Novel continuous copper dissolving process for producing high-purity copper oxide

Abstract

The invention relates to a novel continuous copper dissolving process for high-purity copper oxide production, which belongs to the field of high-purity copper oxide production and comprises the following steps: adding an electrolytic copper plate, stronger ammonia water, an ammonium carbonate aqueous solution, cuprammonia oxide and oxygen-containing tail gas after cuprammonia oxidation into a copper dissolving tower in a continuous feeding manner; the bivalent copper ammonia complex ions, the stronger ammonia water, the oxygen and the ammonium carbonate aqueous solution participate in the reaction of dissolving the electrolytic copper plate at the same time. According to the novel continuous copper dissolving process for producing the high-purity copper oxide, the copper dissolving tower and the oxidizing tower are adopted for continuously dissolving copper, and the stronger ammonia water, the ammonium carbonate aqueous solution, the oxygen-containing tail gas and the electrolytic copper plate are added in a continuous feeding manner, so that the divalent cupric carbonate ammonia complexing solution can be continuously and circularly prepared; the copper dissolving speed is more than ten times that of a traditional process, and air firstly passes through the oxidation tower to completely oxidize a cuprous ammonia complexing solution and then enters the copper dissolving tower to oxidize elemental copper, so that oxygen in the air almost consumes light, the air consumption is only 25-30% of that of the traditional process, the air pressure is low, and the compression energy consumption is only one tenth of that of a traditional method.

Description

Technical Field

[0001] The invention relates to the technical field of high-purity copper oxide production, in particular to a new continuous copper dissolving process for producing high-purity copper oxide. Background Art

[0002] To produce high-purity copper oxide products required by the electronics industry, the electrolytic copper plate must first be dissolved into a copper carbonate ammonia complex solution. After impurities are removed, it is deaminated and dehydrated to convert it into the intermediate product basic copper carbonate. After filtration and drying, it is thermally cracked at high temperature in a rotary kiln to obtain a copper oxide product. The copper dissolving and oxidation process is a key process that directly affects the manufacturing cost of the product.

[0003] The traditional copper dissolving and oxidation process adopts cluster-type reactors to dissolve copper and cluster-type reactors to oxidize. During the copper dissolving process in the copper dissolving reactor, the long-term air blowing will take away part of the ammonia required to form the complex ammonia copper ions, and the air blown in during the air oxidation process in the oxidation reactor also takes away part of the ammonia required to form the complex ammonia copper ions. The solution has less free ammonia, which easily generates basic copper carbonate crystals, resulting in more system maintenance and low copper content in the copper ammonia complex solution, affecting production capacity. In addition, cluster-type reactors are used for copper dissolving and reactor oxidation, which occupy a large area and have high energy consumption. The copper dissolving reactor and the oxidation reactor need to be operated separately, which requires a lot of labor. The air is in contact with the solution in the copper dissolving reactor and the oxidation reactor for a short time, the oxygen utilization rate is low, the air consumption is large, and the air pressure of the bubbling process is high, which leads to high air compression energy consumption. Therefore, a new continuous copper dissolving process for high-purity copper oxide production is proposed to solve the above problems. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a new continuous copper dissolving process for the production of high-purity copper oxide, which has the advantages of low energy consumption and small footprint, and solves the problems of low copper ion concentration in the traditional copper dissolving and oxidation process, large footprint of clustered reactors for copper dissolving and oxidation, large investment and high energy consumption.

[0005] To achieve the above object, the present invention provides the following technical solution: a new continuous copper dissolving process for producing high-purity copper oxide, comprising the following steps:

[0006] S1: electrolytic copper plate, concentrated ammonia water, ammonium carbonate aqueous solution, copper oxide ammonia solution, and oxygen-containing tail gas after oxidation of copper ammonia solution are continuously fed into a copper dissolving tower, and divalent copper ammonia complex ions, concentrated ammonia water, oxygen and ammonium carbonate aqueous solution simultaneously participate in the reaction of dissolving the electrolytic copper plate to generate a complex solution of tetraammine cupric ions and diammine cuprous ions;

[0007] S2 uses No. 1 circulation pump to send the complex solution in the copper dissolving tower to the top of the oxidation tower, and uses Roots air compressor to send air into the oxidation tower. The oxygen in the air reacts with the diammine cuprous ions in the complex solution to generate tetraammine cupric ions.

