CN112093788B - 一种镉-钙-氟磷灰石固溶体制备方法及其应用 - Google Patents
一种镉-钙-氟磷灰石固溶体制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种水热法合成镉‑钙‑氟磷灰石固溶体的方法。通过配制硝酸镉和硝酸钙溶液，并以不同摩尔比混合作为基础液，在摩尔比为0.0、0.1、0.2、0.3、0.4和0.5时，应先加硝酸钙溶液后加入硝酸镉溶液；在摩尔比为0.6、0.7、0.8、0.9和1.0时，应先加硝酸镉溶液后加入硝酸钙溶液，其添加顺序不能颠倒。然后将氟化钠溶液加入至硝酸镉与硝酸钙混合溶液中，再将磷酸氢二胺加入至硝酸镉、硝酸钙和氟化钠的混合溶液中，同时加入浓氨水，调节pH至7.5后持续在室温下搅拌，将其放入100℃恒温水浴锅加热48h，最后取出样品，得到镉‑钙‑氟磷灰石固溶体。
Description
技术领域
本发明属于材料安全领域，涉及镉-钙-氟磷灰石固溶体合成方法及其应用。该方法利用镉离子和氟离子可以替代钙离子和羟基(-OH)进入羟基磷灰石晶格，形成镉-钙-氟磷灰石的完全类质同像固溶体。
背景技术
镉(Cd)，原子序数为48，熔点为320.9℃，沸点为767℃，密度8650kg/m3，呈银白色，具有韧性和延展性。常见的镉有+1和+2两种价态，其形成的氧化镉和氢氧化镉溶解度都很小，可以溶于酸，但不溶于碱。镉具有较大的毒性，“痛痛病”的产生就是由于镉中毒所引起。镉会对呼吸道产生较强刺激，引起嗅觉丧失症；镉化合物易被体内吸收，积存于肝或肾脏。镉是人体非必需元素，其进入人体主要是通过食物、水和空气等介质的传递，并能够在人体内长期累积，当体内累积的镉进入血液中，将会与血液红细胞结合，可能造成贫血；镉进入骨骼中，将会引发骨质软化、骨质疏松及骨骼变形等症状。环境中镉污染的主要来源为有色金属冶炼、电镀和油漆等工业排放的废水，其结果造成了水源及土壤环境中镉含量超标的污染现状。根据2014年《全国土壤污染状况调查公报》显示，土壤重金属污染总超标率为16.1％，而在调查的8种(镉、铅、汞、砷、铜、铬、锌和镍)污染物中，镉污染点位超标率高达7.0％，并且镉成为耕地的首要污染物，因此对于镉污染的治理迫在眉睫。
氟(F)，原子序号为9，位于第二周期ⅦA族，是一种非金属元素。1990年世界卫生组织和国际粮农组织将氟列入“人体可能必需，但有潜在毒性的微量元素”。在未被污染的淡水中，氟的含量大约为0.01～0.3mg/L，中国规定饮用水中氟的含量不超过1mg/L，但是我国部分区域水体中氟含量超过4mg/L，甚至达到20mg/L。当人体摄入氟过量时，将会造成氟斑牙和氟骨病等症状。所以需要一种新方法对于环境中镉和氟进行治理，到达有效控制镉和氟污染。
镉-钙-氟磷灰石属于磷酸盐类矿物，其可以发生同价或异价类质同象替换形成不同类型矿物。有研究者进行研究，结果表明生成的矿物能够稳定存在，可以成为固定重金属的一种新方法。本发明提供一种以水热合成法合成镉-钙-氟磷灰石，除去并固定废水中的二价镉和一价氟。
发明内容
本发明目的是提供一种水热合成镉-钙-氟磷灰石固溶体的方法。对制备固溶体经过X射线衍射(XRD)、扫描电镜(SEM)表征，测试在温度为25℃，pH分别为2.00、5.60和9.00条件下对于镉和氟的浸出浓度，对溶解度和稳定性进行详细实验分析，为固定镉和氟提供数据支撑。
1.一种镉-钙-氟磷灰石固溶体合成方法，其具体步骤为：
