Preparation process and application of superfine copper oxide powder

Abstract

The application discloses a preparation process and application of superfine copper oxide powder, and the preparation process comprises the following steps: (1) mixing cuprous salt and hydrochloric acid to obtain a first solution; (2) atomizing the alkaline solution and the first solution respectively, then simultaneously feeding into a reactor, stirring at a certain temperature, and then separating to obtain a precipitate; and (3) washing, drying, grinding, calcining and cooling the precipitate to obtain the copper oxide powder. The copper oxide powder is generated by the atomization method, has a purity of 99.6%, no agglomeration phenomenon, and uniform particle size distribution.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metal powder, and specifically relates to a preparation process of superfine copper oxide powder and application thereof. BACKGROUND

[0002] Copper oxide belongs to transition metal oxide, and has the characteristics of light, electricity, magnetism and catalysis, which can be applied to many fields. In the field of electroplating and electronics, the requirements for copper oxide are mainly uniform particle size, high purity and strong activity of the powder, and the dissolution rate is greater than 30s. However, in the existing preparation method of copper oxide powder, the product is obtained by mixing copper sulfate solution and alkaline solution, separating, washing, drying and calcining. However, the product obtained by using this method has a small powder dissolution rate, is easy to agglomerate and has low purity.

[0003] Chinese patent CN105084408B discloses a preparation method of copper oxide powder. Copper powder, hydrogen peroxide, sulfuric acid, sodium carbonate and sodium bicarbonate are mixed to generate basic copper carbonate, which is then decomposed into copper oxide powder at high temperature. The process is relatively complex and the cost is high, mainly because the interaction between the volatile solvent and copper oxide controls the formation of the morphology of the copper oxide powder.

[0004] Chinese patent CN107162038B discloses a cuprous oxide powder and a preparation method thereof. The cuprous oxide powder is prepared by an atomization method, and oxygen and nitrogen mixed gas is introduced to make copper powder react with oxygen to obtain cuprous oxide. The particle size of the prepared cuprous oxide is 2-15μm, but the technical problem of low purity of copper oxide powder in the prior art is not solved. SUMMARY

[0005] In order to solve the above problems, the first aspect of the application provides a preparation process of superfine copper oxide powder, characterized in that it comprises the following steps: (1) mixing cuprous salt and hydrochloric acid to obtain a first solution; (2) atomizing the alkaline solution and the first solution respectively and introducing them into a reactor, stirring at a certain temperature and then separating to obtain a precipitate; (3) washing, drying, grinding, calcining and cooling the precipitate to obtain copper oxide powder.

[0006] Further preferably, the mass fraction of hydrochloric acid in step (1) is 37%.

[0007] Preferably, the atomization pressure of the alkaline solution and the first solution in step (2) is 1-3MPa.

[0008] When the atomization pressure is high, the solution droplets are small and adhere to each other, resulting in an increase in the particle size of the copper oxide powder and a sharp decrease in the sphericity of the copper oxide powder. When the atomization pressure is low, the atomized particles cannot be formed, so the atomization pressure is limited to 1-3 MPa. At this time, a homogeneous reaction occurs in the reactor, limiting the growth of the crystal grains and resulting in good dispersion and no agglomeration.

[0009] Further preferably, the atomization pressure of the alkaline solution and the first solution in step (2) is 1-2 MPa.

[0010] Further preferably, the atomization pressure of the alkaline solution and the first solution in step (2) is 1.5 MPa.

[0011] Preferably, the alkaline solution in step (2) is at least one of ammonia, sodium hydroxide and potassium hydroxide solution.

[0012] Further preferably, the alkaline solution in step (2) is ammonia.

[0013] Preferably, the concentration of the alkaline solution is 0.5-2 mol / L.

[0014] Further preferably, the concentration of the alkaline solution is 0.5-1.5 mol / L.

[0015] Further preferably, the concentration of the alkaline solution is 1 mol / L.

[0016] The application limits the concentration of the alkaline solution to 0.5-2 mol / L, avoiding a too low pH value that causes a side reaction and affects the purity of the copper oxide powder. When the ammonia content is high, copper ions are easily combined with ammonia to form a copper complex, resulting in a decrease in the purity of the copper oxide powder. Therefore, the concentration of the ammonia is further limited to 0.5-2 mol / L.

[0017] Preferably, the gas in the reactor in step (2) is an inert gas and oxygen.

[0018] Further preferably, the inert gas is helium and / or argon.

[0019] Preferably, the volume ratio between the inert gas and oxygen is 1:(1-3).

