酯化法高纯硼酸制备中痕量钙残存机理及脱除方法探究

doi:10.19964/j.issn.1006-4990.2022-0123

摘要/Abstract

摘要：

硼酸酯化法是低成本规模化制备核电级及光电级等高纯硼酸的有效方法之一，但该方法获得的硼酸始终含有痕量钙杂质，影响应用性能。结合酯化法制备工艺，探讨了痕量钙杂质残存机理及脱除方法。纯化样品中杂质含量及产品特征用电感耦合等离子体（ICP）、X射线衍射（XRD）和扫描电镜（SEM）进行分析表征。结果表明，酯化法硼酸中残存钙的含量与原料硼酸中所含杂质种类及其含量没有明显相互依存关系，而与硼酸酯蒸馏温度波动有关联；在硼酸酯水解生成硼酸过程中添加适量含孤对电子的干扰剂，可有效降低硼酸中钙的残存量且不引进其他杂质。基于实验结果提出了痕量钙可能的残存机理和脱除原理。

关键词: 硼酸酯, 硼酸, 高纯硼酸, 钙脱除, 纯化

Abstract:

Borate esterification is one of the effective approaches for low-cost and large-scale preparation of nuclear power grade and photoelectric grade high-purity boric acid.However，the boric acid obtained by this method always contains trace calcium impurities，which affects the application performance.Combined with the esterification process，the residual mechanism and removal method of trace calcium impurities were discussed.The impurity content and product characteristics in the purified samples were analyzed and characterized by inductively coupled plasma（ICP），X-ray diffraction（XRD） and scanning electron microscope（SEM）.The results showed that the content of the residual calcium in esterified boric acid was not significantly dependent on the impurity constituents and their contents of raw boric acid，but it was dependent on the distillation temperature turbulence of borate ester.When an appropriate amount of interfering agent containing lone pair electrons was added during the hydrolysis of borate ester to boric acid，the residual amount of calcium in boric acid could be effectively reduced without introducing other impurities.Based on the experimental results，the possible residual mechanism and removal principle of trace calcium were put forward.

Key words: borate, boric acid, high-purity boric acid, calcium removal, purification

中图分类号:

TQ128.54

贺正燕,李长伟,田朋,毕胜南,朱培涵,李欣竹,叶俊伟,宁桂玲. 酯化法高纯硼酸制备中痕量钙残存机理及脱除方法探究[J]. 无机盐工业, 2022, 54(7): 49-54.

HE Zhengyan,LI Changwei,TIAN Peng,BI Shengnan,ZHU Peihan,LI Xinzhu,YE Junwei,NING Guiling. Investigation on holding mechanism and removal method of trace calcium in high purity boric acid prepared by esterification method[J]. Inorganic Chemicals Industry, 2022, 54(7): 49-54.

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项目	w（H₃BO₃）/ %	w（Na⁺）/ 10^-6	w（Cl^-）/ 10^-6	w（SO₄^2-）/ 10^-6	w（PO₄^3-）/10^-6	w（Fe^2+/3+）/10^-6	w（SiO₂）/ 10^-6	w（Ca²⁺）/10^-6	w（Mg²⁺）/ 10^-6	w（Al³⁺）/ 10^-6	w（F^-）/ 10^-6	w（As³⁺）/ 10^-6	w（Pb²⁺）/ 10^-6
核用硼酸标准^［7］	>99.9	<2.0	<0.4	<1.0	<1.0	<1.0	<2.0	<1.0	<5.0	<1.0	<0.4	<2.0	<0.5
工业硼酸1	>98	88.1				17.6		3.2	293.7	3.3			4.9
工业硼酸2	>99	54.2				2.3		35.2	19.0	1.1			5.6
自配硼酸	>99.7	2.1				307.5		6.8	3.4	0.8
酯化法高纯硼酸	>99.9	<1	<0.4	<1.0	<1.0	<1.0	<1.0	0.5~10	<1.0	<0.5	<0.1	<0.5	<0.5

w（添加剂）/%	w（硼酸中钙）/10^-6
w（添加剂）/%	Ca（NO₃）₂	CaSO₄	CaCl₂	CaCO₃	Ca（HCO₂）₂	CaO	Ca（OH）₂
0	1.9	1.9	1.9	1.9	1.9	1.9	1.9
1	1.9	3.4	2.0	1.7	1.4	1.3	2.9
5	2.8	2.5	2.0	1.2	2.8	1.9	1.9
9	1.7	2.0	2.1	1.5	2.8	2.1	1.6

原料	w（原料硼酸中金属杂质）/10^-6					w（产品硼酸中钙）/10^-6
原料	Na⁺	Fe^3+/2+	Ca²⁺	Mg²⁺	Al³⁺	w（产品硼酸中钙）/10^-6
工业硼酸1	88.1	17.6	3.2	293.7	3.3	2.3
工业硼酸2	54.2	2.3	35.2	19.0	1.1	1.9
自配硼酸	2.1	307.5	6.8	3.4	0.8	2.6

w（原料硼酸中铁）/10^-6	w（产品硼酸中钙）/10^-6	w（原料硼酸中铁）/10^-6	w（产品硼酸中钙）/10^-6
1.3	1.9	1 108	1.7
76.3	3.0	3 268	3.6
307.5	2.6

干扰剂	w（产品硼酸中钙）/10^-6	干扰剂	w（产品硼酸中钙）/10^-6
无	1.59	无	2.64
含—NO₃	0.53	含—COOH	0.63

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