(1)首先利用氮气对超纯水进行脱除CO2处理，然后配制0.2mol/L Ca(NO3)2溶液，0.2mol/L Cd(NO3)2溶液，0.2mol/L(NH4)2HPO4溶液，0.2mol/L NaF溶液；
(2)取11个做好记号且干净的1000L聚乙烯瓶，然后准备按Cd/(Cd+Ca)摩尔比分别为0.0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9和1.0的0.2mol/L Cd(NO3)2与Ca(NO3)2混合溶液500mL，并保持Cd+Ca的总离子浓度为0.2mol/L，；
(3)在摩尔比分别为0.0、0.1、0.2、0.3、0.4和0.5的聚乙烯瓶中，先加入Ca(NO3)2溶液并放于磁力搅拌器以450～500rmp转速搅拌1～2min后再加入Cd(NO3)2溶液；
(4)在摩尔比分别为0.6、0.7、0.8、0.9和1.0的聚乙烯瓶中，先加入Cd(NO3)2溶液并放于磁力搅拌器以450～500rmp转速搅拌1～2min后再加入Ca(NO3)2溶液；
(5)在(3)、(4)步骤完成后再持续搅拌2～3min，加入100mL 0.2mol/L NaF溶液，并搅拌3～5min；
(6)调节磁力搅拌器转速为650～700rmp，将300mL 0.2mol/L(NH4)2HPO4溶液加入聚乙烯瓶中，同时向聚乙烯瓶中加入浓氨水，快速将pH调至7.5后持续在室温下搅拌10～11min；
(7)待溶液完全混匀后，盖好瓶盖并放入100℃恒温水浴锅中加热48h；
(8)待反应完全后，取出样品自然冷却，得到镉-钙-氟磷灰石固溶体。
本发明的镉-钙-氟磷灰石固溶体的应用于实现镉和氟在环境中长期稳定化推放，则具体步骤为：
在100℃下反应完成后进行固液分离，所得固相沉淀物经超纯水反复洗涤至中性并离心分离得到白色沉淀物，然后将洗涤后的固相物置于瓷盘中并放于70℃烘箱干燥72h，所得的产物进行推存，即实现镉和氟在环境中长期稳定化推存。
本发明利用镉离子和氟离子可以替代钙离子和羟基进入羟基磷灰石晶格，形成镉-钙-氟磷灰石的完全类质同像固溶体。利用该方法合成的镉-钙-氟磷灰石固溶体具有低成本，易操控，能够实现镉和氟在环境中的长期稳定化推存等优点。
附图说明
图1为本发明合成镉-钙-氟磷灰石固溶体系列材料的XRD图，其中镉-钙-氟磷灰石标准卡片PDF#015-0876、070-1207。
图2为本发明合成镉-钙-氟磷灰石固溶体系列材料场发射扫描电子显微镜图。
图3为本发明镉-钙-氟磷灰石固溶体系列材料在25℃，pH＝2.0、5.6和9.0的溶解浸出镉和氟的浓度变化图。
具体实施方式
实施例1
首先利用氮气对超纯水进行脱除CO2处理，然后配制0.2mol/L Ca(NO3)2溶液，0.2mol/LCd(NO3)2溶液，0.2mol/L(NH4)2HPO4溶液，0.2mol/L NaF溶液，然后，取500mL0.2mol/LCa(NO3)2溶液于聚乙烯瓶中，在磁力搅拌器转速为500rmp条件下搅拌2min，加入100mL 0.2mol/LNaF溶液，搅拌5min充分混匀，最后调节磁力搅拌器转速为700rmp，加入300mL 0.2mol/L(NH4)2HPO4溶液并快速搅拌，同时向聚乙烯瓶中加入浓氨水，快速将pH调至7.5后持续在室温下搅拌10min，待溶液完全混匀后，盖好瓶盖并放入100℃恒温水浴锅中加热48h，待反应完全后，取出样品自然冷却，即可制得Cd/(Cd+Ca)摩尔比为0.0的镉-钙-氟磷灰石固溶体。将制得的沉淀物进行固液分离，固相沉淀物用超纯水反复洗涤至中性，然后在70℃下干燥72h，得到高度结晶的镉-钙-氟磷灰石固溶体。
