CN211497743U - Device for extracting copper through deep replacement under multi-field coupling - Google Patents
Device for extracting copper through deep replacement under multi-field coupling Download PDFInfo
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- CN211497743U CN211497743U CN201922354246.XU CN201922354246U CN211497743U CN 211497743 U CN211497743 U CN 211497743U CN 201922354246 U CN201922354246 U CN 201922354246U CN 211497743 U CN211497743 U CN 211497743U
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Abstract
The utility model discloses a device for extracting copper by deep replacement under multi-field coupling, which comprises an anode zinc plate, a cathode aluminum plate, a reaction tank, a filter tank, a direct current power supply and a constant temperature device; one side of the reaction tank is provided with a flow outlet pipe, and the other side of the reaction tank is provided with a flow inlet pipe; the filter tank is internally divided into a filter residue chamber and a filter liquid chamber through a filter screen, the filter liquid chamber is communicated with the inflow pipe through a circulating pipe, and the circulating pump is arranged on the circulating pipe. The utility model discloses compare with traditional zinc leachate zinc powder purification decoppering technology, adopt the zinc sheet to carry out the target metal replacement with the mode that temperature, stream, electric field made up mutually, realized the high-efficient separation of replacement back zinc-copper. Can use multiple control system directly to control the operation to the reaction, have the reaction thoroughly, the zinc powder consumption reduces, and treatment cost reduces, carries the advantage that copper is efficient, output copper slag content is high, the follow-up advanced treatment of being convenient for. The whole device and the process are simple and reliable, the industrial production is easy to realize, and good economic and environmental benefits are achieved.
Description
Technical Field
The utility model relates to a clean metallurgical technical field of wet process, concretely relates to device of copper is carried in degree of depth replacement under many field couplings.
Background
Copper is the most common metal in the production of the major nonferrous metallurgical industry, and its ions are widely present in nonferrous metallurgical wastes, especially waste streams. However, because of its high biological toxicity and great influence on animals, plants and ecological environment, it is usually separated and extracted in wet nonferrous metallurgy by various clean production methods. At present, the method for extracting copper from metallurgical waste liquid mainly comprises zinc powder replacement, extraction separation, electrodeposition and the like. The most extensive technology for metal extraction belongs to zinc powder replacement, namely, the activity of zinc is far greater than that of copper, the added zinc powder is used as an anode of a micro battery to be dissolved into a liquid phase, a replacement effect is generated in the solution, and then the zinc powder is diffused to the deep part of the solution and participates in the convection motion of the solution, so that the metal copper with poor activity is replaced.
The traditional direct zinc powder replacement has many problems, such as slow reaction speed; the surface of the prepared copper is loose, zinc powder particles are easy to adsorb on the surface, impurities are difficult to clean, and the like; when the copper slag is aggregated into a cluster by stirring, the zinc powder is easily wrapped and clamped in the copper slag particles, and the zinc sulfate solution is wrapped and clamped together, so that the obtained copper slag has low purity, the zinc powder is further incompletely reacted, the consumption of the zinc powder is large, and the quality requirement of common refined copper production is difficult to meet; the method for extracting copper by electrodeposition can effectively recover valuable metals such as Cd, Zn, Cu and the like to obtain the product copper slag with high purity, but has the advantages of long process flow, multiple processes, a series of electrolysis systems, high investment cost, long investment recovery period, high power consumption in the electrolytic deposition process, long period and low current efficiency, and is generally used for refining the blister copper after zinc powder replacement. The extraction separation of the copper leaching solution is suitable for extracting low-concentration copper, and the requirement on an organic reagent is relatively high. Therefore, it is necessary to find a process method which is simple in operation, high in copper extraction efficiency, high in product purity and small in environmental influence.
SUMMERY OF THE UTILITY MODEL
In view of this, the utility model aims at providing a device of copper is carried in degree of depth replacement under the high, easily industrialization of purity of product copper sediment of easy operation, with low costs, carry copper efficient, product copper slag to the problem that the zinc powder consumption that exists is big, the raw materials requires height, the flow is long, with high costs, product purity is not high among the traditional zinc powder replacement carries copper technology.