[0020] When the oxygen content is less, the cuprous ions cannot be completely reacted, resulting in the decrease of the purity of the copper oxide powder and the slow reaction process, and a large amount of copper hydroxide precipitate is easily produced, so that the copper hydroxide precipitate is wrapped by the copper oxide, resulting in the uneven particle size of the copper oxide powder, when the volume ratio of the inert gas and the oxygen is 1:(1-3), at this time, the grain nucleation rate in the reactor is greater than the uniform nucleation rate, so that the particle size distribution in the gas phase system is narrowed, and the more uniform the particle size distribution is, the better the dispersion performance of the composite powder is.

[0021] Further preferably, the volume ratio between the inert gas and the oxygen is 1:2.5.

[0022] Further preferably, the volume ratio between the inert gas and the oxygen is 1:2.5.

[0023] Preferably, the temperature in the step (2) is 60-100℃.

[0024] Further preferably, the temperature in the step (2) is 80-100℃.

[0025] Further preferably, the temperature in the step (2) is 90℃.

[0026] Preferably, the stirring speed in the step (2) is 80-150rpm / min.

[0027] Further preferably, the stirring speed in the step (2) is 100-150rpm / min.

[0028] Further preferably, the stirring speed in the step (2) is 120rpm / min.

[0029] Preferably, the drying temperature in the step (3) is 100-200℃.

[0030] Further preferably, the drying temperature in the step (3) is 130-170℃.

[0031] Further preferably, the drying temperature in the step (3) is 150℃.

[0032] The second aspect of the application provides an application of the preparation process of the ultrafine copper oxide powder in the field of electroplating and electronics.

[0033] Beneficial effects:

[0034] (1) The copper oxide powder prepared by the atomization method has a purity of 99.6%, a large dissolution rate, and can be applied in the fields of electroplating, electronics and the like, and in addition, the average particle size of the copper oxide powder prepared by the application is only 60μm, and there is no agglomeration phenomenon, and the particle size distribution is uniform.

[0035] (2) The acid etching waste liquid of the printed circuit board contains a large amount of copper ions and cuprous ions, and the preparation process can be applied to the regeneration of the acid etching waste liquid of the printed circuit board, and is environment-friendly.

[0036] (3) The preparation process is simple and low in cost, and can be applied to mass production. EMBODIMENT

[0037] Example 1

[0038] A preparation process of superfine copper oxide powder, characterized in that it comprises the following steps: (1) mixing cuprous chloride and hydrochloric acid to obtain a first solution, the weight ratio of cuprous chloride to hydrochloric acid being 5:1; (2) atomizing the alkaline solution and the first solution respectively and then simultaneously feeding them into a reactor, reacting for 30 min under the conditions of a temperature of 90 DEG C and a stirring speed of 120 rpm / min, and obtaining precipitate through gas-solid separation; (3) washing the precipitate in pure water until it is neutral, drying it at a temperature of 150 DEG C, grinding it, calcining it at a temperature of 400 DEG C for 2 h, and then cooling it to obtain copper oxide powder.

[0039] The mass fraction of the hydrochloric acid in step (1) is 37%.

[0040] The atomizing pressure of the alkaline solution and the first solution in step (2) is 1.5 MPa.

[0041] The alkaline solution in step (2) is ammonia water, and the concentration is 1 mol / L.

[0042] The volume ratio between the alkaline solution and the first solution in step (2) is 6:1.

[0043] The gas in the reactor in step (2) is inert gas and oxygen, and the volume ratio between the two is 1:2.5.

[0044] Example 2

[0045] A preparation process of superfine copper oxide powder, characterized in that it comprises the following steps: (1) mixing cuprous chloride and hydrochloric acid to obtain a first solution, the weight ratio of cuprous chloride to hydrochloric acid being 5:1; (2) atomizing the alkaline solution and the first solution respectively and then simultaneously feeding them into a reactor, reacting for 30 min under the conditions of a temperature of 90 DEG C and a stirring speed of 120 rpm / min, and obtaining precipitate through gas-solid separation; (3) washing the precipitate in pure water until it is neutral, drying it at a temperature of 150 DEG C, grinding it, calcining it at a temperature of 400 DEG C for 2 h, and then cooling it to obtain copper oxide powder.

[0046] The mass fraction of the hydrochloric acid in step (1) is 37%.

[0047] The atomization pressure of the basic solution and the first solution in step (2) is 1.5 MPa.

[0048] The basic solution in step (2) is ammonia water, and the concentration is 1.5 mol / L.

[0049] The volume ratio between the basic solution and the first solution in step (2) is 6:1.

[0050] The gas in the reactor in step (2) is inert gas and oxygen, and the volume ratio between the two is 1:3.

