Basic copper chloride particulate matter and preparation method therefor

Abstract

Disclosed are basic copper chloride particulate matter and a preparation method therefor. The basic copper chloride particulate matter is mainly composed of basic copper chloride particles, and the basic copper chloride particles, with a particle size of 60-250 μm, in the basic copper chloride particulate matter comprise 97% or more of the total mass of the basic copper chloride particulate matter.

Claims

1. A preparation method for a basic copper chloride particulate matter, wherein the method comprises the following steps: preparing an ammonium chloride solution with an ammonia nitrogen concentration of 40 g/L to 60 g/L, heating to 70° C. to 90° C., then adding a copper chloride precursor solution and an ammonium chloride precursor solution into the ammonium chloride solution simultaneously in a parallel feeding manner at a flow ratio of 1:0.5 to 1:1.5, maintaining a reaction pH value between 4.2 and 4.8, stopping feeding until a basic copper chloride solid appears at the bottom of a reaction vessel, performing a heat preservation reaction for 1 to 4 hours; then adding a copper chloride raw material solution and an alkaline copper-containing solution simultaneously to the reaction vessel in a parallel feeding manner, maintaining the reaction pH value between 4.2 to 4.8, reacting for 2 to 4 hours, discharging, washing and drying to obtain the basic copper chloride particulate matter; the copper chloride precursor solution is a copper chloride acidic precursor solution with a copper content of 40 g/L to 60 g/L and a pH of 1.0 to 2.0; the ammonium chloride precursor solution is an ammonium chloride alkaline precursor solution with an ammonium chloride content of 170 g/L to 190 g/L and a pH of 8.0 to 9.5; the copper chloride raw material solution is a copper chloride copper-containing solution with a copper content of 40 g/L to 120 g/L and a pH value of 1.0 to 2.0; and the alkaline copper-containing solution is an alkaline copper-containing solution with a copper content of 30 g/L to 100 g/L and a pH value of 8.0 to 9.5, wherein the basic copper chloride particulate matter mainly consists of basic copper chloride particles, the basic copper chloride particles having a particle size of 60 μm to 250 μm in the basic copper chloride particulate matter account for 97% or more of a total mass of the basic copper chloride particulate matter.

2. The preparation method according to claim 1, wherein the copper chloride raw material solution is prepared according to the following method: preforming impurity removal treatment to an acidic waste etching liquid, and adjusting the copper content and pH value to obtain the copper chloride raw material solution.

3. The preparation method according to claim 1, wherein the alkaline copper-containing solution is prepared according to the following method: preforming impurity removal treatment to an alkali waste etching liquid, and adjusting the copper content and pH value to obtain the alkaline copper-containing solution.

4. The preparation method according to claim 1, wherein when the copper chloride raw material solution and the alkaline copper-containing solution are fed to the reaction vessel in parallel, a flow ratio is 1:0.5 to 1:1.5.

5. A preparation method for a basic copper chloride particulate matter, wherein the method comprises the following steps: preparing an ammonium chloride solution with an ammonia nitrogen concentration of 40 g/L to 60 g/L, heating to 70° C. to 90° C., then adding a copper chloride precursor solution and an ammonium chloride precursor solution into the ammonium chloride solution simultaneously in a parallel feeding manner at a flow ratio of 1:0.5 to 1:1.5, maintaining a reaction pH value between 4.2 and 4.8, stopping feeding until a basic copper chloride solid appears at the bottom of a reaction vessel, performing a heat preservation reaction for 1 to 4 hours; then adding a copper chloride raw material solution and an alkaline copper-containing solution simultaneously to the reaction vessel in a parallel feeding manner, maintaining the reaction pH value between 4.2 to 4.8, reacting for 2 to 4 hours, discharging, washing and drying to obtain the basic copper chloride particulate matter; the copper chloride precursor solution is a copper chloride acidic precursor solution with a copper content of 40 g/L to 60 g/L and a pH of 1.0 to 2.0; the ammonium chloride precursor solution is an ammonium chloride alkaline precursor solution with an ammonium chloride content of 170 g/L to 190 g/L and a pH of 8.0 to 9.5; the copper chloride raw material solution is a copper chloride copper-containing solution with a copper content of 40 g/L to 120 g/L and a pH value of 1.0 to 2.0; and the alkaline copper-containing solution is an alkaline copper-containing solution with a copper content of 30 g/L to 100 g/L and a pH value of 8.0 to 9.5, wherein the basic copper chloride particulate matter mainly consists of basic copper chloride particles, the basic copper chloride particles having a particle size of 60 μm to 250 μm in the basic copper chloride particulate matter account for 97% or more of a total mass of the basic copper chloride particulate matter, wherein the basic copper chloride particulate matter is free of adhesives.

