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

摘要/Abstract

摘要：

采用等温溶解平衡法研究了三元体系KH₂PO₄-（NH₂）₂CO-H₂O在313.15 K下的溶解度数据，根据溶解度数据绘制了等温相图，采用湿渣法和X射线衍射法对平衡固相的组成进行了分析。结果表明三元体系KH₂PO₄-（NH₂）₂CO-H₂O为简单共饱和型体系，相图中有1个共饱和点、2条单变量曲线、3个结晶区；采用Wilson和NRTL模型关联该体系的溶解度数据，关联计算值与实验值基本吻合。其中Wilson模型的相对平均偏差（RAD）和均方根差（RMSD）分别为3.34%、0.17%；NRTL模型的RAD和RMSD分别为10.53%、0.38%。对比三元体系KH₂PO₄-（NH₂）₂CO-H₂O在多个温度下相平衡的结晶区域，发现在中、低温阶段降低温度有利于尿素[（NH₂）₂CO]的结晶，而不利于磷酸二氢钾（KH₂PO₄）的结晶；在高温阶段KH₂PO₄对（NH₂）₂CO的溶解会产生抑制作用。为后续四元体系相平衡研究及冷却结晶生产多组分水溶肥的研究提供了理论支撑。

关键词: 相平衡, 溶解度, 尿素, 磷酸二氢钾, 热力学模型

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

中图分类号:

TQ131.13

邓文清,朱静,樊小娟,陈艳,李天祥. 313.15 K下三元体系KH₂PO₄-（NH₂）₂CO-H₂O相平衡研究[J]. 无机盐工业, 2023, 55(1): 100-105.

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.

图/表 7

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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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313.15 K下三元体系KH₂PO₄-（NH₂）₂CO-H₂O相平衡研究

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

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