蚀刻废液制备多种单一晶型碱式氯化铜及性能分析

doi:10.19964/j.issn.1006-4990.2021-0092

Abstract

Abstract:

Copper oxychloride produced from the reaction of acid and alkaline etching waste solution of printed circuit board are normal the mixture of multiple crystal forms,which affects the purity and performance of product.In order to produce copper oxychloride with single crystal form,the reaction conditions of feeding rate,temperature,pH were optimized in the continue crystallization process,and the products with single crystal form of Atacamite（type-A）,Botallackite（type-B） and Clinoatacamite（type-C） and with the respective purity of 99.0%,99.7% and 90.7% were obtained.The XRD and SEM results showed that type-A crystal belonged to orthorhombic and was the long strip and flake aggregates;type-B crystal belonged to monoclinic and was the hexagonal single crystal aggregates;type-C crystal also belonged to monoclinic but was the irregular flaky aggregates.Chemical analysis and TG-DSC showed that the molecular formula of A,B and C products was Cu₄（OH）₆Cl₂·H₂O,Cu₅（OH）₈Cl₂ and CuCl₂·3Cu（OH）₂·0.5H₂O,respectively.The activation energy and heat of decomposition of A,B and C products were different.Among the three products,B-type copper oxychloride had the highest copper content and the strongest thermal stability,which was the best crystal product in copper oxychloride production.

Key words: etching waste solution, copper oxychloride, polycrystalline, industrial crystallization, thermochemistry

CLC Number:

TQ131.21

YANG Junfang,ZHOU Huan,ZHA Zhengjiong,WANG Yongcheng. Preparation process and product characterization of various copper oxychloride with respective crystal form from etching waste solution[J]. Inorganic Chemicals Industry, 2021, 53(11): 107-113.

Figures/Tables 16

Table 1

Fig.1

Table 2

Fig.2

Fig.3

Fig.4

Fig.5

Table 3

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

Table 4

Table 5

Table 6

References 18

[1]	汤政涛, 刘后传, 李丽敏, 等. 酸性氯化铜蚀刻废液一步沉淀法制备碱式碳酸铜[J]. 化工环保, 2021, 41(1):71-76.
[2]	HAWTHORNE F C. Refinement of the crystal structure of Botallac-kite[J]. Mineralogical Magazine, 1985, 49:87-89. doi: 10.1180/minmag.1985.049.350.12
[3]	JAMBOR J L, DUTRIZAC J E, ROBERTS A C, et al. Clinoataca-mite,a new polymorph of Cu₂(OH)₃Cl,and its relationship to para-tacamite and “Anarakite”[J]. The Canadian Mineralogist, 1996, 34(1):73-78.
[4]	WELLS A F. The crystal structure of atacamite and the crystal che-mistry of cupric compounds[J]. Acta Crystallographica, 2010, 2(3):175-180. doi: 10.1107/S0365110X49000461
[5]	OSWALD H R, GUENTER J R. Crystal data on paratacamite,γ-Cu₂(OH)₃Cl[J]. Journal of Applied Crystallography, 2010, 4(6):530-531. doi: 10.1107/S0021889871007611
[6]	刘杨, 吴阳东, 王永成. 饲料添加剂碱式氯化铜晶体结构研究[J]. 广东饲料, 2014, 23(3):32-33.
[7]	温炎燊, 谭路生, 谢钧燕, 等. 再生工业碱式氯化铜产品的质量检验[J]. 中国石油和化工标准与质量, 2017, 37(23):33-34,36.
[8]	刘杨, 吴阳东. 饲料添加剂碱式氯化铜防结块研究[J]. 广东饲料, 2018, 27(4):45-46.
[9]	丁光东. 一种利用含铜废蚀刻液生产碱式氯化铜的方法[J]. 科技经济导刊, 2015, 179(6):275.
[10]	兰永辉, 许世爱, 高仁富. 再生资源产品(α-晶型)与(β-晶型)碱式氯化铜的鉴别方法研究[J]. 资源再生, 2012(10):54-55.
[11]	石荣铭, 钟国清. 利用废铜腐蚀液制取饲料添加剂碱式氯化铜[J]. 中国饲料, 2006(1):25-26.
[12]	王莹, 王玉超, 李光明. HG/T 4826—2015《工业碱式氯化铜》[J]. 无机盐工业, 2018, 50(6):77.
[13]	程龙军, 李钧, 温炎燊, 等. 饲料级碱式氯化铜性质特征分析研究[J]. 无机盐工业, 2019, 51(9):88-90.
[14]	MOTHé C G, MIRANDA I C D. Study of kinetic parameters of ther-mal decomposition of bagasse and sugarcane straw using Friedman and Ozawa-Flynn-Wall isoconversional methods[J]. Journal of Thermal Analysis & Calorimetry, 2013, 113(2):497-505.
[15]	OZAWA T. Kinetic analysis by repeated temperature scanning.Part 1.Theory and methods[J]. Thermochimica Acta, 2000, 356(1/2):173-180. doi: 10.1016/S0040-6031(00)00517-7
[16]	OZAWA T. A new method of analyzing thermogravimetric data[J]. Bulletin of the Chemical Society of Japan, 1965, 38(11):1881-1886. doi: 10.1246/bcsj.38.1881
[17]	邓庚凤, 姬传红, 谢耀, 等. 十水草酸镧的热分解及其动力学分析[J]. 材料与冶金学报, 2017, 16(2):116-123.
[18]	胡荣祖, 高胜利, 赵凤起, 等. 热分析动力学[M].2版. 北京: 科学出版社, 2008.