6. The preparation method according to claim 5, wherein the copper chloride raw material solution is prepared according to the following method: preforming impurity removal treatment to an acidic waste etching liquid, and adjusting the copper content and pH value to obtain the copper chloride raw material solution.

7. The preparation method according to claim 5, wherein the alkaline copper-containing solution is prepared according to the following method: preforming impurity removal treatment to an alkali waste etching liquid, and adjusting the copper content and pH value to obtain the alkaline copper-containing solution.

8. The preparation method according to claim 5, wherein when the copper chloride raw material solution and the alkaline copper-containing solution are fed to the reaction vessel in parallel, a flow ratio is 1:0.5 to 1:1.5.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a particle size distribution diagram of a basic copper chloride product of the present disclosure.

(2) FIG. 2 shows a particle size distribution diagram of a commercially available basic copper chloride product.

(3) FIG. 3 shows a crystal structure distribution diagram of the basic copper chloride product of the present disclosure.

(4) FIG. 4 shows a crystal structure distribution diagram of the commercially available basic copper chloride product.

DESCRIPTION OF THE EMBODIMENTS

(5) The present disclosure is further described below in combination with specific implementations, but the present disclosure is not limited by the embodiments in any ways. Unless otherwise, raw materials and reagents used in the embodiments of the present disclosure are conventional raw materials and reagents which are commercially available.

(6) TABLE-US-00001 TABLE 1 Acidic waste etching liquid provided by a circuit board manufacturer (wt %) Cu As Cd Hg Pb Cr pH 8~12 0.0012 0.0003 <0.0001 0.0002 Negative <0.5

(7) TABLE-US-00002 TABLE 2 Alkaline waste etching liquid provided by a circuit board manufacturer (wt %) Cu As Cd Hg Pb Cr pH 7~11 0.001 0.00005 <0.0001 0.0001 Negative 8~10

EMBODIMENTS

(8) An ammonium chloride solution with an ammonia concentration of A g/L was prepared and heated to B° C., then a copper chloride precursor solution and an ammonium chloride precursor solution were added in to the ammonium chloride solution simultaneously in a parallel feeding manner at a flow ratio of C, a reaction pH value was maintained between D, the feeding was stopped until a basic copper chloride solid appears at in the reaction system, and heat preservation reaction was performed for E hours. Then a copper chloride raw material solution and an alkaline copper-containing solution were added simultaneously in a parallel feeding manner, the reaction pH value was maintained between F, reaction was performed for G hours, discharging, washing and drying were performed to obtained the basic copper chloride particulate matter.

(9) The copper chloride precursor solution was a copper chloride acidic precursor solution with a copper content of H g/L and a pH of I.

(10) The ammonium chloride precursor solution was an ammonium chloride alkaline precursor solution with an ammonium chloride content of J g/L and a pH of K.

(11) The copper chloride raw material solution was a copper chloride copper-containing solution with a copper content of L g/L and a pH value of M.

(12) The alkaline copper-containing solution was an alkaline copper-containing solution with a copper content of N g/L and a pH value of O.

(13) A flow ratio of the copper chloride raw material solution to the alkaline copper-containing solution was P.

(14) In the present disclosure, with the addition of raw materials, small suspended basic copper chloride particles gradually appeared in the reaction system, and as the reaction proceeded, the small basic copper chloride particles would gradually grow larger and settled, which just settled to the bottom of the reaction vessel. By observing the bottom of the reaction vessel (usually a reaction kettle), it was judged that basic copper chloride precursor was generated when basic copper chloride solid was present at the bottom of the reaction vessel.

(15) In the Embodiments 1 to 9, the copper chloride precursor solution was formulated with hydrochloric acid and copper chloride.

(16) In the Embodiments 1 to 9, the ammonium chloride precursor solution was formulated with ammonium chloride.

(17) In the Embodiments 1 to 9, the copper chloride raw material solution was prepared by removing impurities with an acidic waste etching liquid.

(18) In the Embodiments 1 to 9, the alkaline copper-containing solution was prepared by removing impurities with an alkaline waste etching liquid.