[0008] S3 then uses the No. 2 circulation pump to send the divalent tetraamminecopper ion complex solution, oxidation tail gas, external ammonium carbonate solution and concentrated ammonia water in the oxidation tower into the copper dissolving tower filled with copper blocks. The copper blocks react with oxygen and divalent tetraamminecopper ions to produce oxidation and disproportionation reactions, and generate a copper ion complex solution containing divalent tetraamminecopper ions and monovalent diamminecopperous ions. Free ammonia supplements the loss of complex ion ammonia.

[0009] S4 sends the divalent copper ammonia complex solution generated in the oxidation tower to the precision filtration process for impurity removal through the No. 3 pump, and the purified copper ammonia complex solution is sent to the subsequent process to produce high-purity copper oxide products.

[0010] A new continuous copper dissolving process for producing high-purity copper oxide, characterized in that:

[0011] Preferably, the electrolytic copper plates inside the copper dissolving tower in S1 may be fragments processed by an electrolytic copper plate shredder, and the oxygen inside the copper dissolving tower in S1 may be residual oxygen from the reaction inside the oxidation tower in S2.

[0012] Preferably, the concentrated ammonia water inside the copper dissolving tower in S1 provides the ammonia required for generating copper-ammine complex ions, which can accelerate the copper dissolving speed. The ammonium carbonate aqueous solution, the electrolytic copper plate and the residual oxygen inside the copper dissolving tower in S1 simultaneously generate a copper ion complex solution containing divalent tetraammine cupric ions and monovalent diammine cuprous ions, and the divalent tetraammine cuprous ions inside the copper dissolving tower in S1 undergo a disproportionation reaction with the electrolytic copper plate to generate monovalent diammine cuprous ions.

[0013] Preferably, the oxygen inside the oxidation tower in S2 reacts with diammine cuprous ions to generate tetraammine cupric ions.

[0014] Compared with the prior art, the present invention provides a new continuous copper dissolving process for producing high-purity copper oxide, which has the following beneficial effects:

[0015] 1. The new continuous copper dissolving process for producing high-purity copper oxide adopts a copper dissolving tower and an oxidation tower to continuously dissolve copper, and adopts a continuous feeding method to add concentrated ammonia water, ammonium carbonate aqueous solution and electrolytic copper plates, so as to realize the continuous circulation preparation of divalent copper ions. Moreover, the air first passes through the oxidation tower to completely oxidize the monovalent copper ammonia complex solution and then enters the copper dissolving tower to oxidize the elemental copper, so that the oxygen in the air is almost consumed, so that the amount of air consumed is only 25-30% of that of the traditional process, and the air pressure is low, and the compression energy consumption is only one tenth of that of the traditional method.

[0016] 2. The new continuous copper dissolution process for the production of high-purity copper oxide introduces a divalent copper-ammonia complex solution as a copper-dissolving medium. The reaction speed can be ten times faster than that of the traditional process, so that one set of equipment can replace dozens of original copper-dissolving and oxidation kettles, reducing a large amount of equipment space and significantly saving investment. In addition, there is no ammonia loss and little free ammonia loss during the entire oxidation and copper-dissolving process. Moreover, the supplementary ammonia is directly added to the top of the copper-dissolving tower, which maximizes the free ammonia concentration of the copper-ammonia complex solution in the copper-dissolving tower. There is enough complex ammonia required for copper dissolution, which is conducive to improving the copper-dissolving speed and effectively increasing the copper concentration in the complex copper-ammonia solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic diagram of a new continuous copper dissolving process for producing high-purity copper oxide proposed by the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention and the accompanying drawings to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Embodiment 1:

[0020] See also Figure 1 A new continuous copper dissolving process for producing high-purity copper oxide in this embodiment comprises the following steps:

[0021] S1: electrolytic copper plate, concentrated ammonia water, ammonium carbonate aqueous solution, copper oxide ammonia solution, and oxygen-containing tail gas after oxidation of copper ammonia solution are continuously fed into a copper dissolving tower, and divalent copper ammonia complex ions, concentrated ammonia water, oxygen and ammonium carbonate aqueous solution simultaneously participate in the reaction of dissolving the electrolytic copper plate to generate a complex solution of tetraammine cupric ions and diammine cuprous ions;

[0022] It should be noted that the oxygen-containing tail gas after the oxidation tower in S1 enters the copper dissolving tower to oxidize elemental copper, which can efficiently utilize the oxygen in the air, reduce the amount of air required for the continuous copper dissolving process, and achieve high efficiency and energy saving.

[0023] The electrolytic copper plates in the copper dissolving tower in S1 can be pieces processed by an electrolytic copper plate shredder, and the copper block level in the tower is kept constant by continuously adding pieces of electrolytic copper plates. The oxygen in the copper dissolving tower in S1 is the residual oxygen in the reaction in the oxidation tower in S2.

