CN111747440B - Method for preparing high-purity active copper oxide by basic etching solution secondary ammonia distillation method - Google Patents
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Abstract
The invention provides a method for preparing high-purity active copper oxide by a basic etching solution secondary ammonia distillation method, which comprises the steps of adding food-grade sodium carbonate into the basic etching solution, then introducing steam into an ammonia distillation tower, controlling the temperature in the tower to be 120-125 ℃ for reaction for 1-2h to obtain basic copper carbonate (coprecipitation containing basic copper carbonate) precipitate, filtering, washing to obtain crude basic copper carbonate, adding carbonized ammonia water solution into the basic copper carbonate, introducing oxygen, stirring and dissolving to obtain copper ammonia solution, then adding sodium carbonate with a preset metering, introducing steam into the ammonia distillation tower again to obtain basic copper carbonate precipitate, filtering, washing, and calcining at high temperature to obtain active copper oxide for electroplating.
Description
Technical Field
The invention relates to a method for preparing high-purity active copper oxide by a basic etching solution secondary ammonia distillation method.
Background
The main component of the alkaline etching solution is a solution containing copper ammonia ions, and the main component comprises copper chloride, ammonia water, ammonium chloride and the like. When etching a circuit board, the alkaline etching solution has the advantages of low consumption, low price, high copper dissolution, small side etching, high etching speed and the like, and does not damage the ink components on the copper-clad substrate, and is widely applied at present. The main component in the alkaline etching waste liquid is complex Cu (NH) 3 ) 2 Cl 2 The ammonia water, chloride and the like are directly discharged without proper disposal, so that not only is valuable resource wasted, but also huge damage is caused to the environment. In the prior art, one of the common methods for treating alkaline etching solution is to add enough sodium hydroxide solution into alkaline etching waste liquid and heat the alkaline etching waste liquid to generate copper oxide and ammonia gas so as to extract copper ions and ammonium ions in the waste liquid, the process technology is mature, the treatment capacity is large and the like, but the technology is widely adopted, but precious fresh water is greatly salted, the ammonia nitrogen content in the treated waste water is not easy to reach the standard, therefore, the technology has defects, and the copper oxide material obtained by an ammonia distillation method of the alkaline etching solution is treated for a long time at a high temperature of strong alkali, and the obtained copper oxide contains higher impurities and has lower activity, thereby being unfavorable for later stage makingIs used.
Disclosure of Invention
The invention provides a method for preparing high-purity active copper oxide by a basic etching solution secondary ammonia distillation method, which comprises the steps of adding food-grade sodium carbonate into the basic etching solution, then introducing steam into an ammonia distillation tower, controlling the temperature in the tower to be 120-125 ℃ for reaction for 1-2h to obtain basic copper carbonate (coprecipitation containing basic copper carbonate) sediment, filtering, washing to obtain crude basic copper carbonate, adding carbonized ammonia water solution into the basic copper carbonate, then adding sodium carbonate with preset metering, introducing steam into the ammonia distillation tower again, controlling the temperature in the tower to be 145-150 ℃ for reaction for 2-3h to obtain basic copper carbonate sediment, filtering, washing, and calcining at high temperature to obtain active copper oxide for electroplating.
The specific scheme is as follows:
a method for preparing high-purity active copper oxide by a basic etching solution secondary ammonia distillation method, which comprises the following steps:
1) Adding excessive sodium carbonate into the alkaline etching solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 120-125 ℃ for reaction for 1-2h to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, and washing to obtain crude basic copper carbonate;
4) Introducing liquid ammonia into water to prepare concentrated ammonia water with the concentration of 136-138g/L, and then introducing carbon dioxide into the concentrated ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 80-85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.04-0.08 mol/L;
6) Adding a preset amount of hydrogen peroxide, stirring, and then adding a preset amount of sodium carbonate to obtain a mixed solution;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 145-150 ℃ for 2-3h to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing, and drying to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing air, heating to 680-700 ℃ for calcination for 1-1.5h, cooling to 550-570 ℃ for calcination for 1-1.5h, cooling again to 460-480 ℃ for calcination for 2-3h, and thus obtaining the active copper oxide for electroplating.
