Effect of Chlorine Removal on Crystallization in the Mother Liquor of Ammonium Sulfate

doi:10.19894/j.issn.1000-0518.210544

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (9): 1437-1446.DOI: 10.19894/j.issn.1000-0518.210544

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Effect of Chlorine Removal on Crystallization in the Mother Liquor of Ammonium Sulfate

Gao-Yong ZI¹^,², Bang-Fu HUANG¹^,²(), Meng DAI¹^,², Zheng-Yu YANG¹^,², Zhen-Jing WEN¹^,², Wan-Jun LI¹^,², Liu-Bin LUO¹^,²

^1.Faculty of Metallurgical and Energy Engineering，Kunming University of Science and Technology，Kunming 650093，China
^2.Clean Metallurgy Key Laboratory of Complex Iron Resources，University of Yunnan Province，Kunming 650093，China

Received:2021-11-23 Accepted:2022-02-28 Published:2022-09-01 Online:2022-09-08
Contact: Bang-Fu HUANG
About author:kmusthbf@163.com
Supported by:
the General Project of Applied Basic Research Program of Yunnan Province(202001AT070029);the Open Foundation of Key Laboratory of Iron and Steel Metallurgy and Resource Utilization of Ministry of Education(FMRUlab?20?4)

Abstract

Abstract:

Continuous cyclic enrichment of Cl^- in mother liquor of ammonium sulfate causes serious corrosion of equipment， while also affecting the crystallization and quality of ammonium sulfate. Dechlorination of the mother liquor of ammonium sulfate is investigated using calcium aluminum sulfate and desulfurized ash aluminum approach. A sieving approach is used to analyze the crystal size， scanning electron microscope is used to characterize the crystal size and morphology， and X-ray diffraction is used to analyze the crystal phase. The results show that the optimal dechlorination agent dosage is 3.0 g calcium sulfate and 0.8 g sodium metaaluminate， 3.0 g desulfurization ash and 0.8 g sodium metaaluminate， corresponding to dechlorination rates of 31.70% and 36.38%， respectively. At a rate of 200 r/min and a reaction temperature of 75 ℃， the addition of two dechlorinating agents causes the ρ（Cl^-） to drop rapidly. The reaction of Cl^- with Ca²⁺ and AlO₂^- forms insoluble calcium aluminum chloride compounds. Excessive NaAlO₂ causes double hydrolysis， dissociates OH^-， and inhibits the reaction of Cl^- with Ca²⁺ and AlO₂^-， resulting in a decrease in the rate of Cl^- removal. The calcium aluminum chloride compound forms using the calcium aluminum sulfate approach will adhere to the crystal grains′ active surface， thereby increasing the width of the ammonium sulfate crystal metastable zone， inhibiting the crystal′s normal growth， and reducing the number of crystals； the impurity metal in the desulfurization gray aluminum method can OH^- consumption and reduction of the width of the metastable zone of ammonium sulfate crystals， containing a large amount of SO₄^2- increases the amount of ammonium sulfate crystals， but reduce the crystal purity. The results of related studies can be used as a reference for reducing ammonia desulfurization equipment corrosion and enhancing ammonium sulfate crystallization.

Key words: Ammonium sulfate, Chlorine removal, Calcium aluminum sulfate method, Desulfurization ash aluminum method, Crystallization

CLC Number:

O645.5

Gao-Yong ZI, Bang-Fu HUANG, Meng DAI, Zheng-Yu YANG, Zhen-Jing WEN, Wan-Jun LI, Liu-Bin LUO. Effect of Chlorine Removal on Crystallization in the Mother Liquor of Ammonium Sulfate[J]. Chinese Journal of Applied Chemistry, 2022, 39(9): 1437-1446.

