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

表1

图1

图2

图3

表2

表3

表4

参考文献 29

1	张婉玉, 魏君英. 我国农药化肥减量效应与推进对策[J].北方园艺, 2021（18）：167-172.
	ZHANG Wanyu, WEI Junying. Research on the reducing effect of pesticides and fertilizers in my country and the promoting countermeasures[J].Northern Horticulture, 2021（18）：167-172.
2	KHAN H I. Appraisal of biofertilizers in rice：To supplement inorganic chemical fertilizer[J].Rice Science, 2018, 25（6）：357-362.
3	XIE Xiaofei. Study on the effect of chemical fertilizer reduction on new agricultural operation subject[C]//Proceedings of 2nd International Conference on the Frontiers of Innovative Economics and Management（FIEM 2021.Jiangsu，China，2021.
4	GUO Yanle, ZHANG Min, LIU Zhiguang, et al. Applying and optimizing water-soluble，slow-release nitrogen fertilizers for water-saving agriculture[J].ACS Omega, 2020, 5（20）：11342-11351.
5	SAVCI S. Investigation of effect of chemical fertilizers on environment[J].APCBEE Procedia, 2012, 1：287-292.
6	梁嘉敏, 杨虎晨, 张立丹, 等. 我国水溶性肥料及水肥一体化的研究进展[J].广东农业科学, 2021, 48（5）：64-75.
	LIANG Jiamin, YANG Huchen, ZHANG Lidan, et al. Research progress of water-soluble fertilizer and fertigation in China[J].Guangdong Agricultural Sciences, 2021, 48（5）：64-75.
7	SUN Guangzhao, HU Tiantian, LIU Xiaogang, et al. Optimizing irrigation and fertilization at various growth stages to improve mango yield，fruit quality and water-fertilizer use efficiency in xerothermic regions[J].Agricultural Water Management, 2022, 260.Doi：10.1016/j.agwat.2021.107296. doi: 10.1016/j.agwat.2021.107296
8	付强强, 郑瑞永, 李万和, 等. 固体水溶性肥料生产工艺现状[J].磷肥与复肥, 2019, 34（5）：20-22.
	FU Qiangqiang, ZHENG Ruiyong, LI Wanhe, et al. Production process for solid water-soluble fertilizer[J].Phosphate ＆ Compound Fertilizer, 2019, 34（5）：20-22.
9	PAWAR N, SAHA A, NANDAN N, et al. Solution cocrystallization：A scalable approach for cocrystal production[J].Crystals, 2021, 11（3）：303-321.
10	蒋成君, 程桂林. 共结晶分离技术研究进展[J].化工进展, 2020, 39（1）：311-319.
	JIANG Chengjun, CHENG Guilin. Progress in co-crystallization as a separation technology[J].Chemical Industry and Engineering Progress, 2020, 39（1）：311-319.
11	GUI Lintao, YANG Haitao, HUANG Hui, et al. Liquid solid fluidized bed crystallization granulation technology：Development，applications，properties，and prospects[J].Journal of Water Process Engineering, 2022, 45.Doi：10.1016/j.jwpe.2021.102513. doi: 10.1016/j.jwpe.2021.102513
12	邓天龙, 周桓, 陈侠. 水盐体系相图及应用[M].北京：化学工业出版社, 2013.
13	WALAS S M. Phase equilibria in chemical engineering[M].Boston：Butterworth, 1985.
14	王肖丽, 朱静, 吴强, 等. NH₄ ⁺，K⁺//H₂PO₄ ^-，CO（NH₂）₂-H₂O四元体系298.15 K相平衡研究[J].化学工程, 2021, 49（8）：39-44.
	WANG Xiaoli, ZHU Jing, WU Qiang, et al. Phase equilibrium of quaternary system NH₄ ⁺，K⁺//H₂PO₄ ^-，CO（NH₂）₂-H₂O at 298.15 K[J].Chemical Engineering（China）, 2021, 49（8）：39-44.
15	黄林川, 李天祥, 杨家敏, 等. 三元体系KH₂PO₄-CO（NH₂）₂-H₂O在283.15 K的固液相平衡测定与关联[J].化学工业与工程, 2021, 38（3）：64-69.
	HUANG Linchuan, LI Tianxiang, YANG Jiamin, et al. Determination and correlation of solid-liquid equilibrium of ternary system KH₂PO₄-CO（NH₂）₂-H₂O at 283.15 K[J].Chemical Industry and Engineering, 2021, 38（3）：64-69.
