以印刷电路板蚀刻废液为原料生产碱式氯化铜的过程存在产物多种晶型混杂的问题,影响产品的纯度和性能。为获得纯正的晶型产品,以酸、碱蚀刻废液为原料,通过改变连续反应结晶过程的加料速率、反应温度、pH等条件,获得了A型（Atacamite）、B型（Botallackite）和C型（Clinoatacamite）3种单一晶型产物。3种产物中单一晶型纯度分别为99.0%（A型）、99.7%（B型）和90.7%（C型）。3种产物的XRD和SEM分析表明:A型属正交晶系,为长条片状聚集物;B型属单斜晶系,为正六棱柱单晶聚集物;C型属单斜晶系,为不规则片状聚集体。3种产物的化学分析和TG-DSC热分析表明:A、B、C 3种结晶形态具有不同的化学式,分别为A型Cu₄（OH）₆Cl₂·H₂O、B型Cu₅（OH）₈Cl₂和C型CuCl₂·3Cu（OH）₂·0.5H₂O;3种产物具有不同的热分解活化能和分解热。B型碱式氯化铜在3种产物中含铜量最高,且热稳定性最强,是碱式氯化铜生产中最好的晶型产物。

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.