Figures/Tables 8

Fig.1 Effect of dechlorination by calcium sulfate aluminum method

Table 1 Effect of dechlorination by calcium sulfate aluminum method on the crystalline amount， average particle size and C.V. value of ammonium sulfate crystals

序号 Num	除氯剂 Dechlorination agent	结晶量 Crystallization amount/g	平均粒径 The average particle size/mm	C.V.值 C.V.value
1	——	138.600	1.151	509.247
2	3.0 g CaSO₄+0.7 g NaAlO₂	58.652	1.634	720.521
3	3.0 g CaSO₄+0.8 g NaAlO₂	54.311	1.602	768.410
4	3.0 g CaSO₄+0.9 g NaAlO₂	51.003	1.179	524.256
5	3.0 g CaSO₄+1.0 g NaAlO₂	48.011	1.568	685.040
6	3.0 g CaSO₄+1.1 g NaAlO₂	45.554	1.816	647.973

Fig.2 Effect of dechlorination by calcium sulfate aluminum on the morphology of ammonium sulfate crystals（A） Stock solution；（B） 3.0 g CaSO4+0.7 g NaAlO2；（C） 3.0 g CaSO4+0.8 g NaAlO2；（D） 3.0 g CaSO4+0.9 g NaAlO2；（E） 3.0 g CaSO4+1.0 g NaAlO2；（F） 3.0 g CaSO4+1.1 g NaAlO2

Fig.3 XRD diffraction pattern of ammonium sulfate crystals after dechlorination by calcium sulfate aluminum methoda. Stock solution； b. 3.0 g CaSO4+0.7 g NaAlO2； c. 3.0 g CaSO4+0.8 g NaAlO2； d. 3.0 g CaSO4+0.9 g NaAlO2； e. 3.0 g CaSO4+1.0 g NaAlO2； f. 3.0 g CaSO4+1.1 g NaAlO2

Fig.4 Effect of dechlorination by desulfurization ash aluminum method

Table 2 Effect of dechlorination by desulfurization ash aluminum method on the crystallization amount， average particle size and C.V. value of ammonium sulfate crystals

序号 Num	除氯剂 Dechlorination agent	结晶量 Crystallization amount/g	平均粒径 The average particle size/mm	C.V.值 C.V.value
1	——	138.600	1.151	509.247
2	3.0 g脱硫灰+0.7 g NaAlO₂ 3.0 g Desulfurization ash +0.7 g NaAlO₂	149.840	1.150	407.790
3	3.0 g脱硫灰+0.8 g NaAlO₂ 3.0 g Desulfurization ash+0.8 g NaAlO₂	145.614	1.112	427.378
4	3.0 g脱硫灰+0.9 g NaAlO₂ 3.0 g Desulfurization ash+0.9 g NaAlO₂	163.662	1.091	397.555
5	3.0 g脱硫灰+1.0 g NaAlO₂ 3.0 g Desulfurization ash+1.0 g NaAlO₂	153.138	1.063	382.120
6	3.0 g脱硫灰+1.1 g NaAlO₂ 3.0 g Desulfurization ash+1.1 g NaAlO₂	141.383	1.092	403.825

Fig.5 Effect of dechlorination by desulfurization ash aluminum method on the morphology of ammonium sulfate crystals（A） Stock solution；（B） 3.0 g Desulfurization ash +0.7 g NaAlO2；（C） 3.0 g Desulfurization ash+0.8 g NaAlO2；（D） 3.0 g Desulfurization ash +0.9 g NaAlO2；（E） 3.0 g Desulfurization ash+1.0 g NaAlO2；（F） 3.0 g Desulfurization ash+1.1 g NaAlO2

Fig.6 XRD diffraction pattern of ammonium sulfate crystals after dechlorination by desulfurization ash aluminum methoda. Stock solution； b. 3.0 g Desulfurization ash +0.7 g NaAlO2； c. 3.0 g Desulfurization ash +0.8 g NaAlO2； d. 3.0 g Desulfurization ash +0.9 g NaAlO2； e. 3.0 g Desulfurization ash +1.0 g NaAlO2； f. 3.0 g Desulfurization ash +1.1 g NaAlO2

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Effect of Chlorine Removal on Crystallization in the Mother Liquor of Ammonium Sulfate

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