16	杨家敏, 朱静, 胡雪, 等. 283.15 K下三元KCl-NH₄Cl-H₂O和KH₂PO₄-NH₄H₂PO₄-H₂O体系固-液相平衡测定与关联[J].无机盐工业, 2021, 53（1）：30-35.
	YANG Jiamin, ZHU Jing, HU Xue, et al. Determination and correlation for solid-liquid phase equilibrium of ternary KCl-NH₄Cl-H₂O and KH₂PO₄-NH₄H₂PO₄-H₂O systems at 283.15 K[J].Inorganic Chemicals Industry, 2021, 53（1）：30-35.
17	于梅. 钾-铵基固溶体水盐体系的相平衡、结构特性及其分离过程研究[D].银川：宁夏大学, 2019.
	YU Mei. Research on phase equilibrium，structural properties and separation process of potassium-ammonium based solid solution in aqueous solid solution[D].Yinchuan：Ningxia University, 2019.
18	EYSSELTOVÁ J, DIRKSE T P. IUPAC-NIST solubility data series 66.Ammonium phosphates[J].Journal of Physical and Che- mical Reference Data, 1998, 27（6）：1289-1470.
19	叶祥盛, 童军, 赵竹青. 流动注射分析法与钼锑抗比色法分析土壤有效磷含量的比较[J].河北农业科学, 2011, 15（1）：160-164.
	YE Xiangsheng, TONG Jun, ZHAO Zhuqing. Detection of soil available phosphorus content by flow injection analysis method and Mo-Sb antispetrophotography method[J].Journal of Hebei Agricultural Sciences, 2011, 15（1）：160-164.
20	苗晓杰, 蒋恩臣, 王佳, 等. 对二甲氨基苯甲醛显色分光光度法检测水溶液中常微量尿素[J].东北农业大学学报, 2011, 42（8）：87-92.
	MIAO Xiaojie, JIANG Enchen, WANG Jia, et al. Using spectrophotometry with para-dimethyl-amino-benzaldehyde as chromogenic agent to determine macro and micro urea in aqueous solution[J].Journal of Northeast Agricultural University, 2011, 42（8）：87-92.
21	MEHTA A P, MAKOGON T Y, BURRUSS R C, et al. A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach[J].Fluid Phase Equilibria, 1996, 121（1/2）：141-165.
22	王肖丽. K⁺//Cl^-，H₂PO₄ ^-，（NH₂）₂CO-H₂O和NH₄ ⁺，K⁺//Cl^-，（NH₂）₂CO-H₂O体系在 353.15 K下相平衡研究[D].贵阳：贵州大学, 2021.
23	WANG Jian, XU Renjie, XU Anli, et al. Thermodynamic modelling for solubility of 5-chloro-1-methyl-4-nitroimidazole in eleven organic solvents from T=（283.15 to 318.15） K[J].The Journal of Chemical Thermodynamics, 2017, 105：58-70.
24	WILSON G M. Vapor-liquid equilibrium.XI.A new expression for the excess free energy of mixing[J].Journal of the American Chemical Society, 1964, 86（2）：127-130.
25	RENON H, PRAUSNITZ J. Estimation of parameters for the NRTL equation for excess Gibbs energies of strongly nonideal liquid mixtures[J].Industrial & Engineering Chemistry Process Design and Development, 1969, 8：413-419.
26	HUANG Chunxiang, FANG Yun, WANG Jun, et al. Measurement and modelling of ternary solid-liquid phase equilibrium of （DL-malic acid+maleic acid+water） from 283.15 K to 333.15 K[J].The Journal of Chemical Thermodynamics, 2021, 159.Doi：10.1016/j.jct.2021.106470. doi: 10.1016/j.jct.2021.106470
27	LI Rongrong, JIN Yanxian, YU Binbin, et al. Solubility determination and thermodynamic properties calculation of macitentan in mixtures of ethyl acetate and alcohols[J].The Journal of Chemical Thermodynamics, 2021, 156.Doi：10.1016/j.jct.2020.106344. doi: 10.1016/j.jct.2020.106344
28	刘光启, 马连湘, 刘杰. 化学化工物性数据手册-无机卷[M].北京：化学工业出版社, 2002.
29	中国寰球化学工程公司. 氮肥工艺设计手册[M].北京：化学工业出版社, 1988.