浸出测试：温度为25℃，pH为2.00条件下溶解7200h，镉浸出浓度0.000mmol/L，氟浸出浓度0.234mmol/L；
温度为25℃，pH为5.60条件下溶解7200h，镉浸出浓度0.000mmol/L，氟浸出浓度0.252mmol/L；
温度为25℃，pH为9.00条件下溶解7200h，镉浸出浓度0.000mmol/L，氟浸出浓度0.294mmol/L。
实施例2
首先利用氮气对超纯水进行脱除CO2处理，然后配制0.2mol/L Ca(NO3)2溶液，0.2mol/LCd(NO3)2溶液，0.2mol/L(NH4)2HPO4溶液，0.2mol/L NaF溶液，然后，取450mL0.2mol/LCa(NO3)2溶液于聚乙烯瓶中，在磁力搅拌器转速为500rmp条件下搅拌1min后加入50mL Cd(NO3)2溶液，再搅拌2min，加入100mL 0.2mol/L NaF溶液，搅拌5min充分混匀，最后调节磁力搅拌器转速为700rmp，加入300mL 0.2mol/L(NH4)2HPO4溶液并快速搅拌，同时向聚乙烯瓶中加入浓氨水，快速将pH调至7.5后持续在室温下搅拌10min，待溶液完全混匀后，盖好瓶盖并放入100℃恒温水浴锅中加热48h，待反应完全后，取出样品自然冷却，即可制得Cd/(Cd+Ca)摩尔比为0.1的镉-钙-氟磷灰石固溶体。将制得的沉淀物进行固液分离，固相沉淀物用超纯水反复洗涤至中性，然后在70℃下干燥72h，得到高度结晶的镉-钙-氟磷灰石固溶体。
浸出测试：温度为25℃，pH为2.00条件下溶解7200h，镉浸出浓度0.599mmol/L，氟浸出浓度0.236mmol/L；
温度为25℃，pH为5.60条件下溶解7200h，镉浸出浓度0.012mmol/L，氟浸出浓度0.337mmol/L；
温度为25℃，pH为9.00条件下溶解7200h，镉浸出浓度0.011mmol/L，氟浸出浓度0.348mmol/L。
实施例3
首先利用氮气对超纯水进行脱除CO2处理，然后配制0.2mol/L Ca(NO3)2溶液，0.2mol/LCd(NO3)2溶液，0.2mol/L(NH4)2HPO4溶液，0.2mol/L NaF溶液，然后，取250mL0.2mol/LCa(NO3)2溶液于聚乙烯瓶中，在磁力搅拌器转速为500rmp条件下搅拌1min后加入250mL Cd(NO3)2溶液，再搅拌2min，加入100mL 0.2mol/L NaF溶液，搅拌5min充分混匀，最后调节磁力搅拌器转速为700rmp，加入300mL 0.2mol/L(NH4)2HPO4溶液并快速搅拌，同时向聚乙烯瓶中加入浓氨水，快速将pH调至7.5后持续在室温下搅拌10min，待溶液完全混匀后，盖好瓶盖并放入100℃恒温水浴锅中加热48h，待反应完全后，取出样品自然冷却，即可制得Cd/(Cd+Ca)摩尔比为0.5的镉-钙-氟磷灰石固溶体。将制得的沉淀物进行固液分离，固相沉淀物用超纯水反复洗涤至中性，然后在70℃下干燥72h，得到高度结晶的镉-钙-氟磷灰石固溶体。
浸出测试：温度为25℃，pH为2.00条件下溶解7200h，镉浸出浓度4.637mmol/L，氟浸出浓度0.303mmol/L；
温度为25℃，pH为5.60条件下溶解7200h，镉浸出浓度0.107mmol/L，氟浸出浓度0.471mmol/L；
温度为25℃，pH为9.00条件下溶解7200h，镉浸出浓度0.097mmol/L，氟浸出浓度0.488mmol/L。
