机械活化重质碳酸钙制备复合碳酸钙及其对溶液中的Cu2+吸附性能

doi:10.16085/j.issn.1000-6613.2022-2351

化工进展 ›› 2023, Vol. 42 ›› Issue (11): 5861-5870.DOI: 10.16085/j.issn.1000-6613.2022-2351

• 材料科学与技术 • 上一篇

机械活化重质碳酸钙制备复合碳酸钙及其对溶液中的Cu²⁺吸附性能

郭亚宁¹(), 季军荣², 焦妍惠¹, 张庆年², 周洲², 韦德恩², 童张法¹, 李立硕¹()

^1.广西大学化学化工学院，广西南宁 530004
^2.崇左南方水泥有限公司广西钙基材料协同创新中心，广西南宁 530004

收稿日期:2022-12-23 修回日期:2023-03-12 出版日期:2023-11-20 发布日期:2023-12-15
通讯作者: 李立硕
作者简介:郭亚宁（1999—），女，硕士研究生，研究方向为无机材料。E-mail：gyn426@126.com。
基金资助:
广西钙基材料协同创新中心项目(CZNF-JSZX20-03);广西碳酸钙产业化工程院公司级科研项目(GJZX2022-4)

Preparation of calcium carbonate composite by mechanically activated of ground calcium carbonate and its adsorption properties on Cu²⁺ ions in solution

GUO Yaning¹(), JI Junrong², JIAO Yanhui¹, ZHANG Qingnian², ZHOU Zhou², WEI Deen², TONG Zhangfa¹, LI Lishuo¹()

^1.School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^2.Chongzuo South Cement Co. , Ltd. , Guangxi Collaborative Innovation Center of Calcium-based Materials, Nanning 530004, Guangxi, China

Received:2022-12-23 Revised:2023-03-12 Online:2023-11-20 Published:2023-12-15
Contact: LI Lishuo

摘要/Abstract

摘要：

利用机械活化法对重质碳酸钙进行了纳米化表面改性，以聚丙烯酸钠和纳米碳酸钙为改性原料与重质碳酸钙进行混合研磨，成功制备了纳米碳酸钙包覆重质碳酸钙的复合钙，并考察了复合钙对溶液中的Cu²⁺的吸附性能。研究结果如下：扫描电子显微镜和X射线衍射仪分析证实了纳米碳酸钙包覆在重质碳酸钙表面，傅里叶变换红外光谱分析表明复合碳酸钙表面羟基明显增加，比表面积分析表明复合碳酸钙的比表面积为20.5m²/g，具有介孔结构。复合碳酸钙对Cu²⁺的最大吸附量为65.5mg/g，去除率可达98%。吸附性能研究表明，复合碳酸钙对Cu²⁺吸附动力学符合伪二阶动力学模型，等温吸附过程符合Langmuir-Freundich模型，证明吸附过程以离子交换反应为主，该过程为吸热反应。

关键词: 复合碳酸钙, 机械活化, 吸附, 二价铜离子

Abstract:

The surface modification of ground calcium carbonate (GCC) was accomplished by mechanically activated of GCC, sodium polyacrylate and nano calcium carbonate together and the CaCO₃ composite coated with nano calcium carbonate was applied to the adsorption of Cu²⁺ in solution. The adsorption properties were also investigated. The results showed that SEM and XRD analyses confirmed that the nano calcium carbonate was successfully coated on the surface of GCC. FTIR analysis found that the hydroxyl groups increased on the composite surface, and BET analysis indicated that the specific surface area of composite was 20.5m²/g with a mesoporous structure. The maximum adsorption capacity of composite calcium carbonate for Cu²⁺ was 65.5mg/g and the removal rate could reach 98%. The absorption process studies revealed that the adsorption kinetics followed the pseudo-second-order kinetic model and the adsorption isotherms followed the Langmuir-Freundich model, proving that the adsorption was dominated by ions exchange and was exothermal.