Further, in the step 1, the alkaline etching solution is alkaline etching waste liquid, sodium carbonate is food grade, and the adding amount of the sodium carbonate is 3-4 times of the molar amount of copper ions in the solution.
Further, the washing process in the steps 3 and 8 is to wash 3 times with de-ethanol and 3 times with deionized water.
Further, the pressure of introducing carbon dioxide into the concentrated ammonia water is 0.05-0.1MPa; and introducing carbon dioxide into the concentrated ammonia water, and cooling the concentrated ammonia water to make the temperature of the concentrated ammonia water be less than 15 ℃.
Further, in the step 6, the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:6-7, and the ratio of the amount of sodium carbonate added to the amount of basic copper carbonate is 1.5-2:1.
7. Further, the particle diameter D50 of the copper oxide powder is 1-10 micrometers, and the bulk density is 1.0-1.3g/m 3 。
The invention has the following beneficial effects:
compared with the prior art, the invention has the advantages that:
1. sodium carbonate is added as a separating agent, so that the alkaline environment is reduced, and a primary ammonia distillation method adopts low-temperature short-time heating to obtain semi-finished basic copper carbonate, and other impurity metal cations and impurity anions except chlorine are primarily removed;
2. washing basic copper carbonate to further remove impurities, dissolving the basic copper carbonate in carbonized ammonia water solution in a specific concentration range again, adjusting the concentration of copper ions to be in an extremely low numerical range, adding hydrogen peroxide to ensure that the copper ions are oxidized into bivalent copper particles, adding predetermined metering sodium carbonate under the copper ion content of the concentration, performing secondary ammonia distillation, and obtaining basic copper carbonate sediment with the granularity of microns under the specific concentration;
8. then calcining basic copper carbonate in three temperature ranges of the invention, so that the particle diameter D50 of the copper oxide powder is 1-10 microns, and the bulk density is 1.0-1.3g/m 3 Is a high-activity copper oxide powder.
3. The method adopts a secondary ammonia distillation method to remove impurity ions in a divided manner, so that high-purity copper oxide can be obtained, and high-activity copper oxide rice flour with specific particle size and bulk density can be obtained through multiple short-time calcination in a three-temperature interval.
Detailed Description
The present invention will be described in more detail by way of specific examples, but the scope of the present invention is not limited to these examples.
Example 1
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 3 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 120 ℃ for reaction for 1h to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare concentrated ammonia water with the concentration of 136g/L, then introducing carbon dioxide into the concentrated ammonia water, wherein the pressure of the introduced carbon dioxide is 0.05MPa, and cooling the concentrated ammonia water to the temperature of less than 15 ℃ while introducing the carbon dioxide into the concentrated ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 80%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.04 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:6, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 1.5;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 145 ℃ for 2 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing oxygen, heating to 680 ℃ for calcination for 1h, cooling to 550 ℃ for calcination for 1h, cooling again to 460 ℃ for calcination for 2h, and obtaining the active copper oxide for electroplating.
Example 2
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 3.5 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 122 ℃ for reaction to 1.5, so as to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare concentrated ammonia water with the concentration of 137g/L, introducing carbon dioxide into the concentrated ammonia water, wherein the pressure of the introduced carbon dioxide is 0.08MPa, and cooling the concentrated ammonia water to the temperature of less than 15 ℃ while introducing the carbon dioxide into the concentrated ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 83%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.06 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:6.5, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 1.7:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 147 ℃ for 2.5 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing oxygen, heating to 690 ℃ to calcine for 1.2 hours, cooling to 560 ℃ to calcine for 1.2 hours, cooling again to 470 ℃ to calcine for 2.5 hours, and obtaining the active copper oxide for electroplating.
Example 3
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 4 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 125 ℃ for 2 hours to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare strong ammonia water with the concentration of 138g/L, then introducing carbon dioxide into the strong ammonia water, wherein the pressure of the introduced carbon dioxide is 0.1MPa, and cooling the strong ammonia water to make the temperature of the strong ammonia water less than 15 ℃ while introducing the carbon dioxide into the strong ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.08 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:7, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 2:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 150 ℃ for reaction for 3 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing oxygen, heating to 700 ℃ for calcination for 1.5 hours, cooling to 570 ℃ for calcination for 1.5 hours, cooling to 480 ℃ again, and calcining for 3 hours to obtain the active copper oxide for electroplating.
