偏硼酸镁在氯化锂水溶液中水解的硼物种转化与分布规律

doi:10.19964/j.issn.1006-4990.2022-0358

Abstract

Abstract:

Salt lake brine contains lithium chloride and borate，and boron is one of the main interference factors in the process of recovering lithium from salt lake.In order to know the characteristics of boron species distributed in brine，the distribution law of boron species in lithium chloride aqueous solution was mainly studied.The distribution and concentration state of liquid boron species and their variate behavior with lithium chloride concentration were obtained by studying the solid and liquid boron species produced from the reactions of Mg（BO₂）₂hydrolyzed in a series of aqueous solutions with LiCl concentration from zero to saturation.The results showed that inderite formed when Mg（BO₂）₂was decomposed in water；hungchsaoite and pinnoite but notinderite would generate when Mg（BO₂）₂was decomposed in LiCl aqueous solution with a lower concentration； and only pinnoitewould form in high concentration LiCl aqueous solution.Although Mg（BO₂）₂ was coexisted with hydrolyzed solid phase，but it was not a stable salt and could not be in phase equilibrium with the liquid phase.The distribution of liquid boron species was not only related to pH，but also to LiCl concentration.When LiCl concentration was low，B₃O₃（OH）₄^-was more than 55% of the total liquid boron.The distribute rate of B₃O₃（OH）₄^- was decreased and

B₅O₆（OH）₄^- was increased significantly while LiCl concentration was increased.B（OH）₄^- and B₃O₃（OH）₄^-were the boron species with highest concentration in all the LiCl concentration range.B₃O₃（OH）₅^2-，B₄O₅（OH）₄^2- and B（OH）₄^- were the anionic configurations of inderite，hungchsaoite and pinnoite respectively，moreover their concentrations were related to the solubility of the solid phase，while B₃O₃（OH）₄^- and B₅O₆（OH）₄^- were not corresponding to solid salt，but could maintain higher concentrations.These results and a large number of species data provided an important basis for recognizing the characteristics of boron in brine and quantifying the distribution of boron in brine.

Key words: Mg（BO₂）₂, LiCl aqueous solution, raman spectroscopy, solution structure, boron species, chemical reactions

CLC Number:

TQ128.1

WEI Fengdan, ZHOU Huan, XIA Panping, ZHAO Yun. Boron species transformation and distribution law of Mg（BO₂）₂decomposed in LiCl aqueous solution[J]. Inorganic Chemicals Industry, 2023, 55(4): 45-53.

Figures/Tables 10

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硼物种	优势区 pH*	峰位（本文）/ cm^-1	峰位（参考文献）/ cm^-1
H₃BO₃	<4.0	877	877^[35]、878^[36]、870~880^[37]
B（OH）₄^-	>10	750	740~755^[37]
B₃O₃（OH）₄^-	7.8	418、450	440~500^[37]、442^[37]
B₃O₃（OH）₅^2-	10.2	615	610~620^[37]
B₄O₅（OH）₄^2-	8.8	577	577^[36]、560~570^[37]
B₅O₆（OH）₄^-	6.2	530	520~530^[37]

组别	w（LiCl）/%	pH	组别	w（LiCl）/%	pH
A₀	0.00	7.00	A₅	28.83	7.67
A₁	5.78	8.87	A₆	34.72	7.24
A₂	11.54	8.66	A₇	40.29	6.80
A₃	17.37	8.40	A₈	42.90	6.64
A₄	23.04	8.23

