313.15 K下三元体系KH2PO4-（NH2）2CO-H2O相平衡研究

doi:10.19964/j.issn.1006-4990.2022-0211

Abstract

Abstract:

The solubility data of ternary system of KH₂PO₄-（NH₂）₂CO-H₂O at 313.15 K was determined by isothermal solubility equilibrium method，the isothermal phase diagram was drawn according to solubility data，the composition of equilibrium solid phase was analyzed by wet slag method and X-ray diffraction method.The results showed that the ternary system of KH₂PO₄-（NH₂）₂CO-H₂O was a simple co-saturation system with one co-saturation point，two univariate curves and three crystal regions in the phase diagram.Wilson and NRTL models were used to correlate the solubility data of the system，and the correlation values were in good agreement with the experimental values.The relative mean deviation（RAD） and root mean square deviation（RMSD） of Wilson model were 3.34% and 0.17% respectively，and RAD and RMSD of NRTL model were 10.53% and 0.38%，respectively.By comparing the phase equilibrium crystallization regions of ternary system of KH₂PO₄-（NH₂）₂CO-H₂O at multiple temperatures，it was found that lowering the temperature was beneficial to the crystallization of（NH₂）₂CO，but unfavorable to the crystallization of KH₂PO₄ at medium and low temperature stages.KH₂PO₄ inhibitsed the dissolution of（NH₂）₂CO at high temperature.It provided a theoretical support for the subsequent research on phase equilibrium of quaternary system and the production of multi-component water-soluble fertilizer by cooling crystallization.

Key words: phase equilibrium, solubility, urea, KH₂PO₄, thermodynamic model

CLC Number:

TQ131.13

DENG Wenqing,ZHU Jing,FAN Xiaojuan,CHEN Yan,LI Tianxiang. Phase equilibria of ternary system of KH₂PO₄-（NH₂）₂CO-H₂O at 313.15 K[J]. Inorganic Chemicals Industry, 2023, 55(1): 100-105.

Figures/Tables 7

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References 29

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序号	液相质量分数/%			湿渣质量分数/%			平衡固相
序号	KH₂PO₄	（NH₂）₂CO	H₂O	KH₂PO₄	（NH₂）₂CO	H₂O	平衡固相
1，F	25.09	0.00	74.91	—	—	—	KH₂PO₄
2	22.36	7.91	69.73	63.90	4.20	31.90	KH₂PO₄
3	19.21	14.06	66.73	62.98	7.18	29.84	KH₂PO₄
4	17.45	21.24	61.31	60.72	10.76	28.52	KH₂PO₄
5	16.00	25.75	58.24	60.98	11.26	27.76	KH₂PO₄
6	14.91	26.93	58.17	78.21	7.86	13.93	KH₂PO₄
7	14.45	29.00	56.55	69.91	10.21	19.88	KH₂PO₄
8	13.83	32.71	53.46	73.46	11.31	15.23	KH₂PO₄
9	13.12	35.20	51.69	55.51	19.12	25.37	KH₂PO₄
10	12.86	39.46	47.67	59.80	18.24	21.96	KH₂PO₄
11	11.75	43.45	44.80	78.31	11.23	10.46	KH₂PO₄
12	11.43	45.19	43.39	62.03	20.18	17.79	KH₂PO₄
13	10.48	48.98	40.54	66.21	18.21	15.58	KH₂PO₄
14	9.79	50.92	39.29	61.27	22.12	16.61	KH₂PO₄
15	9.38	52.34	38.28	75.30	15.42	9.28	KH₂PO₄
16	9.30	53.63	37.07	38.71	36.72	24.57	KH₂PO₄
17	8.67	54.27	37.06	78.51	14.82	6.67	KH₂PO₄
18	8.45	56.60	34.95	37.26	38.97	23.77	KH₂PO₄
19	7.81	58.96	33.23	39.87	38.90	21.23	KH₂PO₄
20，E	6.96	60.99	32.05	36.78	41.69	21.53	KH₂PO₄+（NH₂）₂CO
21	6.90	60.88	32.22	6.53	65.40	28.07	（NH₂）₂CO
22	6.44	61.32	32.24	4.58	74.55	20.87	（NH₂）₂CO
23	5.17	62.00	32.83	4.03	73.44	22.53	（NH₂）₂CO
24	3.67	62.12	34.21	2.50	73.99	23.51	（NH₂）₂CO
25	1.76	62.71	35.53	1.63	68.08	30.29	（NH₂）₂CO
26，D	0.00	63.05	36.95	—	—	—	（NH₂）₂CO