Comparative example 1
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 4 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 125 ℃ for 2 hours to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare strong ammonia water with the concentration of 138g/L, then introducing carbon dioxide into the strong ammonia water, wherein the pressure of the introduced carbon dioxide is 0.1MPa, and cooling the strong ammonia water to make the temperature of the strong ammonia water less than 15 ℃ while introducing the carbon dioxide into the strong ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.5 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:7, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 2:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 150 ℃ for reaction for 3 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing oxygen, heating to 700 ℃ for calcination for 1.5 hours, cooling to 570 ℃ for calcination for 1.5 hours, cooling to 480 ℃ again, and calcining for 3 hours to obtain the active copper oxide for electroplating.
Comparative example 2
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 4 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 125 ℃ for 2 hours to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare strong ammonia water with the concentration of 138g/L, then introducing carbon dioxide into the strong ammonia water, wherein the pressure of the introduced carbon dioxide is 0.1MPa, and cooling the strong ammonia water to make the temperature of the strong ammonia water less than 15 ℃ while introducing the carbon dioxide into the strong ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.08 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:7, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 2:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 150 ℃ for reaction for 3 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) And placing the basic copper carbonate into a calciner, introducing oxygen, and calcining for 6 hours at the temperature of 700 ℃ to obtain the active copper oxide for electroplating.
Comparative example 3
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 4 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 125 ℃ for 2 hours to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare strong ammonia water with the concentration of 138g/L, then introducing carbon dioxide into the strong ammonia water, wherein the pressure of the introduced carbon dioxide is 0.1MPa, and cooling the strong ammonia water to make the temperature of the strong ammonia water less than 15 ℃ while introducing the carbon dioxide into the strong ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.08 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:7, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 2:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 150 ℃ for reaction for 3 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) And placing the basic copper carbonate into a calciner, introducing oxygen, heating to 570 ℃, and calcining for 6 hours to obtain the active copper oxide for electroplating.
Comparative example 4
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 4 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 125 ℃ for 2 hours to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare strong ammonia water with the concentration of 138g/L, then introducing carbon dioxide into the strong ammonia water, wherein the pressure of the introduced carbon dioxide is 0.1MPa, and cooling the strong ammonia water to make the temperature of the strong ammonia water less than 15 ℃ while introducing the carbon dioxide into the strong ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.08 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:7, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 2:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 150 ℃ for reaction for 3 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) And placing the basic copper carbonate into a calciner, introducing oxygen, heating to 480 ℃, and calcining for 6 hours to obtain the active copper oxide for electroplating.
Comparative example 5
1) Adding food-grade sodium carbonate into the alkaline etching waste liquid, wherein the adding amount of the sodium carbonate is 4 times of the molar amount of copper ions in the solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 125 ℃ for 2 hours to obtain basic copper carbonate precipitate;
3) Filtering to obtain the precipitate, removing ethanol, washing for 3 times, and washing with deionized water for 3 times to obtain basic copper carbonate;
4) Introducing liquid ammonia into water to prepare strong ammonia water with the concentration of 138g/L, then introducing carbon dioxide into the strong ammonia water, wherein the pressure of the introduced carbon dioxide is 0.1MPa, and cooling the strong ammonia water to make the temperature of the strong ammonia water less than 15 ℃ while introducing the carbon dioxide into the strong ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.08 mol/L;
6) Adding a predetermined amount of hydrogen peroxide, stirring, adding sodium carbonate with a predetermined amount, wherein the volume ratio of the hydrogen peroxide to the cuprammonium solution is 1:7, adding the sodium carbonate with a predetermined amount, and stirring to obtain a mixed solution, wherein the ratio of the amount of the added sodium carbonate to the amount of the basic copper carbonate is 2:1;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 150 ℃ for reaction for 3 hours to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 65 ℃ to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing oxygen, heating to 700 ℃ for calcination for 3 hours, cooling to 480 ℃ for calcination for 3 hours, and obtaining the active copper oxide for electroplating.