(19) The specific method of removing impurities in the acidic waste etching liquid was as follows: the acidic waste etching liquid was added with water, the copper content was adjusted to 40 g/L to 120 g/L; hydrogen peroxide was added, the pH value was adjusted to 1.0 to 2.0, and the copper content was adjusted to 40 g/L to 120 g/L, and the copper chloride raw material solution was obtained after filtration.

(20) The specific method of removing impurities in the alkaline waste etching liquid was as follows: the alkaline waste etching liquid was added with ferric chloride, ammonium water or water, the copper content was adjusted to 30 g/L to 100 g/L, and the pH was adjusted to 8.0 to 9.5 to obtain the alkaline copper-containing solution.

(21) Specific parameters of each embodiment are shown in Table 3.

(22) TABLE-US-00003 TABLE 3 Embodiment Technological Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- parameter ment 1 ment 2 ment 3 ment 4 ment 5 ment 6 ment 7 ment 8 ment 9 A 40 40 40 40 60 40 40 40 60 B 70 70 70 70 70 90 70 70 90 C 1:0.5 1:0.5 1:0.5 1:1.5 1:0.5 1:0.5 1:0.5 1:0.5 1:1.5 D 4.2 4.2 4.8 4.2 4.2 4.2 4.2 4.2 4.8 E 1 1 1 1 1 1 1 4 2 F 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 G 2 2 2 2 2 2 2 2 4 H 40 60 40 40 40 40 50 40 60 I 1 2 1 1 1 1 1.5 1 2 J 170 190 170 170 170 170 180 170 190 K 8 9.5 8 8 8 8 8 8 9.5 L 40 40 40 40 40 40 80 40 120 M 1 1 1 1 1 1 1 1 2 N 30 30 30 30 30 30 30 30 100 O 8 8 8 8 8 8 8 8 9.5 P 1:0.5 1:0.5 1:0.5 1:0.5 1:0.5 1:0.5 1:0.5 1:0.5 1:1.5

Comparative Example 1

(23) It was basically the same as Embodiment 1, except that the copper content H in the copper chloride precursor solution was 30 g/L.

Comparative Example 2

(24) It was basically the same as Embodiment 1, except that the copper content H in the copper chloride precursor solution was 70 g/L.

Comparative Example 3

(25) It was basically the same as Embodiment 1, except that the pH value I of the copper chloride precursor solution was 0.5.

Comparative Example 4

(26) It was basically the same as Embodiment 1, except that pH value I of the copper chloride precursor solution was 2.5.

Comparative Example 5

(27) It was basically the same as Embodiment 1, except that the ammonium chloride content J in the ammonium chloride precursor solution was 150 g/L.

Comparative Example 6

(28) It was basically the same as Embodiment 1, except that the ammonium chloride content J in the ammonium chloride precursor solution was 200 g/L.

Comparative Example 7

(29) It was basically the same as Embodiment 1, except that the ammonium chloride precursor solution pH value K was 10.

Comparative Example 8

(30) It was basically the same as Embodiment 1, except that the ammonia concentration A of the ammonium chloride solution was 30 g/L.

Comparative Example 9

(31) It was basically the same as Embodiment 1, except that the ammonia concentration A of the ammonium chloride solution was 70 g/L.

Comparative Example 10

(32) It was basically the same as Embodiment 1, except that before the precursor was put in, the temperature B of the system was 60° C.

Comparative Example 11

(33) It was basically the same as Embodiment 1, except that before the precursor was put in, the temperature B of the system was 100° C.

Comparative Example 12

(34) It was basically the same as Embodiment 1, except that after the precursor was put in, the pH value D of the system was maintained at 4.

Comparative Example 13

(35) It was basically the same as Embodiment 1, except that after the precursor was put in, the pH value D of the system was maintained at 5.

Comparative Example 14

(36) The following method was used to prepare basic copper chloride (refer to patent CN101391800 B).

(37) The specific method was as follows: the above-mentioned alkaline copper chloride waste etching liquid and acidic copper chloride waste etching liquid were pre-treated respectively, i.e., hydrogen peroxide, magnesium chloride, and polyiron were successively added to oxidize cuprous ions to divalent copper and precipitate arsenate and arsenite ions.

(38) The pre-treated acidic and alkaline copper chloride waste etching liquids were pumped to a reaction kettle with a feeding pump for neutralization and precipitation, and the respective flow rates were controlled with a pH electrode to control the pH between 4.9 and 5.3. After the reaction was completed, basic copper chloride precipitate was obtained, washed with suction filtration, and centrifuged to obtain basic copper chloride.

