Active copper oxide preparation system capable of recycling ammonia and carbon

Abstract

The utility model provides an active copper oxide preparation system capable of recycling ammonia carbon. The active copper oxide preparation system comprises a carbonization unit, an ammonia leaching unit, an ammonia carbon removal unit, a centrifugal drying unit and a calcination unit which are communicated in sequence, the carbonization unit is used for preparing a copper dissolving reagent from ammonia water and carbon dioxide; the ammonia leaching unit is used for mixing a copper raw material with a copper dissolving reagent to prepare a copper ammonia complex; the ammonia and carbon removal unit is used for heating the copper ammonia complex to generate basic cupric carbonate slurry and ammonia and carbon mixed gas; the centrifugal drying unit is used for centrifuging and drying the basic cupric carbonate slurry to prepare a basic cupric carbonate solid; and the calcining unit is used for calcining the basic cupric carbonate solid at high temperature to produce active copper oxide. The active copper oxide preparation system capable of recycling ammonia and carbon can be used for directly preparing active copper oxide with high purity and uniform particle size.

Description

Technical Field

[0001] The utility model relates to the technical field of active copper oxide production, in particular to an active copper oxide preparation system with ammonia-carbon recycling. Background Art

[0002] In the prior art, the production of activated copper oxide has the following problems:

[0003] It is impossible to produce active copper oxide directly. Copper oxide must be produced first, and then the active copper oxide is prepared through subsequent operations such as crushing and grinding.

[0004] The purity of activated copper oxide is low and the impurity content is high;

[0005] The use of intermittent heating in an ammonia still results in long deamination times and low ammonia removal rates. For processing 1 ton of copper raw material, the corresponding kettle of copper-ammonia complex requires more than 10 hours of heating and deamination.

[0006] Therefore, it is of great significance to provide an activated copper oxide preparation system that can directly produce high-purity, uniform-sized activated copper oxide with a short reaction time and ammonia-carbon recycling. Summary of the Invention

[0007] Based on the above objectives, the present invention provides an activated copper oxide preparation system with ammonia-carbon recycling to solve or partially solve the above technical problems:

[0008] An activated copper oxide preparation system with ammonia-carbon recycling, comprising:

[0009] A carbonization unit, an ammonia leaching unit, a deamination carbon unit, a centrifugal drying unit and a calcination unit connected in sequence;

[0010] The carbonization unit is used to prepare a copper-dissolving reagent using ammonia water and carbon dioxide;

[0011] The ammonia leaching unit is used to mix the copper raw material with the copper-dissolving reagent to prepare the copper-ammine complex;

[0012] The deamination carbon unit is used to heat the copper ammonia complex to produce basic copper carbonate slurry and ammonia carbon mixed gas;

[0013] The centrifugal drying unit is used to centrifuge and dry the basic copper carbonate slurry to prepare basic copper carbonate solid;

[0014] The calcination unit is used to calcine basic copper carbonate solid at high temperature to produce active copper oxide.

[0015] Furthermore, the centrifugal drying unit is connected to the ammonia leaching unit.

[0016] Furthermore, the deamination carbon unit includes a distillation tower, a vacuum pump and an absorption tower connected in sequence.

[0017] The distillation tower is connected to the ammonia leaching unit and the centrifugal drying unit respectively; the absorption tower is connected to the carbonization unit.

[0018] Furthermore, the deamination carbon unit also includes a cooler, the heat flow inlet of the cooler is connected to the bottom of the absorption tower, and the heat flow outlet of the cooler is divided into two paths, one path refluxes to the top of the absorption tower, and the other path is connected to the carbonization unit.

[0019] Furthermore, the deamination carbon unit also includes a reboiler, and the reboiler is connected to the distillation tower.

[0020] Furthermore, the distillation tower has an operating pressure of 35-80 KPa and an operating temperature of 75-95°C.

[0021] Furthermore, the distillation tower comprises an upper head, a cylinder and a lower cone section welded in sequence from top to bottom;

[0022] The upper cover is provided with a gas phase port, which is connected to the vacuum pump;

[0023] The cylinder is provided with a feed port, which is connected to the ammonia leaching unit;

[0024] The lower cone section is provided with a discharge port, which is communicated with the centrifugal drying unit.

[0025] Furthermore, a vertical sieve plate is provided in the cylinder.

[0026] Furthermore, the vacuum pump is a jet vacuum pump.

[0027] Furthermore, the absorption tower is a packed tower.