组别	液相pH
组别	1 d	2 d	3 d	4 d	5 d	6 d	7 d	8 d	9 d	10 d
A₀	10.34	10.33	10.23	10.21	10.20	10.20	10.19	10.20	10.18	10.16
A₁	10.12	10.06	9.95	9.96	9.93	9.93	9.95	9.89	9.92	9.95
A₂	9.66	9.69	9.58	9.59	9.61	9.63	9.64	9.55	9.60	9.62
A₃	9.19	9.20	9.15	9.15	9.13	9.15	9.14	9.17	9.17	9.07
A₄	8.76	8.71	8.62	8.62	8.55	8.57	8.61	8.65	8.67	8.68
A₅	8.12	8.04	8.03	8.05	8.03	8.03	8.02	8.05	8.04	8.02
A₆	7.41	7.37	7.35	7.39	7.38	7.38	7.40	7.37	7.37	7.38
A₇	6.98	6.91	6.90	6.76	6.83	6.70	6.68	6.58	6.56	6.64
A₈	6.39	6.53	6.52	6.47	6.33	6.30	6.25	6.45	6.44	6.45

试验编号		液相组成质量分数/%				密度/ （kg·L^-1）	pH	固相组成质量分数/%				水解固相
试验编号		Mg²⁺	Li⁺	Cl^-	B₂O₃	密度/ （kg·L^-1）	pH	Mg²⁺	Li⁺	Cl^-	B₂O₃	水解固相
1 d	A₀	0.01	0.00	0.00	0.18	1.001	10.34	28.05	0.00	0.00	43.12	—
	A₁	0.01	0.10	4.75	0.24	1.035	10.12	26.18	0.45	1.24	46.86	—
	A₄	0.01	3.38	18.97	0.28	1.140	8.76	15.79	1.81	8.00	32.96	—
	A₇	0.02	5.97	33.20	0.30	1.269	6.98	16.28	2.37	8.33	32.09	—
2 d	A₀	0.01	0.00	0.00	0.16	1.000 6	10.23	27.47	0.00	0.00	45.02	—
	A₁	0.02	0.44	4.74	0.24	1.034 4	9.95	26.25	0.34	1.58	42.24	—
	A₄	0.02	3.44	18.99	0.26	1.141 9	8.62	16.57	2.33	1.67	27.73	—
	A₇	0.02	6.01	33.07	0.28	1.268 8	6.90	17.26	2.58	9.99	43.38	—
5 d	A₀	0.02	0.00	0.00	0.17	1.000 8	10.20	35.51	0.00	0.00	55.17	—
	A₁	0.02	0.41	4.84	0.24	1.034 4	9.93	26.69	0.27	7.09	42.55	—
	A₄	0.02	3.41	19.13	0.25	1.141 9	8.55	16.28	1.96	24.52	33.68	—
	A₇	0.03	6.02	33.53	0.29	1.268 6	6.83	18.97	1.84	24.81	43.13	—
10 d	A₀	0.01	0.00	0.00	0.16	1.000 2	10.16	20.06	0.00	0.00	32.25	S0+S1+S4
	A₁	0.02	0.39	4.78	0.22	1.034 3	9.92	19.43	2.01	10.60	35.32	S0+S2+S3+S4
	A₂	0.02	1.64	9.60	0.25	1.068 3	9.62	18.86	2.00	10.84	34.67	S0+S2+S3+S4
	A₃	0.02	2.84	14.28	0.25	1.104 4	9.17	19.00	2.05	10.73	33.92	S0+S2+S3+S4
	A₄	0.02	3.41	18.85	0.26	1.137 6	8.68	18.98	1.64	9.29	55.34	S0+S3
	A₅	0.02	4.41	23.81	0.27	1.181 5	8.02	18.29	2.23	11.16	32.48	S0+S3
	A₆	0.02	5.10	28.53	0.28	1.223 8	7.38	18.71	2.37	11.91	29.53	S0+S3
	A₇	0.03	6.07	32.40	0.29	1.261 0	6.56	16.81	1.40	13.34	32.26	S0+S3
	A₈	0.03	6.64	35.78	0.30	1.287 0	6.45	10.64	5.35	27.88	18.31	S0+S3+S5

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Boron species transformation and distribution law of Mg（BO₂）₂decomposed in LiCl aqueous solution

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