of SiO2Fully and uniformly stirring.
(2) Placing the uniformly stirred mixture into a tube furnace (a quartz tube is arranged in the tube furnace, an air inlet and an air outlet are respectively connected with two ends of the quartz tube, the middle part of the quartz tube is a heating region, two ends of the quartz tube are low-temperature condensation regions, an air outlet is connected with a gas washing bottle for tail gas absorption), heating to 1000 ℃ at a heating rate of 10 ℃/min under an air atmosphere with a flow rate of 6m/min, roasting for 60min, cooling, and recovering a product of high-purity nano CuCl in the low-temperature condensation region of the tube furnace2·2H2O, calculated copper recovery efficiency 97.19%, and a purity of 95.52% as measured by indirect sodium thiosulfate titration.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge is characterized by comprising the following steps:
(1) drying, grinding and sieving the copper-containing sludge, adding SiO into the copper-containing sludge according to a certain proportion2And hydrochloric acid, and stirring uniformly;
(2) roasting the mixture obtained in the step (1) in a flowing air atmosphere at the temperature of 700-1200 ℃, volatilizing the product and condensing to obtain CuCl2·2H2O。
2. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the drying, grinding and sieving in the step (1) means drying at 105 ℃ for 10-12 h, and grinding and sieving by a 100-mesh sieve.
3. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the copper-containing sludge in the step (1) refers to copper-containing sludge with the copper content of not less than 3% by mass.
4. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the hydrochloric acid in the step (1) is concentrated hydrochloric acid with the mass fraction of 36%.
5. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the copper-containing sludge and SiO in the step (1)2The mass ratio of (A) to (B) is 1: 0.1-0.5.
6. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the mass ratio of the copper-containing sludge to the hydrochloric acid in the step (1) is 1 (1-2).
7. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the roasting treatment in the step (2) is carried out in a roasting system comprising an air inlet and an air outlet; the roasting system comprises a central heating zone and a low-temperature condensation zone.
8. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 7, wherein the method comprises the following steps: the roasting system is a tube furnace with a built-in quartz tube, an air inlet and an air outlet are respectively connected to two ends of the quartz tube, and the air outlet is connected with a gas washing bottle for tail gas absorption; the middle part of the quartz tube is a heating area, and the two ends are low-temperature condensation areas; the flow velocity of the air atmosphere flowing in the roasting treatment process in the quartz tube is 5-10 m/min.
9. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: and (3) the temperature rise rate of the roasting treatment in the step (2) is 5-10 ℃/min.
10. The method for preparing high-purity copper chloride dihydrate by using SiO2 to regulate and control copper-containing sludge according to claim 1, characterized in that: the temperature of the roasting treatment in the step (2) is 800-1000 ℃, and the roasting treatment time is 60-120 min.
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Citations (3)
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| CN109234540A (en) * | 2018-11-15 | 2019-01-18 | 湖南锐异资环科技有限公司 | A kind of method of copper ashes and electroplating sludge collaboration processing recycling valuable metal |
| CN109280777A (en) * | 2018-11-29 | 2019-01-29 | 华南理工大学 | A kind of method of heavy metal in chlorinating roasting selective recovery electroplating sludge |
| CN109554536A (en) * | 2018-11-23 | 2019-04-02 | 华南理工大学 | A kind of device and method of vacuum chloridising roasting processing heavy metal dangerous waste |
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- 2019-11-28 CN CN201911189660.8A patent/CN110980794A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109234540A (en) * | 2018-11-15 | 2019-01-18 | 湖南锐异资环科技有限公司 | A kind of method of copper ashes and electroplating sludge collaboration processing recycling valuable metal |
| CN109554536A (en) * | 2018-11-23 | 2019-04-02 | 华南理工大学 | A kind of device and method of vacuum chloridising roasting processing heavy metal dangerous waste |
| CN109280777A (en) * | 2018-11-29 | 2019-01-29 | 华南理工大学 | A kind of method of heavy metal in chlorinating roasting selective recovery electroplating sludge |
Non-Patent Citations (1)
| Title |
|---|
| LIU JIAN,ET AL: "Process Optimization and Reaction Mechanism of Removing Copper From an Fe-Rich Pyrite Cinder Using Chlorination Roasting", 《JOURNAL OF IRON AND STEEL RESEARCH INTERNATIONAL》 * |
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