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

Abstract

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

CLC Number:

TQ128.54

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.

Figures/Tables 8

Fig.1

Table 1

Table 2

Table 3

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Table 5

Table 6

Fig.2

References 29

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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

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Investigation on holding mechanism and removal method of trace calcium in high purity boric acid prepared by esterification method

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