[0028] From the above description, it can be seen that the activated copper oxide preparation system using ammonia-carbon recycling provided by the present invention has the following beneficial effects:

[0029] Active copper oxide has high purity and uniform grains:

[0030] The copper dissolving reagent of ammonia and ammonium bicarbonate solution is directly prepared online with ammonia water and carbon dioxide, without using ammonium bicarbonate crystals containing additives for dissolution and preparation. The copper dissolving reagent has high purity and copper oxide has high purity.

[0031] Deamination is achieved by distillation, resulting in high purity of basic copper carbonate and, consequently, high purity of copper oxide: (1) The distillation operating temperature is 75-95°C, which is low enough to prevent high-temperature decomposition of basic copper carbonate and oxidation of copper; (2) The ammonia nitrogen in the tower bottom liquid - basic copper carbonate slurry - is ≤20 ppm, resulting in a high ammonia nitrogen removal rate, which prevents the subsequent high-temperature calcination of basic copper carbonate to produce copper oxide, where ammonia decomposes to produce hydrogen and reduces copper oxide to elemental copper. (3) The distillation tower and its components are connected by welding, which provides good sealing and prevents oxygen from leaking into the copper element, oxidizing it and causing scarring inside the tower. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0033] Figure 1 This is a schematic diagram of an activated copper oxide preparation system using ammonia-carbon recycling according to an embodiment of the present invention.

[0034] In the figure: 1-carbonization unit; 2-ammonia leaching unit; 3-deamination carbon unit; 31-distillation tower; 311-upper head; 311a-gas phase port; 312a-feed port; 313a-discharge port; 312-cylinder; 313-lower cone section; 313a-discharge port; 32-vacuum pump; 33-absorption tower; 34-cooler; 35-reboiler; 4-centrifugal drying unit; 5-calcination unit. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0036] It should be noted that, unless otherwise defined, the technical terms or scientific terms used in the embodiments of the present invention should have the usual meanings understood by people with ordinary skills in the field to which the present invention belongs. The "first", "second" and similar words used in the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. "Include" or "comprise" and similar words mean that the elements or objects appearing before the word include the elements or objects listed after the word and their equivalents, without excluding other elements or objects. "Connect" or "connect" and similar words are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "Up", "down", "left", "right" and the like are only used to indicate relative position relationships. When the absolute position of the described object changes, the relative position relationship may also change accordingly.

[0037] One or more embodiments of the present invention provide an activated copper oxide preparation system using ammonia-carbon recycling, comprising:

[0038] The carbonization unit 1, the ammonia leaching unit 2, the deamination carbon unit 3, the centrifugal drying unit 4 and the calcination unit 5 are connected in sequence;

[0039] The carbonization unit 1 is used to prepare a copper-dissolving reagent using ammonia water and carbon dioxide;

[0040] The ammonia leaching unit 2 is used to mix the copper raw material with the copper dissolving reagent to prepare the copper ammonia complex;

[0041] The deamination carbon unit 3 is used to heat the copper ammonia complex to produce basic copper carbonate slurry and ammonia carbon mixed gas;

[0042] The centrifugal drying unit 4 is used to centrifuge and dry the basic copper carbonate slurry to prepare basic copper carbonate solid;

[0043] The calcination unit 5 is used to calcine basic copper carbonate solid at high temperature to produce active copper oxide.

[0044] Carbonization Unit 1: Prepares a copper-dissolving reagent using ammonia and carbon dioxide. This process involves diluting the ammonia to the desired concentration, vaporizing the liquid carbon dioxide, mixing the vaporized carbon dioxide with the ammonia, and then absorbing it through a carbonization reaction, generating the copper-dissolving reagent online—a mixed solution containing ammonia and ammonium bicarbonate.

[0045] In the existing technology, copper dissolving reagents are: ammonia water and ammonium bicarbonate; during the ammonia leaching complex reaction: ammonia water, ammonium bicarbonate and copper raw materials are mixed, heated and stirred to generate copper ammonia complex. There are several main problems:

[0046] (1) Ammonium bicarbonate is a white crystalline compound. During its preparation, additives need to be added to ensure crystallization and reduce the water content in the product. The copper ammonia complex generated by ammonia leaching will also be mixed with additives, thereby affecting the purity of the final product, copper oxide.

[0047] (2) The conventional ammonia concentration is generally 25% w. The higher the ammonia concentration, the greater the volatilization loss. The ammonia content in the copper dissolving reagent is generally controlled at 5%-20% w. During the ammonia leaching complexation reaction, external water needs to be added for dilution, which increases the difficulty of controlling the ammonia leaching complexation reaction and increases the reaction time.

