CN107759464B - Controllable preparation method of monodisperse copper oxalate powder - Google Patents
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Abstract
The invention relates to the technical field of preparation of monodisperse powder materials, and provides a controllable preparation method of monodisperse copper oxalate powder, which comprises the steps of uniformly mixing soluble copper salt, soluble oxalate solution and Ethylene Diamine Tetraacetic Acid (EDTA) solution according to the molar ratio of 1:1:0-1:1:5, standing at a certain temperature, filtering, washing and drying to obtain the monodisperse copper oxalate powder. The invention has the beneficial effects that: the operation is simple, the monodispersity of the copper oxalate is good, the scale-up preparation is easy, and the preparation can be carried out at room temperature; the precise control of the size of the copper oxalate particles is realized, and the size of the copper oxalate particles can be controlled to be 2-4 microns; can be used as a precursor, and can obtain copper oxide, cuprous oxide and metal copper powder through thermal decomposition.
Description
Technical Field
The invention relates to the technical field of preparation of monodisperse powder materials, in particular to a controllable preparation method of monodisperse copper oxalate powder.
Background
The controllable preparation of nano and micron powder material is very critical to the material performance of various macro-size and structure made from the nano and micron powder material as basic raw material. A fine powder material having uniform basic characteristics such as particle size, morphology and component and good dispersibility, i.e., a so-called monodisperse particle material, is particularly preferred in the industry. The properties of the monodisperse powder material are uniform and consistent, and the monodisperse powder material is beneficial to processing into functional material products in a refined, stabilized and consistent manner; secondly, the preparation process of the monodisperse powder material is demanding, so the preparation cost is particularly high in large-scale preparation cost, and the production and preparation of the monodisperse powder material are challenging except that special industrial applications put special requirements on the monodisperse powder material in actual production. With the rapid development of various application industries, the requirements on the characteristics of the basic raw material powder such as morphology, granularity and the like are inevitably higher and higher, and the requirements are more and more personalized. The requirement of micron and nanometer powder materials with monodisperse characteristics is the most common and popular one.
The wet method for preparing the monodisperse powder particle material has the characteristics of low price, convenience, economy, fine cutting granularity and morphology and the like, and has the defects of easy agglomeration of powder particles, difficult large-scale reproduction and amplification and the like. In contrast, the wet milling technique is still more commonly adopted, mainly due to its strong flexibility and adaptability, and almost most powder materials can be prepared by the method. The preparation process of the monodisperse powder material relates to professional knowledge in aspects of solution chemistry, solution crystallography, colloid chemistry and the like, but still belongs to experience level knowledge in terms of fine control preparation, which shows the complexity and diversity of the preparation of the powder material.
Copper oxalate is an important chemical product, is mainly used as a precursor raw material of powder materials such as copper powder, copper oxide, cuprous oxide and the like, and can be used in the fields of conductive paste, pigment, photocatalysis and the like. For the preparation of the monodisperse granular material with micron-scale or even nano-scale, the copper oxalate is taken as a precursor, and compared with copper hydroxide and basic copper carbonate, the copper oxalate composite material has more outstanding comprehensive advantages. For example, copper oxalate is crystalline, and the morphology of precipitated crystal is well controlled, while copper hydroxide and basic copper carbonate are mostly amorphous, the appearance is difficult to control well, and most importantly, amorphous precipitated particles are easy to agglomerate and difficult to be independently and individually dispersed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a controllable preparation method of monodisperse copper oxalate powder.
The invention relates to a controllable preparation method of monodisperse copper oxalate powder, which comprises the steps of uniformly mixing soluble copper salt, soluble oxalate solution and Ethylene Diamine Tetraacetic Acid (EDTA) solution according to the molar ratio of 1:1:0-1:1:5, standing, filtering, washing and drying at a certain temperature, thus obtaining the monodisperse copper oxalate powder.
Further, the soluble copper salt is copper sulfate, copper chloride and copper nitrate; the soluble oxalate is sodium oxalate, potassium oxalate or ammonium oxalate.
