盐酸法磷酸萃取相的洗涤和磷酸反萃取过程初探

doi:10.19964/j.issn.1006-4990.2020-0545

Abstract

Abstract:

The process of back extraction of phosphoric acid from tributyl phosphate（TBP） was studied.The quality of the different stripped phosphoric acid obtained by the one-step process（simultaneously precipitating CaCl₂and stripping H₃PO₄with H₂SO₄ solution） and by the two-step process（firstly precipitating and removing CaCl₂ with H₂SO₄,then stripping H₃PO₄with deionized water） was investigated.The results showed that in the one-step process the purity of the stripped phosphoric acid was affected by the dissolution balance of calcium sulfate with high content of calcium,while in the two-step process,the contents of CaCl₂ in the stripped reduced to below 0.002 7%,and the value of n（H₃PO₄）/n（Ca²⁺） increased by more than 65 times,but the H₃PO₄ loss in organic phase caused by scrubbing process was about 20%.The focused beam reflectance measurement（FBRM） technology was used to monitor the crystallization of calcium sulfate on line in the organic phase during the scrubbing process.The morphology and phase composition of the calcium sulfate were analyzed by scanning electron microscope（SEM） and X-ray diffraction（XRD） methods.The results showed that after scrubbing for 10 min under the experimental conditions,Ca²⁺ in the system basically generated hemihydrate gypsum（CaSO₄·0.5H₂O）.Theoretical calcula-tion indicated that the production of the by-product gypsum（calculated as CaSO₄·2H₂O） in scrubbing step of the wet phosp-horic acid process by hydrochloric acid route was only equivalent to 8.7% of that by sulfuric acid route,significantly reduces the amount of gypsum treated in the wet process phosphoric acid process.

Key words: wet process phosphoric acid, hydrochloric acid route, solvent extraction, scrubbing, stripping

CLC Number:

TQ126.35

Zhang Shaojie,Tang Shengwei,Wang Yang,Zheng Dongyue,Zhong Benhe,Chen Yanxiao. Preliminary study on scrubbing and stripping operation of the extracted organic phase in wet phosphoric acid process by hydrochloric acid route[J]. Inorganic Chemicals Industry, 2021, 53(8): 36-43.

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名称	试剂级别
实验室用超纯水	电导率≤10^-4 S/m
盐酸	AR,≥37%（质量分数）
硫酸	AR,95%~98%（质量分数）
磷酸三丁酯（TBP）	AR,≥99%（质量分数）
磺化煤油	沸程180~280 ℃

w（P₂O₅）	w（CaO）	w（Fe₂O₃）	w（Al₂O₃）	w（MgO）
28.88	37.61	1.10	1.72	0.19
w（K₂O）	w（F）	w（SiO₂）	烧失量	w（其他）
0.46	1.85	21.33	2.40	4.46

序号	温度/ ℃	V（A）/ V（O）	时间/ min	c（H₂SO₄）浓度/ （mol·L^-1）	反萃酸组成		n（H₃PO₄）/ n（Ca²⁺）	反萃取率 SE/%
序号	温度/ ℃	V（A）/ V（O）	时间/ min	c（H₂SO₄）浓度/ （mol·L^-1）	w （H₃PO₄）/%	w （CaCl₂）/%	n（H₃PO₄）/ n（Ca²⁺）	反萃取率 SE/%
a₁	20	1∶3	70	0.404 5	8.35	0.21	45.19	56.33
a₂	20	2∶3	70	0.212 3	5.45	0.23	26.51	85.92
a₃	20	1∶1	70	0.134 9	3.87	0.20	21.76	92.28
b₁	40	1∶3	70	0.404 5	9.47	0.26	41.03	67.12
b₂	40	2∶3	70	0.212 3	5.46	0.25	24.71	89.84
b₃	40	1∶1	70	0.134 9	3.58	0.20	20.11	93.23
c₁	60	1∶3	70	0.404 5	9.56	0.24	45.21	75.71
c₂	60	2∶3	70	0.212 3	5.94	0.24	28.51	92.62
c₃	60	1∶1	70	0.134 9	3.92	0.20	22.17	96.05

温度/ ℃	相比 V（A）/V（O）	时间/ min	反萃取酸组成		n（H₃PO₄）/ n（Ca²⁺）	反萃取率SE / %
温度/ ℃	相比 V（A）/V（O）	时间/ min	w （H₃PO₄）/%	w （CaCl₂）/%	n（H₃PO₄）/ n（Ca²⁺）	反萃取率SE / %
20	1∶3	30	7.17	0.002 7	3 039.47	59.29
20	2∶3	30	4.36	0.001 4	5 731.35	68.73
20	1∶1	30	2.95	0.001 1	4 384.53	70.83

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Preliminary study on scrubbing and stripping operation of the extracted organic phase in wet phosphoric acid process by hydrochloric acid route

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