Comparative example 6
In the prior art, sodium hydroxide is added as a precipitator in a one-time ammonia distillation method, the ammonia distillation temperature is 150 ℃ and the time is 3 hours, and after basic copper carbonate is obtained, the basic copper carbonate is filtered and washed, and the copper oxide particles are obtained by calcining at 600 ℃ for 6 hours.
Testing and results
The copper oxides of examples 1-3 and comparative examples 1-6 were tested for particle size, bulk density, and chloride ion content. As can be seen from Table 1, the method provided by the invention has relatively uniform average particle size and excellentHigh bulk density, and extremely low impurity levels. When the concentration of Cu ions is higher, the particle size of the obtained product is larger, and the impurity content of chloride ions is more than 2 ppm; the inventors found that lowering the concentration of Cu ions is beneficial to lowering the impurity concentration at the time of precipitation; and the inventors found that when a one-stage sintering or two-stage sintering process is employed, a particle having a particle diameter in a range out of the range of the present invention is obtained in large amounts, and even when the particle diameter is in the range of the present invention, the bulk density cannot achieve the high bulk density of the present invention. The particle size of the invention is in the range of 1-10 microns in D50 and 1.0-1.3g/m in bulk density 3 And the product has high purity and chloride ion content lower than 1ppm.
TABLE 1
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention.
Claims (5)
1. A method for preparing high-purity active copper oxide by a basic etching solution secondary ammonia distillation method, which comprises the following steps:
1) Adding excessive sodium carbonate into the alkaline etching solution to obtain a mixed solution;
2) Introducing the mixed solution into an ammonia distillation tower, introducing heating steam, and controlling the temperature in the tower to be 120-125 ℃ for reaction for 1-2h to obtain a precipitate containing basic copper carbonate;
3) Filtering to obtain the precipitate, and washing to obtain crude basic copper carbonate;
4) Introducing liquid ammonia into water to prepare concentrated ammonia water with the concentration of 136-138g/L, and then introducing carbon dioxide into the concentrated ammonia water to prepare carbonized ammonia water, wherein the carbonization degree is 80-85%;
5) Adding the basic copper carbonate obtained in the step 5 into carbonized ammonia water solution, introducing oxygen, and stirring and dissolving to obtain copper ammonia solution with copper ion concentration of 0.04-0.08 mol/L;
6) Adding a preset amount of hydrogen peroxide, stirring, and then adding a preset amount of sodium carbonate to obtain a mixed solution;
7) Introducing the mixed solution in the step 6 into an ammonia distillation tower, introducing steam, and controlling the temperature in the tower to be 145-150 ℃ for 2-3h to obtain basic copper carbonate precipitate;
8) Filtering to obtain the precipitate, washing, and drying to obtain basic copper carbonate;
9) Placing the basic copper carbonate into a calciner, introducing air, heating to 680-700 ℃ to calcine for 1-1.5h, cooling to 550-570 ℃ to calcine for 1-1.5h, cooling again to 460-480 ℃ to calcine for 2-3h to obtain active copper oxide for electroplating, wherein the particle size D50 of the copper oxide powder is 1-2 microns, and the stacking density is 1.0-1.3g/m 3 。
2. The method for preparing high-purity active copper oxide according to claim 1, wherein the alkaline etching solution in the step 1 is alkaline etching waste liquid, sodium carbonate is food grade, and the adding amount of the sodium carbonate is 3-4 times of the molar amount of copper ions in the solution.
3. The method for preparing high purity activated copper oxide according to claim 1, wherein the washing process in steps 3 and 8 is a de-ethanol washing process for 3 times and a deionized water washing process for 3 times.
4. The method for preparing high-purity activated copper oxide according to claim 1, wherein the pressure of introducing carbon dioxide into the concentrated ammonia water is 0.05-0.1MPa; and introducing carbon dioxide into the concentrated ammonia water, and cooling the concentrated ammonia water to make the temperature of the concentrated ammonia water be less than 15 ℃.
5. The method for preparing high-purity activated copper oxide according to claim 1, wherein in the step 6, the ratio of the volume of hydrogen peroxide to the volume of copper ammonia solution is 1:6-7, and the ratio of the amount of sodium carbonate added to the amount of basic copper carbonate is 1.5-2:1.
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