Further, the method comprises the following specific steps:
step one, weighing raw materials: taking soluble copper salt, soluble oxalate, Ethylene Diamine Tetraacetic Acid (EDTA) and deionized water as raw materials;
preparing weighed soluble copper salt and soluble oxalate into solution by using deionized water, preparing weighed EDTA into base solution with the concentration of 0-0.05 mol/l, and controlling the pH value of the base solution to be 3-7;
adding 0.1-0.5mol/l of copper salt solution into a base solution containing EDTA, stirring for 5-30 minutes, then adding oxalate solution with the same amount as the copper salt solution to obtain a mixed solution, stirring the mixed solution for 1-5 minutes, and standing at room temperature;
and step four, sampling and filtering the mixed solution obtained in the step three at different time, repeatedly cleaning to remove impurity ions, and collecting solid copper oxalate powder to obtain the flaky monodisperse copper oxalate powder.
Further, 1.6 liters of deionized water is taken, EDTA is not added, the mixture is stirred to be completely dissolved, and the pH value is controlled to be 5; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, stirring for 5-30 minutes, then adding 200ml of soluble oxalate solution with the concentration of 0.1mol/l, stirring for 5 minutes, and then standing for 1 hour at room temperature; sampling and filtering, removing impurity ions through repeated cleaning, and collecting solid copper oxalate powder with the average particle size of 2.3 microns.
Further, 1.6 liters of deionized water is taken, 4g of EDTA is added, the mixture is stirred to be completely dissolved, and the pH value is controlled to be 7; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, and stirring for 5-10 minutes; then adding 200ml of soluble oxalate solution with the concentration of 0.1mol/l, stirring for 5 minutes, and then standing for 1 hour at room temperature; sampling and filtering for 10 minutes and 1 hour respectively, removing impurity ions through repeated cleaning, and collecting solid copper oxalate powder; the average particle size of the filtered solid copper oxalate powder was 2.1 microns at 10 minutes and 4.3 microns at 1 hour.
Further, 1.6 liters of deionized water is taken, 4g of EDTA is added, the mixture is stirred to be completely dissolved, and the pH value is controlled to be 7; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, and stirring for 5-30 minutes; then adding 200ml of soluble oxalate solution with the concentration of 0.1mol/l, and stirring for 2 minutes; standing for 1 hour at room temperature; then sampling and filtering are respectively carried out for 10 minutes and 1 hour, impurity ions are removed through repeated cleaning, solid copper oxalate powder is collected, the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.1 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 3.1 micrometers.
Further, 1.6 liters of deionized water is taken, 0.4g of EDTA is added, the mixture is stirred to be completely dissolved, and the pH value is controlled to be 5; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, and stirring for 5-10 minutes; then adding 200ml of 0.1mol/l oxalate solution, and stirring for 1 minute; standing for 1 hour at room temperature, sampling and filtering for 10 minutes and 1 hour respectively, removing impurity ions by repeated cleaning, and collecting solid copper oxalate powder, wherein the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.0 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 2.7 micrometers.
The invention has the beneficial effects that:
1. the operation is simple, the monodispersity of the copper oxalate is good, the scale-up preparation is easy, and the operation can be carried out at room temperature;
2. the precise control of the size of the copper oxalate particles is realized, and the size of the copper oxalate particles can be controlled to be 2-4 microns;
3. the cupric oxalate powder can be used as a precursor, and can be used for obtaining cupric oxide, cuprous oxide and metallic copper powder through thermal decomposition.
Drawings
Fig. 1 is a scanning electron micrograph of monodisperse copper oxalate powder particles obtained in example 1.
FIG. 2 is a scanning electron micrograph of monodisperse copper oxalate powder particles (10 min sampling) obtained in example 2.
FIG. 3 is a scanning electron micrograph of monodisperse copper oxalate powder particles (1 hour sampling) obtained in example 2.
FIG. 4 is a scanning electron micrograph of monodisperse copper oxalate powder particles (10 min sampling) obtained in example 3.
FIG. 5 is a scanning electron micrograph of monodisperse copper oxalate powder particles (1 hour sampling) obtained in example 3.
FIG. 6 is a scanning electron micrograph of monodisperse copper oxalate powder particles (10 min sampling) obtained in example 4.
