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

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Table 3

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Table 6

Fig.2

References 29

1	ZHENG H， CAO P， WANG Y，et al.Ultralong room-temperature phosphorescence from boric acid［J］.Angew.Chem.Int.Ed.，2021，60（17）：9500-9506.
2	VITOLA V， LAGANOVSKA K， BITE I，et al.The role of boric acid in optical information storage properties in Eu doped BaSi₂O₅ ［J］.Journal of Luminescence，2022，243.Doi：10.1016/j.jlumin.2021 . doi: 10.1016/j.jlumin.2021
	118682. doi: 10.1016/j.jlumin.2021
3	毕胜南，仲剑初，齐野，等.硼酸等含硼化学品最新研究进展与产业化趋势［J］.无机盐工业，2020，52（1）：5-8.
	BI Shengnan， ZHONG Jianchu， QI Ye，et al.Latest research progress and industrialization trend of boron-containing chemicals such as boric acid［J］.Inorganic Chemicals Industry，2020，52（1）：5-8.
4	LI T， PENG Z Z， FAN Y C，et al.Boric acid corrosion in the primary system of PWRs［J］.Advanced Materials Research，2015，1081：58-62.
5	CABUS U， SECME M， KABUKCU C，et al.Boric acid as a promising agent in the treatment of ovarian cancer：Molecular mechanisms［J］.Gene，2021（1）.Doi：10.1016/j.gene.2021.145799 . doi: 10.1016/j.gene.2021.145799
6	HOU X， LI Z， ZHANG Z.Selectively producing acetic acid via boric acid-catalyzed fast pyrolysis of woody biomass［J］.Catalysts，2021，11（4）.Doi：10.3390/catal11040494 . doi: 10.3390/catal11040494
7	ANP：NEEM-F DC 20009 核电项目化学添加剂规范［S］.
	ANP：NEEM-F DC 20009 Specification for chemical additives for nuclear power projects ［S］.
8	RAO A S， VENKATESWARLU B， HANUMAN V V，et al.Conversion of chemically impure enriched elemental boron（low grade） to nuclear grade boric acid by hydrogen peroxide oxidation［J］.Materials Chemistry and Physics，2019，239.Doi：10.1016/j.matchemphys.2019.121999 . doi: 10.1016/j.matchemphys.2019.121999
9	叶铁林.化工结晶过程原理及应用［M］.北京：北京工业大学出版社，2006.
	YE Tielin.Principle and application of chemical crystallization process［M］.Beijing：Beijing University of Technology Press，2006.
10	ZHANG W， LIU T， XU J.Preparation and characterization of high purity enriched 10B boric acid via anti-solvent recrystallization［J］.Transactions of Tianjin University，2016，22（3）：279-283
11	Chuken RYO， Shintaku SAI， Ktsu HO，et al.Boric acid purification and reutilization system，and method，using reverse osmosis separation method：JP，2005147788（A）［P］.2005-06-09.
12	周莉骅，吴可荆，秦炜，等.连续环状色谱柱吸附分离硼酸的性能［J］.化学工程，2015，43：15-19.
	ZHOU Lihua， WU Kejing， QIN Wei，et al.Adsorption characteristics of boric acid in continuous annular chromatography［J］.Che-
	Engineering（China） mical，2015，43：15-19.
13	龚殿婷，李凤华，樊占国，等.高纯硼酸的制备及其影响因素［J］.中南大学学报：自然科学版，2010，41（5）：1756-1760.
	GONG Dianting， LI Fenghua， FAN Zhanguo，et al.Preparation of high purity boric acid and its influencing factors［J］.Journal of Central South University：Science and Technology，2010，41（5）：1756-1760.
14	叶俊伟，宁桂玲，潘欣艾，等.一种核电级高纯硼酸的制备方法：中国，102001675A［P］.2011-04-06.
	YE Junwei， NING Guiling， PAN Xin´ai，et al.Method for preparing nuclear power-grade high-purity boracic acid：CN，
	102001675A［P］.2011-04-06.
15	宁桂玲，叶俊伟，潘欣艾，等.一种络合结晶法脱除硼酸中金属杂质的方法：中国，101575100B［P］.2011-02-02.