[0048] In the present application, an ammonia and ammonium bicarbonate solution-type copper-dissolving reagent is directly prepared online using ammonia water and carbon dioxide, without using ammonium bicarbonate crystals containing additives for dissolution and configuration. The copper-dissolving reagent has high purity, thereby ensuring the purity of the final product copper oxide.

[0049] The carbonization unit 1 specifically includes: introducing ammonia and carbon dioxide into a carbonization tower to carry out a carbonization reaction and prepare a copper-dissolving reagent. The carbonization tower is provided with fillers, and the carbonized liquid in the tower bottom - the copper-dissolving reagent - is cooled and sent to the top of the carbonization tower for reflux and reabsorption. This has a good carbon dioxide absorption effect and high copper-dissolving reagent preparation efficiency. In addition, the copper-dissolving reagent composition requirements are guaranteed by controlling the feed amount of ammonia and carbon dioxide, the carbonization temperature, and the pressure.

[0050] Ammonia leaching unit 2: The copper raw material is mixed with the copper dissolving reagent, oxygen or air is introduced, and the ammonia leaching complex reaction is carried out under heating and pressure to obtain a copper-ammine complex.

[0051] Furthermore, in the ammonia leaching unit 2: the ammonia leaching complexation reaction is carried out in a closed reactor.

[0052] Copper raw materials and a copper-dissolving reagent are added to a sealed reactor. Oxygen or air is introduced and heated under pressure for a certain period of time. This forms soluble copper-ammonia complex ions that enter the solution, completing the dissolution and leaching of copper to form a copper-ammonia complex. Pressurized copper leaching increases the ammonia leaching rate and reduces the reaction time. The sealed reactor also reduces ammonia escape.

[0053] Copper raw materials can include copper ore, scrap copper catalyst, copper foil, etc. Copper raw materials with high impurities and low copper content, such as copper ore and scrap copper catalyst, can be pre-treated by crushing and impurity removal before ammonia leaching. High-purity copper raw materials, such as copper foil, can be directly leached with ammonia.

[0054] In order to ensure the ammonia leaching complex reaction, the amount of copper dissolving reagent added is excessive, so that the copper ammonia complex solution contains excessive ammonia and ammonium bicarbonate.

[0055] Deamination carbon unit 3: After the copper ammonia complex is filtered, it is distilled to remove the ammonia carbon. Ammonia and carbon dioxide are produced at the top of the tower, and basic copper carbonate slurry is produced at the bottom of the tower.

[0056] There are two main purposes of distillation: one is to remove excess ammonia and ammonium bicarbonate by distillation, and the other is to decompose the copper ammonia complex into basic copper carbonate, ammonia and carbon dioxide under heat. The chemical equation is:

[0057] 2[Cu(NH3)4C03]+H20--Cu2(0H)2C03↓+C02↑+8NH3↑.

[0058] In the prior art, copper-ammonia complex decomposition and deamination methods involve intermittently decomposing a fixed amount of copper-ammonia complex in an ammonia still. Specifically, a fixed amount of copper-ammonia complex is added to the still all at once, steam / thermal oil is introduced into the jacket of the still to heat and decompose the complex, and a fan is installed on top of the still to remove ammonia and carbon dioxide. This method has the following problems:

[0059] (1) Decomposition and deamination in an ammonia still is a single-stage deamination process, similar to flash distillation. This process takes a long time. For example, a plant processes 1 ton of copper raw material, and the corresponding kettle of copper-ammonia complex requires more than 10 hours of heating and deamination, resulting in low processing efficiency. This long heating time prevents the material from being delivered to subsequent processing steps in a timely manner, increasing the likelihood that the material will come into contact with oxygen and undergo qualitative changes. For example, oxygen leaks into the kettle, oxidizing the copper element to form copper oxide, which can cause black scarring in the ammonia still.

[0060] (2) The deamination effect is poor. The ammonia nitrogen content in the ammonia still liquid-basic copper carbonate solution is generally as high as 3000-6000ppm. Therefore: 1. The ammonia nitrogen impurity content of basic copper carbonate is large and the purity is low; 2. In the subsequent high-temperature calcination of basic copper carbonate to produce copper oxide, ammonia decomposes into hydrogen, and hydrogen reduces copper oxide to copper elemental mixed in copper oxide, reducing the purity and yield of copper oxide.

[0061] (3) The ammonia still is a kettle-type container, operated intermittently, and can process a large batch of materials. Furthermore, it uses a jacket for indirect heating, resulting in uneven heating within the kettle. In areas where the heating is insufficient, the copper ammonia complex is difficult to decompose; in areas where the heating is excessive, basic copper carbonate decomposes to produce copper oxide. Ultimately, the products in the kettle are diverse, including copper ammonia complex, basic copper carbonate, copper oxide, and other substances.