(39) Evaluation of Result

(40) Samples of each of the Embodiments and Comparative Examples were uniformly selected and passed through a test sieve with a pore diameter of 60 μm and a test sieve with a pore diameter of 250 μm is passed in order. The mass W1 of the basic copper chloride product passed through the 60 μm test sieve and the mass W2 of the basic copper chloride product entrapped at the 250 μm test sieve were calculated. Then the following formula was used:
mass content of particles with a particle size of 60 μm to 250 μm in the basic copper chloride particulate matter=(total mass W−W1−W2)/total mass W×100%.
The results are shown in Table 4.

(41) TABLE-US-00004 TABLE 4 Mass 60 to 250 μm Copper passing Mass particles account content in Total mass through 60 entrapped for mass content particulate of sample μm at 250 μm of sample matter (W/g) (W1/g) (W2/g) (%) (%) Embodiment 1 100 1.2 0.8 98 58.8 Embodiment 2 100 1.4 0.5 98.1 59.2 Embodiment 3 100 0.9 1.2 97.9 59.1 Embodiment 4 100 1.5 0.3 98.2 58.7 Embodiment 5 100 0.9 1.1 98 59.0 Embodiment 6 100 1.8 0.8 97.4 59.1 Embodiment 7 100 1.3 1.0 97.7 58.8 Embodiment 8 100 1.1 1.1 97.8 58.8 Embodiment 9 100 0.9 1.2 97.9 59.1 Comparative 100 23.8 1.5 74.7 58.34 Example 1 Comparative 100 24.7 1.3 74.0 58.30 Example 2 Comparative 100 25.1 1.1 73.8 58.27 Example 3 Comparative 100 24.2 2.0 73.8 58.33 Example 4 Comparative 100 24.3 1.9 73.8 58.28 Example 5 Comparative 100 25.2 1.3 73.5 58.33 Example 6 Comparative 100 24.9 1.2 73.9 58.39 Example 7 Comparative 100 24.7 1.7 73.4 58.30 Example 8 Comparative 100 25.1 1.8 73.1 58.35 Example 9 Comparative 100 25.3 1.9 72.8 58.27 Example 10 Comparative 100 24.9 1.8 73.3 58.32 Example 11 Comparative 100 25.4 1.6 73.0 58.39 Example 12 Comparative 100 25.0 1.4 73.6 58.36 Example 13 Comparative 100 99.8 0.1 0.1 58.61 Example 14

(42) From the above data of Embodiments and Comparative Examples, it can be seen that factors, such as the ammonia concentration of ammonium chloride solution, the pH value of the system, the ammonium chloride content in the ammonium chloride precursor solution, the pH value of the ammonium chloride precursor solution, the copper content of the copper chloride precursor solution, the pH value of the copper chloride precursor solution, all affect the formation of the basic copper chloride precursor and determine whether the basic copper chloride particulate matter in larger particles can be obtained. If the method of generating precursor first and then preparing particles according to the present disclosure is not adopted, it is also impossible to prepare the basic copper chloride particulate matter with the size of the present disclosure (see FIG. 2 and FIG. 4).

(43) Samples of the basic copper chloride particulate matters of some of the Embodiments and commercially available basic copper chloride particulate matters were taken to perform agglomeration performance testing: 10 g of the sample was placed in a constant temperature and humidity box at a relative humidity of 75% and a temperature of 60° C. for 15 days, and the results were recorded as shown in Table 5.

(44) TABLE-US-00005 TABLE 5 Color changed or not Agglomeration or not Embodiment 1 No color changed No agglomeration Embodiment 3 No color changed No agglomeration Embodiment 5 No color changed No agglomeration Embodiment 6 No color changed No agglomeration Embodiment 9 No color changed No agglomeration Comparative Color changed Agglomeration Example 14

(45) The samples of Embodiments 1, 3, 5, 6 and 9 and the samples not prepared by the method of the present disclosure were analyzed for crystal forms. The results between the embodiments are similar, and the crystal form is mainly a mixture of the atacamite crystal form and the paratacamite crystal form. The results of Embodiment 1 are shown in FIG. 3. It can be known from the analysis of crystal form of the sample of Comparative Example 14 that it contains a large amount of botallackite crystal form, which is unstable and prone to agglomeration.