The utility model discloses an above-mentioned problem is solved to following technical means:
a device for extracting copper by deep replacement under multi-field coupling comprises an anode zinc plate, a cathode aluminum plate, a reaction tank, a filter tank and a direct-current power supply; the anode zinc plate and the cathode aluminum plate are respectively inserted at two sides of the reaction tank and are electrically connected with a direct current power supply through leads; the bottom of the side wall of one side of the reaction tank is provided with a flow outlet pipe, the top of the side wall of the other side of the reaction tank is provided with a flow inlet pipe, and the outside of the reaction tank is provided with a constant temperature device; the filter tank sets up in one side of reaction tank outlet pipe, separates into the filter residue room and the filtrate chamber of arranging from top to bottom through the filter screen in the filter tank, filter residue room and outlet pipe intercommunication, the filtrate chamber passes through circulating pipe and inflow pipe intercommunication, be provided with the circulating pump on the circulating pipe.
Furthermore, an overflow groove is arranged on one side of the top of the reaction tank in parallel.
Furthermore, the thermostatic device is an electric heating type thermostatic heating box sleeved on the reaction tank or an electric heating type heating sheet uniformly distributed on the outer wall of the reaction tank.
Furthermore, the thickness of the anode zinc plate is consistent with that of the cathode aluminum plate, and the thickness of the anode zinc plate and the thickness of the cathode aluminum plate are both controlled to be 0.3-0.8 mm.
Furthermore, the distance between the anode zinc plate and the cathode aluminum plate is 2-6 cm.
Furthermore, a polar plate clamping groove used for clamping and fixing the anode zinc plate and the cathode aluminum plate is arranged in the reaction tank.
Furthermore, the purity of the anode zinc plate is 85-95%, the purity of the cathode aluminum plate is 80-99%, and the area ratio of the cathode aluminum plate to the anode zinc plate is 0.8-1.2: 1.
The utility model has the advantages that: the utility model discloses a device for extracting copper by deep replacement under multi-field coupling, which comprises an anode zinc plate, a cathode aluminum plate, a reaction tank, a filter tank and a direct current power supply; the anode zinc plate and the cathode aluminum plate are respectively inserted at two sides of the reaction tank and are electrically connected with a direct current power supply through leads; the bottom of the side wall of one side of the reaction tank is provided with a flow outlet pipe, the top of the side wall of the other side of the reaction tank is provided with a flow inlet pipe, and the outside of the reaction tank is provided with a constant temperature device; the filter tank sets up in one side of reaction tank outlet pipe, separates into the filter residue room and the filtrate chamber of arranging from top to bottom through the filter screen in the filter tank, filter residue room and outlet pipe intercommunication, the filtrate chamber passes through circulating pipe and inflow pipe intercommunication, be provided with the circulating pump on the circulating pipe. The utility model discloses compare with traditional zinc leachate zinc powder purification decoppering technology, adopt the zinc sheet to carry out the target metal replacement with the mode that temperature, stream, electric field made up mutually, realized the high-efficient separation of replacement back zinc-copper. Can use multiple control system directly to control the operation to the reaction, have the reaction thoroughly, the zinc powder consumption reduces, and treatment cost reduces, carries the advantage that copper is efficient, output copper slag content is high, the follow-up advanced treatment of being convenient for. The whole device and the process are simple and reliable, the industrial production is easy to realize, and good economic and environmental benefits are achieved.
On the other hand, the application also provides a method for carrying out deep replacement copper extraction by adopting the device, which comprises the following steps:
s1: adding a feed liquid containing copper and zinc to be replaced into a reaction tank;
s2: setting reaction conditions: adjusting the circulation speed of the feed liquid, the pH value and the reaction temperature;
s3: the anode zinc plate and the cathode aluminum plate naturally react in the reaction tank for 1-5 hours, then an electric field is started to assist in carrying out deep replacement reaction, and the reaction time after the electric field is coupled is 2-4 hours;
s4: and carrying out solid-liquid separation through a filter tank, and collecting the copper slag after reaction.