Key words: composite calcium carbonate, mechanical activation, adsorption, Cu²⁺ ions

中图分类号:

TQ13

郭亚宁, 季军荣, 焦妍惠, 张庆年, 周洲, 韦德恩, 童张法, 李立硕. 机械活化重质碳酸钙制备复合碳酸钙及其对溶液中的Cu²⁺吸附性能[J]. 化工进展, 2023, 42(11): 5861-5870.

GUO Yaning, JI Junrong, JIAO Yanhui, ZHANG Qingnian, ZHOU Zhou, WEI Deen, TONG Zhangfa, LI Lishuo. Preparation of calcium carbonate composite by mechanically activated of ground calcium carbonate and its adsorption properties on Cu²⁺ ions in solution[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5861-5870.

图/表 18

图1 样品SEM图

图2 GCC、PCC、GCC10、SP、GCC-SP和CCC的FTIR谱图

图3 GCC、PCC、GCC10、GCC-SP和CCC的XRD谱图

表1 不同碳酸钙的比表面积

项目	不同碳酸钙
项目	GCC	GCC10	GCC-SP	CCC	PCC
比表面积/m²·g^-1	4.25	8.40	6.92	20.50	35.20

图4 复合碳酸钙的BET曲线

图5 不同碳酸钙对Cu2+去除率、吸附量的影响

表2 不同碳酸钙的吸附量

项目	不同碳酸钙
项目	GCC	PCC	GCC-SP	GCC10	CCC
吸附量/m²·g^-1	2.23	36.10	56.54	62.05	65.53

图6 溶液初始pH对Cu2+去除率、吸附量的影响

图7 溶液初始浓度对Cu2+去除率、吸附量的影响

图8 CCC添加量对Cu2+去除率、吸附量的影响

图9 摇床转速对Cu2+去除率、吸附量的影响

图10 温度对Cu2+去除率、吸附量的影响

图11 伪一阶和伪二阶动力学模型拟合图

表3 使用伪一阶和伪二阶模型对复合碳酸钙吸附Cu2+的拟合结果

模型	k/min^-1	q/mg·g^-1	R²
伪一阶动力学模型	0.02987	62.50497	0.90587
伪二阶动力学模型	0.00067	66.87839	0.99190

图12 吸附等温模型拟合图

表4 使用Langmuir模型、Freundlich模型和Langmuir-Freundich模型对复合碳酸钙吸附Cu2+的拟合结果

模型

$k L$ /L·min^-1

$k f$ /mg ⁿ⁺¹·L^-ⁿ ·g^-1

q e

R²

Langmuir- Freundich

模型

表4 使用Langmuir模型、Freundlich模型和Langmuir-Freundich模型对复合碳酸钙吸附Cu2+的拟合结果

模型

$k L$ /L·min^-1

$k f$ /mg ⁿ⁺¹·L^-ⁿ ·g^-1

q e

/mg·g^-1

R²

Langmuir模型

0.03012

76.21394

—

0.96225

Freundich模型

15.11485

—

3.69497

0.76707

Langmuir- Freundich

模型

0.03441

68.97473

0.68857

0.98725

图13 吸附热力学方程拟合图

表5 复合碳酸钙热力学参数

温度/K	$l n K f$	ΔG/kJ·mol^-1	ΔH^θ/kJ·mol^-1	ΔS^θ/J·mol^-1·K^-1
298	2.66	-6.58	43.60	170.01
300	2.93	-7.31
303	3.23	-8.13
308	3.38	-8.66

表5 复合碳酸钙热力学参数

温度/K	$l n K f$	ΔG/kJ·mol^-1	ΔH^θ/kJ·mol^-1	ΔS^θ/J·mol^-1·K^-1
298	2.66	-6.58	43.60	170.01
300	2.93	-7.31
303	3.23	-8.13
308	3.38	-8.66

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机械活化重质碳酸钙制备复合碳酸钙及其对溶液中的Cu²⁺吸附性能

Preparation of calcium carbonate composite by mechanically activated of ground calcium carbonate and its adsorption properties on Cu²⁺ ions in solution

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