[0024] S2 uses No. 1 circulation pump to send the complex solution in the copper dissolving tower to the top of the oxidation tower, and uses Roots air compressor to send air into the oxidation tower. The oxygen in the air reacts with the diammine cuprous ions in the complex solution to generate tetraammine cupric ions, continuously converting monovalent copper into divalent copper;

[0025] S3 then uses the No. 2 circulation pump to send the divalent tetraamminecopper ion complex solution, oxidation tail gas, external ammonium carbonate solution and concentrated ammonia water in the oxidation tower into the copper dissolving tower filled with copper blocks. The copper blocks react with oxygen and divalent tetraamminecopper ions to produce oxidation and disproportionation reactions, and generate a copper ion complex solution containing divalent tetraamminecopper ions and monovalent diamminecopperous ions. Free ammonia supplements the loss of complex ion ammonia.

[0026] S4 sends the divalent copper ammonia complex solution generated in the oxidation tower to the precision filtration process for impurity removal through the No. 3 pump, and the purified copper ammonia complex solution is sent to the subsequent process to produce high-purity copper oxide products.

[0027] The above technical scheme is adopted, and a new continuous copper dissolving process combining a copper dissolving tower and an oxidation tower is adopted. The principle of disproportionation reaction between divalent copper ammonia complex ions and copper blocks is fully utilized. The air utilization rate in the efficient oxidation tower is high, and a sufficient amount of divalent copper ammonia complex solution required for copper dissolving can be obtained. The continuous production process of tower oxidation and tower copper dissolving replaces the backward process of cluster unit bubbling copper dissolving and oxidation, realizing the organic unity of high efficiency, investment saving and significant energy consumption reduction.

[0028] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A new continuous copper dissolving process for producing high-purity copper oxide, characterized in that: The steps include: S1: electrolytic copper plate, concentrated ammonia water, ammonium carbonate aqueous solution, copper oxide ammonia solution, and oxygen-containing tail gas after oxidation of copper ammonia solution are continuously fed into a copper dissolving tower, and divalent copper ammonia complex ions, concentrated ammonia water, oxygen and ammonium carbonate aqueous solution simultaneously participate in the reaction of dissolving the electrolytic copper plate to generate a complex solution of tetraammine cupric ions and diammine cuprous ions; S2 uses No. 1 circulation pump to send the complex solution in the copper dissolving tower to the top of the oxidation tower, and uses Roots air compressor to input air into the oxidation tower. The oxygen in the air reacts with the diammine cuprous ions in the complex solution to generate tetraammine cupric ions. S3 then uses the No. 2 circulation pump to send the divalent tetraamminecopper ion complex solution, oxidation tail gas, external ammonium carbonate solution and concentrated ammonia water in the oxidation tower into the copper dissolving tower filled with copper blocks. The copper blocks react with oxygen and divalent tetraamminecopper ions to produce oxidation and disproportionation reactions, and generate a copper ion complex solution containing divalent tetraamminecopper ions and monovalent diamminecopperous ions. Free ammonia supplements the loss of complex ion ammonia. S4 sends the divalent copper ammonia complex solution generated in the oxidation tower to the precision filtration process for impurity removal through the No. 3 pump, and the purified copper ammonia complex solution is sent to the subsequent process to produce high-purity copper oxide products.

2. The novel continuous copper dissolving process for producing high-purity copper oxide according to claim 1, characterized in that: The electrolytic copper plates in the copper dissolving tower in S1 may be fragments processed by an electrolytic copper plate shredder, and the oxygen in the copper dissolving tower in S1 may be residual oxygen from the reaction in the oxidation tower in S2.

3. The novel continuous copper dissolving process for producing high-purity copper oxide according to claim 1, characterized in that: The concentrated ammonia water inside the copper dissolving tower in S1 provides the ammonia required for generating copper-ammine complex ions, which can accelerate the copper dissolving speed. The ammonium carbonate aqueous solution, the electrolytic copper plate and the residual oxygen inside the copper dissolving tower in S1 react to simultaneously generate a copper ion complex solution containing divalent tetraammine cupric ions and monovalent diammine cuprous ions. The tetraammine cupric ions inside the copper dissolving tower in S1 undergo a disproportionation reaction with the electrolytic copper plate to generate diammine cuprous ions.

4. The novel continuous copper dissolving process for producing high-purity copper oxide according to claim 1, characterized in that: The oxygen in the oxidation tower in S2 reacts with the diammine cuprous ions to generate tetraammine cupric ions.

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