FIG. 7 is a SEM photograph of monodisperse copper oxalate powder particles (1 hr sampling) obtained in example 4.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that technical features or combinations of technical features described in the following embodiments should not be considered as being isolated, and they may be combined with each other to achieve better technical effects. In the drawings of the embodiments described below, the same reference numerals appearing in the respective drawings denote the same features or components, and may be applied to different embodiments.
Example 1
Taking 1.6 liters of deionized water, adding no EDTA, stirring to completely dissolve the deionized water, and controlling the pH value to be 5; then 200ml of copper salt solution with the concentration of 0.1mol/l is added, the stirring is carried out for 5 to 30 minutes, then 200ml of oxalate solution with the concentration of 0.1mol/l is added, the stirring is carried out for 5 minutes, and then the mixture is stood for 1 hour at room temperature; sampling and filtering, removing impurity ions through repeated cleaning, and collecting solid copper oxalate powder with the average particle size of 2.3 microns. The typical topography is shown in fig. 1.
Example 2
Adding 4g of EDTA into 1.6 liters of deionized water, stirring to completely dissolve the EDTA, and controlling the pH value to be 7; then 200ml of copper salt solution with the concentration of 0.1mol/l is added, and the mixture is stirred for 5 to 10 minutes; then 200ml of oxalate solution with the concentration of 0.1mol/l is added, and the mixture is stirred for 5 minutes; standing for 1 hour at room temperature; then sampling and filtering are respectively carried out for 10 minutes and 1 hour, impurity ions are removed through repeated cleaning, solid copper oxalate powder is collected, the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.1 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 3.1 micrometers. Typical topography is shown in fig. 2 and 3, respectively.
Example 3
Adding 4g of EDTA into 1.6 liters of deionized water, stirring to completely dissolve the EDTA, and controlling the pH value to be 7; then 200ml of copper salt solution with the concentration of 0.1mol/l is added, and the mixture is stirred for 5 to 30 minutes; then 200ml of oxalate solution with the concentration of 0.1mol/l is added, and the mixture is stirred for 2 minutes; standing for 1 hour at room temperature; then sampling and filtering are respectively carried out for 10 minutes and 1 hour, impurity ions are removed through repeated cleaning, solid copper oxalate powder is collected, the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.1 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 3.1 micrometers. Typical topography is shown in fig. 4 and 5, respectively.
Example 4
Taking 1.6 liters of deionized water, adding 0.4g of EDTA, stirring to completely dissolve the EDTA, and controlling the pH value to be 5; then 200ml of copper salt solution with the concentration of 0.1mol/l is added, and the mixture is stirred for 5 to 10 minutes; then adding 200ml of 0.1mol/l oxalate solution, and stirring for 1 minute; standing for 1 hour at room temperature, sampling and filtering for 10 minutes and 1 hour respectively, removing impurity ions by repeated cleaning, and collecting solid copper oxalate powder, wherein the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.0 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 2.7 micrometers. Typical topography is shown in fig. 6 and 7, respectively.
While several embodiments of the present invention have been presented herein, it will be appreciated by those skilled in the art that changes may be made to the embodiments herein without departing from the spirit of the invention. The above examples are merely illustrative and should not be taken as limiting the scope of the invention.
Claims (5)
1. A controllable preparation method of monodisperse copper oxalate powder is characterized in that soluble copper salt, soluble oxalate solution and Ethylene Diamine Tetraacetic Acid (EDTA) solution are uniformly mixed according to a molar ratio of 1:1: x, then the mixture is stood at a certain temperature, filtered, washed and dried to obtain the monodisperse copper oxalate powder, wherein x is more than 0 and less than or equal to 5;
the method comprises the following specific steps:
step one, weighing raw materials: taking soluble copper salt, soluble oxalate, Ethylene Diamine Tetraacetic Acid (EDTA) and deionized water as raw materials;
step two, preparing weighed copper salt and oxalate into solution by using deionized water, preparing weighed EDTA into base solution with the concentration of y mol/l, and controlling the pH of the base solution to be between 3 and 7, wherein y is more than 0 and less than or equal to 0.05;
adding 0.1-0.5mol/l soluble copper salt solution into base solution containing y mol/l EDTA, stirring for 5-30 minutes, then adding oxalate solution with the same amount as the copper salt solution to obtain mixed solution, stirring the mixed solution for 1-5 minutes, and standing at room temperature;
and step four, sampling and filtering the mixed solution obtained in the step three at different time, repeatedly cleaning to remove impurity ions, and collecting solid copper oxalate powder to obtain the flaky monodisperse copper oxalate powder.