反应物	ρ（Cu²⁺）/（g·L^-1）	ρ（Cl^-）/（g·L^-1）	ρ（NH₄Cl）/（g·L^-1）
酸性蚀刻废液	81.40	224.41	30.18
碱性蚀刻废液	97.62	152.93	293.70

产物	w（>75 μm 粒子）/%	w（<45 μm 粒子）/%	平均粒径/ μm	最大粒径/ μm
Ⅰ	51.44	4.99	77.64	251.79
Ⅱ	90.82	0.02	120.72	282.51
Ⅲ	18.84	41.14	46.81	112.47

碱式氯化铜	w（Cu）	w（Cl）	w（H₂O）	w₂（Cu）	n（Cu）:n（Cl）	n（Cu）:n（H₂O）	等同分子式	分子式
A	56.35	16.96	15.01	57.10	1.85	1.06	CuCl₂·3CuO·4H₂O	Cu₄（OH）₆Cl₂·H₂O
B	60.28	13.84	13.93	60.56	2.43	1.23	CuCl₂·4CuO·4H₂O	Cu₅（OH）₈Cl₂
C	58.67	16.49	15.03	58.28	1.98	1.11	CuCl₂·3CuO·3.5H₂O	CuCl₂·3Cu（OH）₂·0.5H₂O

β/ （℃·min^-1）	A			B			C
β/ （℃·min^-1）	T₁/℃	T₂/℃	m∞/%	T₁/℃	T₂/℃	m∞/%	T₁/℃	T₂/℃	m∞/%
10	204.74	330.85	84.29	215.33	326.12	85.96	173.89	336.16	85.48
15	206.18	360.23	84.54	214.49	342.70	85.68	176.83	362.30	85.89
20	207.29	362.10	84.81	214.84	347.21	86.44	176.83	349.58	84.13
25	207.89	382.29	84.95	214.87	345.99	86.07	169.31	356.49	84.52
30	208.47	372.21	86.02	208.75	363.58	86.20	158.01	363.87	84.85
平均			84.92			86.07			84.98

α	A		B		C
α	斜率/ b	E/ （kJ·mol^-1）	斜率/ b	E/ （kJ·mol^-1）	斜率/ b	E/ （kJ·mol^-1）
0.1	-2144.3	39.04	-2347.7	42.74	-2134.0	38.85
0.2	-2314.6	42.14	-2764.1	50.32	-2229.0	40.58
0.3	-2382.7	43.38	-2736.7	49.82	-2574.0	46.86
0.4	-2538.8	46.22	-2860.5	52.07	-2649.1	48.23
0.5	-2670.2	48.61	-2847.3	51.83	-2454.1	44.68
0.6	-2760.9	50.26	-2792.3	50.83	-2476.4	45.08
0.7	-2820.4	51.34	-2721.1	49.54	-2432.7	44.29
0.8	-2861.1	52.08	-2660.3	48.43	-2445.7	44.52
平均		46.63		49.45		44.13

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Preparation process and product characterization of various copper oxychloride with respective crystal form from etching waste solution

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 16

References 18

Related Articles 3

Metrics

Comments

Recommended 0

碱式氯化铜	T₁/℃	T₂/℃	Tp/℃	ΔH₁/ （mW·g^-1）
A	201.415	370.355	311.392	4 755.006
B	201.253	388.301	305.871	4 994.990
C	225.911	391.648	284.959	4 449.961

[1]	ZOU Yang, LU Zhiyan, HU Zhilin, SUN Ze. Study on metastable zone width and primary nucleation kinetics for cooling crystallization of KNO₃ [J]. Inorganic Chemicals Industry, 2024, 56(9): 67-74.
[2]	Wen Yanshen,Chen Gang,Wang Weihong,Chen Changming,Gong Chuangzhou,Zhao Jie. Standardization and development trend of utilization of copper-containing etching waste solution on circuit boards [J]. Inorganic Chemicals Industry, 2021, 53(8): 27-30.
[3]	He Yugang,Wang Fang,Sun Qiang,Zhang Xiaowei,Shi Qinghe,Fu Qiang. Effect of adsorption device position on boron and phosphorus removal in polycrystalline silicon [J]. Inorganic Chemicals Industry, 2020, 52(3): 72-74.