	NING Guiling， YE Junwei， PAN Xin′ai，et al.Method for removing metallic impurities in boric acid by complex crystallizing method：CN，101575100B［P］.2011-02-02.
16	田朋，宁桂玲，庞洪昌，等.一种高转化率制备硼酸三甲酯的方法：中国，104478916A［P］.2015-04-01.
	TIAN Peng， NING Guiling， PENG Hongchang，et al.Method for preparing trimethyl borate at high conversion rate：CN，104478916A［P］.2015-04-01.
17	CHIRAS S J.Process of preparing trimethl borate：US，
	2947776［P］.1960-08-02.
18	ENGLISH W D， KIDWELL R L.Azeotrope of isopropyl alcohol and isopropyl borate［J］.Science，1963，139（3552）：341-342.
19	SUWANTHAI W， PUNSUVON V， VAITHANOMSAT P.Calcium methoxide synthesis from quick lime using as solid catalyst in refined palm oil biodiesel production［J］.Advanced Materials Research，2014，834-836：550-554.
20	宁桂玲，仲剑初.高等无机合成［M］.上海：华东理工大学出版社，2007：329-355.
	NING Guiling， ZHONG Jianchu.Advanced inorganic synthe-
	sis［M］.Shanghai：East China University of Science and Technology Press，2007：329-355.
21	LIU X， PIAO X， WANG Y，et al.Calcium methoxide as a solid base catalyst for the transesterification of soybean oil to biodiesel with methanol［J］.Fuel，2008，87（7）：1076-1082.
22	赖海明，李成岳，郑丹星.氯化钙-甲醇化学热泵循环特性的模拟与分析［J］.高校化学工程学报，1993，7（2）：118-124.
	LAI Haiming， LI Chengyue， ZHENG Danxing.Simulation of performance for CaCl₂/CH₃OH chemical heat pump［J］.Journal of Chemical Engineering of Chinese Universities，1993，7（2）：118-124.
23	李靖华，白同春.化学热泵的供热和致冷Ⅰ.氯化钙甲醇络合物的合成反应动力学［J］.太阳能学报，1985，6（3）：319-
327	LI jinghua， BAI tongchun.How a chemical heat pump heats or cools a house：the synthetic kinetics of calcium chloride-methanol complex compounds［J］.Acta Energiae Solaris Sinica，1985，6（3）：319-327.
24	宁桂玲，贺正燕，毕胜南，等.一种脱除高纯硼酸中痕量钙的方法：中国，2021122302721210［P］.2021-12-23.
	NING Guiling， HE Zhengyan， BI Shengnan，et al.Method for removing trace calcium from high purity boric acid：CN，2021122302721210［P］.2021-12-23.
25	GE B， LIN Z Q， ZHOU Z R，et al.Boric acid mediated formation and doping of NiO _X layers for perovskite solar cells with effici- doi: 10.1002/solr
	ency over 21%［J］.Solar RRL，2021，5（4）.Doi：10.1002/solr . doi: 10.1002/solr
	202000810. doi: 10.1002/solr
26	WANG Y， WANG C， WANG Y，et al.Boric acid assisted reduction of graphene oxide：A promising material for sodium-ion batteries［J］.ACS Applied Materials & Interfaces，2016，8（29）：18860-18866.
27	SHIM J， JI S L， JIN H L，et al.Gel polymer electrolytes containing anion-trapping boron moieties for lithium-ion battery applications［J］.ACS Applied Materials & Interfaces，2016，8（41）：27740-27752.
28	WU Z A， LIU Y B， DENG C B，et al.The critical role of boric acid as electrolyte additive on the electrochemical performance of lead-acid battery［J］.Journal of Energy Storage，2020，27.Doi：10.1016/j.est.2019.101076 . doi: 10.1016/j.est.2019.101076
29	JIN M， ZHANG Y， YAN C，et al.A high-performance ionic liquid-based gel polymer electrolyte incorporating anion-trapping boron sites for all-solid-state supercapacitor application［J］.ACS Applied Materials & Interfaces，2018，10：39570-39580.
	pelletized graphite addition on properties of Al 2 O₃-SiC-C casta-
	bles［J］.Refractories，2014，48（1）：54-57.

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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