实施例4
首先利用氮气对超纯水进行脱除CO2处理，然后配制0.2mol/L Ca(NO3)2溶液，0.2mol/LCd(NO3)2溶液，0.2mol/L(NH4)2HPO4溶液，0.2mol/L NaF溶液，然后，取450mL0.2mol/LCd(NO3)2溶液于聚乙烯瓶中，在磁力搅拌器转速为500rmp条件下搅拌1min后加入50mL Ca(NO3)2溶液，再搅拌2min，加入100mL 0.2mol/L NaF溶液，搅拌5min充分混匀，最后调节磁力搅拌器转速为700rmp，加入300mL 0.2mol/L(NH4)2HPO4溶液并快速搅拌，同时向聚乙烯瓶中加入浓氨水，快速将pH调至7.5后持续在室温下搅拌10min，待溶液完全混匀后，盖好瓶盖并放入100℃恒温水浴锅中加热48h，待反应完全后，取出样品自然冷却，即可制得Cd/(Cd+Ca)摩尔比为0.9的镉-钙-氟磷灰石固溶体。将制得的沉淀物进行固液分离，固相沉淀物用超纯水反复洗涤至中性，然后在70℃下干燥72h，得到高度结晶的镉-钙-氟磷灰石固溶体。
浸出测试：温度为25℃，pH为2.00条件下溶解7200h，镉浸出浓度6.889mmol/L，氟浸出浓度0.455mmol/L；
温度为25℃，pH为5.60条件下溶解7200h，镉浸出浓度0.129mmol/L，氟浸出浓度0.667mmol/L；
温度为25℃，pH为9.00条件下溶解7200h，镉浸出浓度0.114mmol/L，氟浸出浓度0.701mmol/L。
Claims (1)
1.一种镉-钙-氟磷灰石固溶体合成方法，其具体步骤为：
(1)首先利用氮气对超纯水进行脱除CO2处理，然后配制0.2mol/L Ca(NO3)2溶液，0.2mol/L Cd(NO3)2溶液，0.2mol/L(NH4)2HPO4溶液，0.2mol/L NaF溶液；
(2)取11个做好记号且干净的1000L聚乙烯瓶，然后准备按Cd/(Cd+Ca)摩尔比分别为0.0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9和1.0的0.2mol/L Cd(NO3)2与Ca(NO3)2混合溶液500mL，并保持Cd+Ca的总离子浓度为0.2mol/L；
(3)在摩尔比分别为0.0、0.1、0.2、0.3、0.4和0.5的聚乙烯瓶中，先加入Ca(NO3)2溶液并放于磁力搅拌器以500rmp转速搅拌1min后再加入Cd(NO3)2溶液；
(4)在摩尔比分别为0.6、0.7、0.8、0.9和1.0的聚乙烯瓶中，先加入Cd(NO3)2溶液并放于磁力搅拌器以500rmp转速搅拌1min后再加入Ca(NO3)2溶液；
(5)在(3)、(4)步骤完成后再持续搅拌2min，加入100mL 0.2mol/L NaF溶液，并搅拌5min；
(6)调节磁力搅拌器转速为700rmp，将300mL 0.2mol/L(NH4)2HPO4溶液加入聚乙烯瓶中，同时向聚乙烯瓶中加入浓氨水，快速将pH调至7.5后持续在室温下搅拌10min；
(7)待溶液完全混匀后，盖好瓶盖并放入100℃恒温水浴锅中加热48h；
(8)待反应完全后，取出样品自然冷却，所得固相沉淀物经超纯水反复洗涤至中性并离心分离得到白色沉淀物，然后将洗涤后的固相物置于瓷盘中并放于70℃烘箱干燥72h，得到镉-钙-氟磷灰石固溶体进行推存，即实现镉和氟在环境中长期稳定化推存。
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