物质	T_m/K	ΔH/（J·mol^-1）	ρ/（g·cm^-3）	M/（g·mol^-1）
KH₂PO₄	511.25	52 156.22	2.338	136.09
（NH₂）₂CO	406.00	14 519.90	1.335	63.04

i-j	Wilson			NRTL
i-j	a	b	Λ	a	b	τ
KH₂PO₄-H₂O	5.87	-3 860.72	197.52	-1.47	-491.56	-3.04
H₂O-KH₂PO₄	6.18	-1 262.15	0.38	-15.86	8 867.52	12.46
（NH₂）₂CO-H₂O	-1.54	-169.38	3.21	4.13	-1 569.63	-0.88
H₂O-（NH₂）₂CO	3.33	-123.86	0.13	15.01	-2 569.84	6.80
KH₂PO₄- （NH₂）₂CO	-37.07	0.51	9.70×10¹⁵	-19.87	-3 310.29	-30.44
（NH₂）₂CO- KH₂PO₄	-2.82	1.97	21.56	-0.59	-0.56	-0.59

序号	液相物质的量分数，m		Wilson计算值，m		NRTL计算值，m
序号	KH₂PO₄	（NH₂）₂CO	KH₂PO₄	（NH₂）₂CO	KH₂PO₄	（NH₂）₂CO
1，F	0.042 5	0.000 0	0.039 2	—	0.040 3	—
2	0.039 4	0.031 6	0.037 1	—	0.037 7	—
3	0.034 6	0.057 4	0.035 6	—	0.039 7	—
4	0.033 0	0.091 0	0.033 4	—	0.035 0	—
5	0.031 1	0.113 5	0.032 0	—	0.033 0	—
6	0.028 9	0.118 4	0.031 8	—	0.035 3	—
7	0.028 5	0.129 5	0.031 1	—	0.033 3	—
8	0.028 1	0.150 7	0.029 8	—	0.029 3	—
9	0.027 1	0.165 0	0.028 9	—	0.027 8	—
10	0.027 8	0.193 4	0.027 1	—	0.022 0	—
11	0.026 2	0.219 5	0.025 7	—	0.020 1	—
12	0.025 9	0.231 9	0.024 9	—	0.018 9	—
13	0.024 5	0.259 5	0.023 4	—	0.017 5	—
14	0.023 2	0.273 4	0.022 7	—	0.017 9	—
15	0.022 5	0.284 3	0.022 1	—	0.018 0	—
16	0.022 6	0.295 8	0.021 4	—	0.016 9	—
17	0.021 1	0.298 8	0.021 4	—	0.019 5	—
18	0.021 1	0.320 1	0.020 2	—	0.018 0	—
19	0.019 9	0.340 4	0.019 2	—	0.019 9	—
20，E	0.018 0	0.356 9	—	0.358 1	—	0.356 5
21	0.017 8	0.355 3	—	0.358 0	—	0.356 5
22	0.016 6	0.357 3	—	0.356 6	—	0.356 7
23	0.013 1	0.356 9	—	0.352 8	—	0.355 1
24	0.009 1	0.3494	—	0.349 2	—	0.351 4
25	0.004 3	0.344 7	—	0.344 3	—	0.344 9
26，D	0.000 0	0.338 6	—	0.340 1	—	0.338 0
RAD/%			3.34 0.17		10.53 0.38
RMSD/%			3.34 0.17		10.53 0.38

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Phase equilibria of ternary system of KH₂PO₄-（NH₂）₂CO-H₂O at 313.15 K

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Phase equilibria of ternary system of KH2PO4-（NH2）2CO-H2O at 313.15 K