Further, the circulation speed of the feed liquid is controlled at 100-500ml/s, the pH is controlled at 1-5, and the reaction temperature is controlled at 40-80 ℃.
Since the method adopts the device, the technical effects corresponding to the device are achieved, and the details are not repeated.
Drawings
The invention is further described with reference to the following figures and examples.
Fig. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a schematic view of the structure of the reaction tank.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, as shown in fig. 1-2: the utility model provides a device of copper is carried in degree of depth replacement under multi-field coupling, including reaction tank 3, positive pole zinc sheet 1, negative pole aluminum plate 2, filter-tank 4 and DC power supply 5.
An overflow groove 12 with an overflow pipe is arranged on one side of the top of the reaction tank 3 in parallel, and polar plate clamping grooves are arranged on two sides inside the reaction tank 3. The bottom of the side wall of one side of the reaction tank 3 is provided with an outlet pipe 6, and the top of the side wall of the other side is provided with an inlet pipe 7. The outside of the reaction tank is provided with a constant temperature device 8, the constant temperature device is an electric heating type constant temperature heating box sleeved outside the reaction tank or an electric heating type heating plate uniformly distributed on the outer wall of the reaction tank.
The anode zinc plate 1 and the cathode aluminum plate 2 are respectively inserted and fixed in the polar plate clamping grooves on the two sides, the anode zinc plate 1 and the cathode aluminum plate 2 are electrically connected with the direct current power supply 5 through wires, and the direct current power supply can provide an auxiliary electric field for the reaction process. The thickness of the anode zinc plate is consistent with that of the cathode aluminum plate, and the thickness of the anode zinc plate and the thickness of the cathode aluminum plate are both controlled to be 0.3-0.8 mm; the distance between the anode zinc plate and the cathode aluminum plate is 2-6 cm. The purity of the anode zinc plate is 85-95%, the purity of the cathode aluminum plate is 80-99%, and the area ratio of the cathode aluminum plate to the anode zinc plate is 0.8-1.2: 1.
The filter tank 4 sets up in one side of reaction tank outlet flow pipe, separates into filter residue room 401 and the filtrate chamber 402 of arranging from top to bottom through filter screen 9 in the filter tank 4, filter residue room 401 and outlet flow pipe 6 intercommunication, filtrate chamber 402 passes through circulating pipe 10 and inflow pipe 7 intercommunication, be provided with circulating pump 11 on the circulating pipe 10, the circulating pump carries out the circulation to the feed liquid and pumps, can make the reaction process be in the circulation flow field.
The embodiment also discloses a method for carrying out deep replacement copper extraction by adopting the device, which comprises the following steps:
s1: adding a feed liquid containing copper and zinc to be replaced into a reaction tank;
s2: setting reaction conditions: adjusting the circulation speed of the feed liquid, the pH value and the reaction temperature; the circulation speed of the material liquid is controlled at 100-500ml/s, the pH value is controlled at 1-5, and the reaction temperature is controlled at 40-80 ℃;
s3: the anode zinc plate and the cathode aluminum plate naturally react in the reaction tank for 1-5 hours, then an electric field is started to assist in carrying out deep replacement reaction, and the reaction time after the electric field is coupled is 2-4 hours;
s4: and carrying out solid-liquid separation through a filter tank, and collecting the copper slag after reaction. Specifically, the surface copper slag and the inner zinc plate are naturally peeled off by the turbulence of the circulating flow field from top to bottom, flow out along with the feed liquid at the bottom of the reaction tank, and are subjected to solid-liquid separation and collection by the filter tank.