[0051] Example 3

[0052] A preparation process of superfine copper oxide powder, characterized in that it comprises the following steps: (1) mixing cuprous chloride and hydrochloric acid to obtain a first solution, and the weight ratio of cuprous chloride to hydrochloric acid is 5:1; (2) atomizing the basic solution and the first solution respectively and then simultaneously feeding them into a reactor, and reacting for 30 min under the conditions of a temperature of 90°C and a stirring speed of 120 rpm / min, and then separating the precipitate by gas-solid separation; (3) washing the precipitate in pure water until it is neutral, drying it at a temperature of 150°C, grinding it, calcining it at a temperature of 400°C for 2 h, and then cooling it to obtain the copper oxide powder.

[0053] The mass fraction of hydrochloric acid in step (1) is 37%.

[0054] The atomization pressure of the basic solution and the first solution in step (2) is 3 MPa.

[0055] The basic solution in step (2) is ammonia water, and the concentration is 1 mol / L.

[0056] The volume ratio between the basic solution and the first solution in step (2) is 6:1.

[0057] The gas in the reactor in step (2) is inert gas and oxygen, and the volume ratio between the two is 1:2.5.

[0058] Comparative Example 1

[0059] The atomization pressure of the basic solution and the first solution in step (2) is changed to 5 MPa, and the rest is the same as in Example 1.

[0060] Comparative Example 2

[0061] The application discloses a preparation process of superfine copper oxide powder, which is characterized by comprising the following steps: (1) mixing cuprous chloride and hydrochloric acid to obtain a first solution, wherein the weight ratio of the cuprous chloride to the hydrochloric acid is 5:1; (2) atomizing the alkaline solution and the first solution respectively, then simultaneously feeding the atomized solutions into a reactor, and reacting for 30 min under the conditions that the temperature is 90 DEG C and the stirring speed is 120 rpm / min, and then separating the precipitate from gas by a gas-solid separation method; and (3) washing the precipitate in pure water until the precipitate is neutral, drying the precipitate at a temperature of 150 DEG C, grinding the dried precipitate, calcining the ground precipitate at a temperature of 400 DEG C for 2 h, and then cooling the calcined precipitate to obtain the superfine copper oxide powder.

[0062] The mass fraction of the hydrochloric acid in the step (1) is 37%.

[0063] The atomizing pressure of the alkaline solution and the first solution in the step (2) is 3 MPa.

[0064] The alkaline solution in the step (2) is ammonia water, and the concentration of the ammonia water is 0.2 mol / L.

[0065] The volume ratio between the alkaline solution and the first solution in the step (2) is 6:1.

[0066] The gas in the reactor in the step (2) is inert gas and oxygen, and the volume ratio between the inert gas and the oxygen is 1:2.5.

[0067] Comparative Example 3

[0068] The volume ratio between the inert gas and the oxygen is changed to 2:1, and the rest is the same as in the embodiment 1.

[0069] Performance Evaluation

[0070] 1. Copper oxide content test: the content of the copper oxide is tested according to the method in the national standard GB / T26046-2010.

[0071] 2. Average particle size test of the copper oxide powder: the average particle sizes of the copper oxide powders in the embodiments 1-3 and the comparative examples 1-3 are measured by using a laser particle size analyzer.

[0072] Table 1

[0073] Example Copper oxide content (%) Average particle size (μm) Example 1 99.6 60 Example 2 99.5 61 Example 3 99.6 63 Comparative Example 1 99.5 69 Comparative Example 2 98.5 63 Comparative Example 3 Performance Evaluation 98.6 72

[0074] Compared with the embodiment 1, the atomizing pressure is increased in the comparative example 1, the solution droplets are small and are likely to be adhered, the particle size of the copper oxide powder is increased, the concentration of the ammonia water is low in the comparative example 2, the pH value in the reaction process is small, a side reaction is caused, and the purity is reduced, and the content of the oxygen is reduced in the comparative example 3, cuprous ions cannot be completely reacted, the reaction process is slow, and the purity is reduced and the particle size is increased.

Claims

1. A preparation process for ultrafine copper oxide powder, characterized in that, The steps are as follows: (1) Mix cuprous chloride and hydrochloric acid to obtain a first solution, with a weight ratio of cuprous chloride to hydrochloric acid of 5:1; (2) Atomize the alkaline solution and the first solution separately and simultaneously introduce them into the reactor. React for 30 minutes at a temperature of 90°C and a stirring speed of 120 rpm / min. Obtain the precipitate through gas-solid separation; (3) Wash the precipitate with pure water until neutral, dry it at 150°C, grind it, calcine it at 400°C for 2 hours, and then cool it to obtain copper oxide powder. The mass fraction of hydrochloric acid in step (1) is 37%; In step (2), the atomization pressure of both the alkaline solution and the first solution is 1.5 MPa. In step (2), the alkaline solution is ammonia water with a concentration of 1 mol / L; In step (2), the volume ratio between the alkaline solution and the first solution is 6:1; In step (2), the gas in the reactor is an inert gas and oxygen, with a volume ratio of 1:2.5.