2. A controlled preparation method of monodisperse copper oxalate powder according to claim 1 wherein the soluble copper salt is copper sulfate, copper chloride, copper nitrate; the soluble oxalate is sodium oxalate, potassium oxalate or ammonium oxalate.
3. A controlled preparation method of monodisperse copper oxalate powder as described in claim 1, wherein 1.6 liters of deionized water is taken, 4g of EDTA is added, stirring is carried out to completely dissolve the EDTA, and the pH value is controlled to be 7; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, and stirring for 5 minutes; then adding 200ml of oxalate solution with the concentration of 0.1mol/l, stirring for 5 minutes, and then standing for 1 hour at room temperature; sampling and filtering for 10 minutes and 1 hour respectively, removing impurity ions through repeated cleaning, and collecting solid copper oxalate powder; the average particle size of the filtered solid copper oxalate powder was 2.1 microns at 10 minutes and 4.3 microns at 1 hour.
4. A controlled preparation method of monodisperse copper oxalate powder as described in claim 1, wherein 1.6 liters of deionized water is taken, 4g of EDTA is added, stirring is carried out to completely dissolve the EDTA, and the pH value is controlled to be 7; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, and stirring for 5 minutes; then 200ml of oxalate solution with the concentration of 0.1mol/l is added, and the mixture is stirred for 2 minutes; standing for 1 hour at room temperature; then sampling and filtering are respectively carried out for 10 minutes and 1 hour, impurity ions are removed through repeated cleaning, solid copper oxalate powder is collected, the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.1 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 3.1 micrometers.
5. A controlled preparation method of monodisperse copper oxalate powder as described in claim 1, wherein 1.6 liters of deionized water is taken, 0.4g of EDTA is added, stirring is carried out to completely dissolve the EDTA, and the pH value is controlled to be 5; then adding 200ml of soluble copper salt solution with the concentration of 0.1mol/l, and stirring for 5 minutes; then adding 200ml of 0.1mol/l oxalate solution, and stirring for 1 minute; standing for 1 hour at room temperature, sampling and filtering for 10 minutes and 1 hour respectively, removing impurity ions by repeated cleaning, and collecting solid copper oxalate powder, wherein the average particle size of the solid copper oxalate powder sampled and filtered for 10 minutes is 2.0 micrometers, and the average particle size of the solid copper oxalate powder sampled and filtered for 1 hour is 2.7 micrometers.
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| CN114181068A (en) * | 2021-11-25 | 2022-03-15 | 江西省科学院能源研究所 | Cerium-doped copper oxalate nano material and preparation method thereof |
| CN115504875A (en) * | 2022-10-09 | 2022-12-23 | 昆明理工大学 | Spherical-like lithium/sodium ion battery copper oxalate and negative electrode material of decomposition derivative thereof |
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| TW200722382A (en) * | 2005-12-02 | 2007-06-16 | Ting-Chung Liu | Method of obtaining the cupric oxalate from discharging acidic copper containing waste liquid in the production of printed circuit board (PCB) |
| CN102381958A (en) * | 2011-09-22 | 2012-03-21 | 浙江华友钴业股份有限公司 | Ammonia circulative preparation method for cobaltous oxalate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200722382A (en) * | 2005-12-02 | 2007-06-16 | Ting-Chung Liu | Method of obtaining the cupric oxalate from discharging acidic copper containing waste liquid in the production of printed circuit board (PCB) |
| CN102381958A (en) * | 2011-09-22 | 2012-03-21 | 浙江华友钴业股份有限公司 | Ammonia circulative preparation method for cobaltous oxalate |
Non-Patent Citations (1)
| Title |
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| 单分散纳米硫酸锶粉体的制备;李彩虹;《化工学报》;20040131;第55卷(第1期);第119页2.3.1 EDTA的作用 * |
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