高盐废水中硫酸铵和硫酸钠的分质结晶工艺研究

doi:10.19964/j.issn.1006-4990.2023-0161

Abstract

Abstract:

The treatment of high salinity wastewater and the recycling of salt resources in wastewater are challenging task faced by enterprises.The liquid-solid equilibrium data of Na₂SO₄-（NH₄）₂SO₄-H₂O at 10，15，60 and 80 ℃ were determined by isothermal solution equilibrium method，and the crystallization regions were divided based on phase equilibrium data.A fractional crystallization process was then proposed for the separation and recovery of（NH₄）₂SO₄ and Na₂SO₄ based on the composition of the high salinity wastewater and the liquid-solid equilibrium data.The technological parameters of the crystallization process were designed and experimentally verified.The results showed that the purity of（NH₄）₂SO₄and Na₂SO₄ by three-step crystallization reached 99.2% and 98.9% respectively，which met the purity index of national standard of GB/T 535—2020 and GB/T 6009—2014.This study provided valuable reference for the recovery of（NH₄）₂SO₄ and Na₂SO₄ from high salinity wastewater.

Key words: high salt wastewater, ammonium sulfate, sodium sulfate, fractional crystallization

CLC Number:

X703

WEI Tianshun, JI Lijun, SHENG Yong, CHEN Kui, WU Yanyang, WU Bin. Study on fractional crystallization process of ammonium sulfate and sodium sulfate in high salt wastewater[J]. Inorganic Chemicals Industry, 2024, 56(1): 102-106.

Figures/Tables 7

Table 1

Fig.1

Table 2

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Table 3

References 11

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序号	液相质量分数/%		平衡固相
序号	（NH₄）₂SO₄	Na₂SO₄	平衡固相
10 ℃
1，A₁	0.00	7.96	Na₂SO₄·10H₂O
2	7.69	9.62	Na₂SO₄·10H₂O
3	9.73	9.83	Na₂SO₄·10H₂O
4	13.74	10.49	Na₂SO₄·10H₂O
5	15.99	10.69	Na₂SO₄·10H₂O
6	18.38	10.97	Na₂SO₄·10H₂O
7	20.93	11.31	Na₂SO₄·10H₂O
8，B₁	24.75	11.79	Na₂SO₄·（NH₄）₂SO₄·4H₂O +Na₂SO₄·10H₂O
9	26.47	10.54	Na₂SO₄·（NH₄）₂SO₄·4H₂O
10	29.85	8.84	Na₂SO₄·（NH₄）₂SO₄·4H₂O
11	33.55	7.30	Na₂SO₄·（NH₄）₂SO₄·4H₂O
12	37.69	5.71	Na₂SO₄·（NH₄）₂SO₄·4H₂O
13，C₁	38.67	5.35	（NH₄）₂SO₄+ Na₂SO₄·（NH₄）₂SO₄·4H₂O
14	39.04	4.83	（NH₄）₂SO₄
15	40.64	2.51	（NH₄）₂SO₄
16	41.21	1.41	（NH₄）₂SO₄
17，D₁	41.97	0.00	（NH₄）₂SO₄
15 ℃
1，A₂	0.00	10.96	Na₂SO₄·10H₂O
2	6.59	12.16	Na₂SO₄·10H₂O
3	11.18	13.26	Na₂SO₄·10H₂O
4	12.51	13.68	Na₂SO₄·10H₂O
5	14.98	14.04	Na₂SO₄·10H₂O
6，B₂	21.65	15.09	Na₂SO₄·（NH₄）₂SO₄·4H₂O +Na₂SO₄·10H₂O
7	23.10	14.31	Na₂SO₄·（NH₄）₂SO₄·4H₂O
8	25.86	12.98	Na₂SO₄·（NH₄）₂SO₄·4H₂O
9	29.23	11.08	Na₂SO₄·（NH₄）₂SO₄·4H₂O
10	31.91	9.62	Na₂SO₄·（NH₄）₂SO₄·4H₂O
11	33.18	8.76	Na₂SO₄·（NH₄）₂SO₄·4H₂O
12，C₂	38.88	5.52	（NH₄）₂SO₄+ Na₂SO₄·（NH₄）₂SO₄·4H₂O
13	38.98	5.36	（NH₄）₂SO₄
14	40.32	3.55	（NH₄）₂SO₄
15	41.43	1.84	（NH₄）₂SO₄
16，D₂	42.94	0.00	（NH₄）₂SO₄

序号	液相质量分数/%		平衡固相
序号	（NH₄）₂SO₄	Na₂SO₄	平衡固相
60 ℃
1，A₃	0.00	30.99	Na₂SO₄
2	12.42	26.11	Na₂SO₄
3	21.89	21.46	Na₂SO₄
4	30.26	18.47	Na₂SO₄
5，B₃	37.12	15.70	Na₂SO₄+（NH₄）₂SO₄
6	37.88	14.47	（NH₄）₂SO₄
7	40.90	9.51	（NH₄）₂SO₄
8	43.02	6.25	（NH₄）₂SO₄
9	44.75	3.38	（NH₄）₂SO₄
10，C₃	46.59	0.00	（NH₄）₂SO₄
80 ℃
1，A₄	0.00	30.00	Na₂SO₄
2	12.08	26.23	Na₂SO₄
3	21.69	22.40	Na₂SO₄
4	30.85	18.81	Na₂SO₄
5，B₄	39.60	15.72	Na₂SO₄+（NH₄）₂SO₄
6	40.61	13.69	（NH₄）₂SO₄
7	42.62	10.26	（NH₄）₂SO₄
8	45.41	5.69	（NH₄）₂SO₄
9，C₄	48.26	0.00	（NH₄）₂SO₄

工艺步骤	母液量/g		母液组成/%
工艺步骤	M_cal	M_exp	w_1，cal	w_2，cal	w_1，exp	w_2，exp
80 ℃浓缩结晶	753.02	748.03	16.11	38.37	16.02	38.43
80 ℃滤液冷却至15 ℃结晶	682.29	682.91	5.85	38.45	5.79	38.57
60 ℃浓缩结晶	612.68	620.73	13.77	38.39	13.62	38.35
60 ℃滤液冷却至15 ℃结晶	754.75	755.33	5.85	38.45	5.92	38.39

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Study on fractional crystallization process of ammonium sulfate and sodium sulfate in high salt wastewater

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