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

[1]	王彦飞, 杨超凡, 曹迪, 许史杰. 多温下三元体系Li⁺，Na⁺∥Cl^--H₂O固液相平衡研究[J]. 无机盐工业, 2024, 56(1): 33-39.
[2]	冯霞, 于雪峰, 姚智豪, 罗军, 任思颖, 赵志星, 于旭东. 三元体系Na⁺（Mg²⁺），Ca²⁺∥Cl^--H₂O 278.2 K稳定相平衡研究[J]. 无机盐工业, 2024, 56(1): 47-52.
[3]	巩学敏, 张荣瑜, 李娜, 郝雅楠, 张千. 海水体系碳酸钠水合物结晶形成过程研究及应用[J]. 无机盐工业, 2023, 55(3): 55-59.
[4]	闫芳宁,郭锦春,黄雪莉,周婷婷,王雪莹,罗清龙,邹雪净. 258.15 K下五元体系Li⁺，Na⁺，Mg²⁺//SO₄^2-，Cl^--H₂O相平衡研究[J]. 无机盐工业, 2023, 55(2): 61-66.
[5]	宋智, 刘伯霞, 陈瑶瑶. FeWO₄/WO₃复合物的溶胶-凝胶合成及降解纺织染料废水研究[J]. 无机盐工业, 2022, 54(5): 131-137.
[6]	陈帅,杨博,陈念粗,罗军,任思颖,曾英,于旭东. 三元体系NH₄Cl+MgCl₂+H₂O 323.2 K相平衡研究[J]. 无机盐工业, 2022, 54(4): 100-103.
[7]	杨文博,吴潘,何坚,刘长军,蒋炜. 升温速率对尿素热解制g-C₃N₄光催化剂构效影响研究[J]. 无机盐工业, 2022, 54(4): 169-174.
[8]	卢子钰,柳召刚,吴锦绣,胡艳宏,刘兴宇. 三元体系Na₂CO₃-NaF-H₂O 298.15 K和318.15 K相平衡研究[J]. 无机盐工业, 2022, 54(3): 66-70.
[9]	王逸夫,金央,李军. 微尺度流动体系的介稳区测定方法及影响[J]. 无机盐工业, 2022, 54(2): 45-49.
[10]	樊小娟,朱静,邓文清,陈艳,李天祥. 交互四元体系K⁺,NH₄⁺//Cl^-,H₂PO₄^--H₂O 在313.15 K时相平衡研究[J]. 无机盐工业, 2022, 54(10): 102-108.
[11]	马玉军,王晓,李淑雅,张付康,李娟. 四元体系NaCl+NaBO₂+Na₂CO₃+H₂O 298.15 K 相平衡研究[J]. 无机盐工业, 2022, 54(10): 42-46.
[12]	张焕焕,程卓,汤秀华,张峰榛. 磷酸二氢钾在乙腈-水溶剂中溶解度的测定与关联[J]. 无机盐工业, 2022, 54(1): 83-85.
[13]	刘治国,张娜,陈川,徐显朕. 水盐体系汽液平衡的热力学模型研究[J]. 无机盐工业, 2021, 53(8): 55-59.
[14]	王斌,邓小川,史一飞,董超超,樊发英,朱朝梁,樊洁. 碳酸锂在水和NaCl-KCl溶液体系中溶解度的在线测定[J]. 无机盐工业, 2021, 53(7): 73-79.
[15]	陈云飞,毛丽莉,刘丹,王海增. 六水氯化镁在六种多元醇中溶解度的测定和关联[J]. 无机盐工业, 2021, 53(12): 85-90.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 29

相关文章 15

Metrics

本文评价

推荐阅读 0

首 页