The utility model discloses compare with traditional zinc leachate zinc powder purification decoppering technology, adopt the zinc sheet to carry out the target metal replacement with the mode that temperature, stream, electric field made up mutually, realized the high-efficient separation of replacement back zinc-copper. Can use multiple control system directly to control the operation to the reaction, have the reaction thoroughly, the zinc powder consumption reduces, and treatment cost reduces, carries the advantage that copper is efficient, output copper slag content is high, the follow-up advanced treatment of being convenient for. The whole device and the process are simple and reliable, the industrial production is easy to realize, and good economic and environmental benefits are achieved. The technical principle of the present application is detailed below:
the problem that copper slag is clamped by a zinc powder bag can be directly avoided by adopting a zinc plate in the replacement process, and meanwhile, more corrosion points can be generated on the surface of the zinc which is exfoliated in a layered mode, so that the formation of a local micro battery is promoted. The reaction kinetic process can be promoted to be converted from electrochemical control to diffusion control through superposition temperature control, so that the surface loosening of the sediment is facilitated, and the reaction is accelerated; the surface concentration polarization can be eliminated through the circulating flow field, the ion diffusion is promoted, and the displacement deposition and the stripping are accelerated; the reaction potential difference can be increased through the current field, the formation of copper crystal nucleus and the pitting corrosion of the zinc surface are promoted, and the lamellar spalling is generated.
And when the flow field is coupled, a mode of entering from the back side of the cathode and entering from top to bottom is adopted. Wherein, the flow direction of the upper inlet and the lower outlet can accelerate the falling copper slag to deposit downwards, thereby being convenient for the automatic collection of the copper slag. The diffusion of copper ions in the feed liquid to the surface of the anode can be enhanced by the flow direction entering from the back side of the cathode, the occurrence of concentration polarization is avoided, and meanwhile, the stripping of layered copper slag on the surface of the zinc anode can be effectively caused by turbulent flow generated by the impact of fluid on the surface of the anode. Promoting the formation of new pitting on the surface of the zinc anode.
In the coupled electric field, zinc dissolution and copper deposition are performed when there is a difference in both the dissolution voltage and the osmotic pressure and a potential difference is formed (i.e., a difference in charge between an electric double layer near the electrode and the entire solution). The dissolving voltage of zinc is greater than osmotic pressure, the difference is negative, the dissolving voltage of copper is less than osmotic pressure, the difference is positive, the concentration of zinc ions in the solution is increased along with the proceeding of the displacement reaction, the concentration of copper ions is reduced, the negative potential of zinc is reduced due to the increase of the osmotic pressure of ions, the positive potential of copper is reduced due to the reduction of the osmotic pressure of ions, and when the two potential values are equal, the reaction is stopped. After the electric field is superposed, the surface of the zinc plate is subjected to pitting corrosion to increase the specific surface area for replacement, so that the replacement process is promoted. The electric potential between the anode zinc plate and the cathode aluminum plate in the electric field superposition process cannot be larger than the electrodeposition potential of copper, otherwise, the copper is electrodeposited on the cathode.
In the process of coupling the temperature field, the reaction kinetic process of direct zinc plate replacement in the first stage is electrochemical diffusion control, and the kinetic process of replacement reaction after the electric field is superposed in the second stage is diffusion control. Therefore, during the deepening reaction process of the second stage, the reaction temperature is not favorable for the reaction when being too low, and the energy consumption is considered to be increased rapidly when being too high. Therefore, the constant temperature field below 70 ℃ is controlled, which is beneficial to the replacement process.