[0062] Due to these factors, the subsequent drying of the basic copper carbonate slurry results in a green mass dotted with black impurities. Basic copper carbonate itself, as a chemical, can be used to make flares, fireworks, paints, pesticides, and antidotes. However, impurities in basic copper carbonate significantly limit its applications.

[0063] Furthermore, pure basic copper carbonate is a loose powder. However, when a basic copper carbonate slurry contains multiple impurities such as copper-ammonia complexes, basic copper carbonate, copper oxide, and ammonia, it forms a cohesive mass after drying. The copper oxide produced by subsequent high-temperature calcination of the basic copper carbonate solid also forms a cohesive mass and requires pulverization and grinding to reach the standard for active copper oxide.

[0064] Furthermore, in the deamination carbon unit 3: the deamination carbon unit 3 includes a distillation tower 31, a vacuum pump 32 and an absorption tower 33 connected in sequence, the distillation tower 31 is connected to the ammonia leaching unit 2 and the centrifugal drying unit 4 respectively; the absorption tower 33 is connected to the carbonization unit 1.

[0065] The distillation is carried out in the distillation tower 31. The distillation adopts negative pressure distillation. The operating pressure of the distillation tower 31 is controlled to be 35-80KPa and the operating temperature is 75-95°C.

[0066] This application utilizes a distillation process, which is carried out in a distillation tower 31. Steam is introduced directly into the bottom of the tower, or indirectly through a reboiler 35, ensuring uniform heating within the tower. The distillation utilizes negative pressure distillation, controlling the operating pressure of the distillation tower 31 at 35-80 kPa and the operating temperature at 75-95°C. At these temperatures, the decomposition rate of the copper ammonia complex is high, while the temperature at which basic copper carbonate decomposes and the copper element oxidizes is not reached. This uniform heating and low-temperature decomposition result in a uniform bottom product: basic copper carbonate.

[0067] Furthermore, the ammonia nitrogen content in the bottoms liquid is controlled to ≤20 ppm. Low ammonia nitrogen in the bottoms liquid (basic copper carbonate) reduces the reducing effect of hydrogen generated by the decomposition of ammonia on copper oxide during the subsequent calcination of basic copper carbonate to produce copper oxide. This low ammonia nitrogen content ensures the purity of the basic copper carbonate and the subsequent copper oxide.

[0068] Furthermore, the distillation tower 31 includes an upper head 311, a cylinder 312 and a lower cone section 313 welded in sequence from top to bottom; a gas phase port 311a is provided on the upper head 311, and the gas phase port 311a is connected to the vacuum pump 32; a feed port 312a is provided on the cylinder 312, and the feed port 312a is connected to the ammonia leaching unit 2; a discharge port 313a is provided on the lower cone section 313, and the discharge port 313a is connected to the centrifugal drying unit 4.

[0069] Furthermore, a vertical sieve plate is provided in the cylinder 312 .

[0070] The distillation tower 31 is sealed to prevent oxygen from entering and oxidizing the copper, ensuring the purity of the bottom liquid. The bottom liquid of the distillation tower 31 is a basic copper carbonate slurry. The bottom of the distillation tower 31 is designed with a steep tapered angle to facilitate liquid discharge. The tower trays are vertical sieve plates, which are resistant to blockage.

[0071] Furthermore, the distillation is continuous distillation. The residence time of the material in the tower is short, which prevents the material from being heated for a long time or coming into contact with air, thereby preventing the material from being decomposed or oxidized to produce impurity products.

[0072] Uniform heating, low-temperature decomposition, low ammonia nitrogen content, and a sealed seal prevent oxygen intrusion, ensuring the purity of the basic copper carbonate slurry and, by extension, the copper oxide. The high purity of the basic copper carbonate slurry results in a uniform particle size, and the resulting copper oxide also has a uniform and fine particle size, meeting the standards for active copper oxide, eliminating the need for subsequent grinding.

[0073] Furthermore, the vacuum pump 32 is a jet vacuum pump.

[0074] Furthermore, the absorption tower 33 is a packed tower with high absorption efficiency.

[0075] The present application uses a jet vacuum pump 32 to control the pressure of the distillation tower 31 to 35-80 kPa. Furthermore, the ammonia, carbon dioxide, and water vapor produced at the top of the tower are sent to the absorption tower 33 through the jet vacuum pump 32 and absorbed by water to form carbon-containing ammonia water.

[0076] When the overhead gas is condensed in the overhead condenser, ammonia, carbon dioxide, and water vapor are condensed to form ammonium bicarbonate. Ammonium bicarbonate easily crystallizes when cooled, but the overhead condenser has narrow flow channels and is easily clogged. Therefore, ammonia and carbon dioxide enter absorption tower 33 directly, where they are absorbed by water to form an ammonia-ammonium bicarbonate mixture. The tower has a large flow channel, is less susceptible to clogging, and is easy to clean and control.

[0077] Furthermore, the deamination carbon unit 3 also includes a cooler 34, the heat flow inlet of the cooler 34 is connected to the bottom of the absorption tower 33, and the heat flow outlet of the cooler 34 is divided into two paths, one of which refluxes to the top of the absorption tower 33, and the other is connected to the carbonization unit 1.

[0078] The carbon-containing ammonia water is sent to the carbonization unit 1 to prepare the copper-dissolving reagent, thereby realizing the recycling and resource utilization of carbon and ammonia.

[0079] Furthermore, the deamination carbon unit 3 further includes a reboiler 35 , which is in communication with the distillation tower 31 and is used to supply heat to the distillation tower 31 .

[0080] Furthermore, the centrifugal drying unit 4 is connected to the ammonia leaching unit 2. In the centrifugal drying unit 4, the supernatant after centrifugation of the basic copper carbonate slurry is the basic copper carbonate mother liquor, which contains not only basic copper carbonate but also some ammonia carbon, and is sent to the ammonia leaching unit 2 for recycling and participation in the ammonia leaching complexation reaction.

[0081] Furthermore, in the calcination unit 5, the high-temperature calcination reaction of basic copper carbonate is: Cu2(OH)2CO3=2CuO+CO2↑+H2O, generating tail gas containing carbon dioxide, which is sent to the tail gas treatment system for tail gas treatment.

[0082] From the above, it can be seen that the activated copper oxide preparation system with ammonia-carbon recycling of the present invention can realize the ammonia-carbon recycling of the system, and the prepared copper oxide has a uniform and fine particle size, which can meet the standards of activated copper oxide.

[0083] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention, including the claims, is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may also be combined, the steps may be implemented in any order, and there are many other variations of different aspects of the present invention as above, which are not provided in detail for the sake of simplicity.

[0084] The embodiments of the present invention are intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An activated copper oxide preparation system using ammonia-carbon recycling, characterized in that: include: A carbonization unit, an ammonia leaching unit, a deamination carbon unit, a centrifugal drying unit and a calcination unit connected in sequence; The carbonization unit is used to prepare a copper-dissolving reagent using ammonia water and carbon dioxide; The ammonia leaching unit is used to mix the copper raw material with the copper-dissolving reagent to prepare the copper-ammine complex; The deamination carbon unit is used to heat the copper ammonia complex to produce basic copper carbonate slurry and ammonia carbon mixed gas; The centrifugal drying unit is used to centrifuge and dry the basic copper carbonate slurry to prepare basic copper carbonate solid; The calcination unit is used to calcine basic copper carbonate solid at high temperature to produce active copper oxide.

2. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 1, characterized in that: The centrifugal drying unit is communicated with the ammonia leaching unit.

3. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 1, characterized in that: The deamination carbon unit includes a distillation tower, a vacuum pump and an absorption tower connected in sequence. The distillation tower is connected to the ammonia leaching unit and the centrifugal drying unit respectively; the absorption tower is connected to the carbonization unit.

4. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 3, characterized in that: The deamination carbon unit also includes a cooler, the heat flow inlet of the cooler is connected to the bottom of the absorption tower, and the heat flow outlet of the cooler is divided into two paths, one path refluxes to the top of the absorption tower, and the other path is connected to the carbonization unit.

5. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 3, characterized in that: The deamination carbon unit further includes a reboiler, which is communicated with the distillation tower.

6. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 3, characterized in that: The distillation tower has an operating pressure of 35 to 80 KPa and an operating temperature of 75 to 95°C.

7. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 3, characterized in that: The distillation tower comprises an upper head, a cylinder and a lower cone section welded in sequence from top to bottom; The upper cover is provided with a gas phase port, which is connected to the vacuum pump; The cylinder is provided with a feed port, which is connected to the ammonia leaching unit; The lower cone section is provided with a discharge port, which is communicated with the centrifugal drying unit.

8. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 7, characterized in that: A vertical sieve plate is provided in the cylinder.

9. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 3, characterized in that: The vacuum pump is a jet vacuum pump.

10. The activated copper oxide preparation system for ammonia-carbon recycling according to claim 3, characterized in that: The absorption tower is a packed tower.

Images