The advantages of the present application are illustrated below in the specific example process:
example 1
The method comprises the steps of firstly, adjusting the temperature of a constant-temperature heating box to 40 ℃, turning on and adjusting a circulating pump, adjusting the circulating flow rate of the feed liquid to 1.4mL/s, and secondly, turning on a direct-current power supply and controlling the current density on a zinc plate to 40 mA/cm/s, wherein the original concentration of the feed liquid is Zn 4g/L and Cu 6g/L, the pH is 2, placing 500mL of the feed liquid into a reaction tank, the size of an anode zinc plate is 4 × 6cm, the thickness is 0.5cm, the purity is 95%, the size of a cathode aluminum plate is 4 × 6cm, the thickness is 0.5cm, the purity is 90%, all the materials are polished smoothly by using abrasive paper, and the distance between the zinc plate and the aluminum plate is 4 cm.2. The two-stage reaction time was adjusted and the results were as follows:
TABLE 1 feed liquid copper extraction yield
Example 2
The original concentration of the raw material liquid is as follows: zn 4g/L, Cu 6g/L, pH 2. 500mL of the feed liquid is taken and placed into a reaction tank, the size of an anode zinc plate is 4 multiplied by 6cm, the thickness is 0.5cm, and the purity is 95 percent; the cathode aluminum plate inch is 4 multiplied by 5cm, the thickness is 0.5cm, the purity is 90%, the cathode aluminum plate inch and the cathode aluminum plate inch are polished smoothly by using sand paper, and the distance between the zinc plate and the aluminum plate is set to be 5 cm.
A first reaction stage: adjusting the temperature of the constant-temperature heating box to 60 ℃; and (3) starting and adjusting a circulating pump, adjusting the circulating flow rate of the feed liquid to be 2ml/s, and adjusting the reaction time to be 3 h.
And (3) a second reaction stage: starting a direct current power supply and controlling the current density on the zinc plate to be 60mA/cm2The reaction time is 2 h.
And (3) obtaining filtrate and copper slag, weighing 1g of copper slag, cleaning, drying, completely dissolving with sulfuric acid, and determining the volume to 100mL, wherein the content of zinc and copper is measured by ICP (inductively coupled plasma), and the result is shown in Table 2.
TABLE 2 residue filtrate composition
According to the results, the grade of the copper slag obtained after the reaction can reach 94.18%, and the result proves that the grade of the extracted single copper slag is high and the effect is good.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or replaced by other means without departing from the spirit and scope of the present invention, which should be construed as limited only by the appended claims.
Claims (7)
1. The utility model provides a device of copper is carried in degree of depth replacement under multi-field coupling which characterized in that:
comprises an anode zinc plate, a cathode aluminum plate, a reaction tank, a filter tank and a direct current power supply;
the anode zinc plate and the cathode aluminum plate are respectively inserted at two sides of the reaction tank and are electrically connected with a direct current power supply through leads;
the bottom of the side wall of one side of the reaction tank is provided with a flow outlet pipe, the top of the side wall of the other side of the reaction tank is provided with a flow inlet pipe, and the outside of the reaction tank is provided with a constant temperature device;
the filter tank sets up in one side of reaction tank outlet pipe, separates into the filter residue room and the filtrate chamber of arranging from top to bottom through the filter screen in the filter tank, filter residue room and outlet pipe intercommunication, the filtrate chamber passes through circulating pipe and inflow pipe intercommunication, be provided with the circulating pump on the circulating pipe.
2. The device for extracting copper by deep displacement under multi-field coupling according to claim 1, wherein: and overflow grooves are arranged on one side of the top of the reaction tank in parallel.
3. The device for extracting copper by deep displacement under multi-field coupling according to claim 2, wherein: the constant temperature device is an electric heating type constant temperature heating box sleeved on the reaction tank or an electric heating type heating sheet uniformly distributed on the outer wall of the reaction tank.
4. The device for extracting copper by deep displacement under multi-field coupling according to claim 3, wherein: the thickness of the anode zinc plate is consistent with that of the cathode aluminum plate, and the thickness of the anode zinc plate and the thickness of the cathode aluminum plate are both controlled to be 0.3-0.8 mm.
5. The device for extracting copper by deep displacement under multi-field coupling according to claim 4, wherein: the distance between the anode zinc plate and the cathode aluminum plate is 2-6 cm.
6. The device for extracting copper by deep displacement under multi-field coupling according to claim 5, wherein: the area ratio of the cathode aluminum plate to the anode zinc plate is 0.8-1.2: 1.
7. The device for extracting copper by deep displacement under multi-field coupling according to any one of claims 1 to 6, wherein: and a polar plate clamping groove for clamping and fixing the anode zinc plate and the cathode aluminum plate is arranged in the reaction tank.
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