硫酸铵分解过程及其热分解动力学研究

doi:10.19964/j.issn.1006-4990.2022-0105

Abstract

Abstract:

Thermal decomposition of ammonium sulfate can provide ammonium bisulfate solution and ammonia water for the process of leaching fly ash with ammonium bisulfate solution to extract alumina.It is of great significance to study the mechanism and thermal decomposition kinetics of its thermal decomposition process.The products of the decomposition process were characterized by X-ray diffraction，mass spectrometry and Fourier transform infrared spectroscopy，proving that the decomposition products of ammonium sulfate were ammonium hydrogen sulfate，ammonium pyrosulfate，ammonia，water，nitrogen and sulfur dioxide.The characterization method combined with thermogravimetric analysis showed that the thermal decomposition process of ammonium sulfate was divided into three stages：the decomposition of ammonium sulfate to form ammonium bisulfate and ammonia gas，the dehydration of ammonium bisulfate to form ammonium pyrosulfate，and the decomposition of ammonium pyrosulfate.The Ozawa-Flynn-Wall and Kissinger-Akahira-Sunose model-free methods were used to calculate the activation energy for each stage.The Coats–Redfern method was used to determine the most likely dyna-mic mechanism function for each stage.The results showed that the average activation energy was E=125.21 kJ/mol in the first stage，and ln A=18.46；the average activation energy of the second stage was E=110.21 kJ/mol and ln A=13.94；the average activation energy of the third stage was E=97.70 kJ/mol and ln A=8.44.

Key words: ammonium sulfate, thermal decomposition, decomposition kinetics, thermogravimetric analysis

CLC Number:

TQ113.7

WU Di, LI Laishi, WANG Junkai, WU Yusheng, WANG Yuzheng, LI Mingchun. Study on decomposition process and thermal decomposition kinetics of ammonium sulfate[J]. Inorganic Chemicals Industry, 2023, 55(10): 86-92.

Figures/Tables 12

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Table 1

Fig.6

Table 2

Fig.7

Table 3

Fig.8

Table 4

References 25

1	韦聚才，石霖，吴旭.膜电极电解器电解脱硫废水制备硫酸铵副产氢［J］.电化学，2022，28（5）：4-12.
	WEI Jucai， SHI Lin， WU Xu.Simultaneous hydrogen and （NH₄）₂SO₄ productions from desulfurization wastewater electrolysis using MEA electrolyser［J］.Journal of Electrochemistry，2022，28（5）：4-12.
2	ALAM T， SURYANTO P， KASTONO D，et al.Interactions of biochar briquette with ammonium sulfate fertilizer for controlled nitrogen loss in soybean intercopping with melaleuca cajuputi［J］.Legume Research，2021，44：339-343.
3	YIN Shu， ALDAHRI T， ROHANI S，et al.Insights into the roasting kinetics and mechanism of blast furnace slag with ammonium sulfate for CO₂ mineralization［J］.Industrial & Engineering Chemistry Research，2019，58：14026-14036.
4	BATTISTA F， MASALA C， ZAMBONI A，et al.Valorisation of agricultural digestate for the ammonium sulfate recovery and soil improvers production［J］.Waste and Biomass Valorization，2021，12（12）：6903-6916.
5	SONG Xingfu， ZHAO Jingcai， LI Yunzhao，et al.Thermal decomposition mechanism of ammonium sulfate catalyzed by ferric oxi-de［J］.Frontiers of Chemical Science and Engineering，2013，7（2）：210-217.
6	KIYOURA R， URANO K.Mechanism，kinetics，and equilibrium of thermal decomposition of ammonium sulfate［J］.Industrial & Engineering Chemistry Process Design and Development，1970，9（4）：489-494.
7	KUMMER J T.Thermal decomposition of ammonium nitrate［J］.Journal of the American Chemical Society，1947，69（10）.Doi：10.1021/ja01202a507.
8	DIXON P.Formation of sulphamic acid during the thermal decomposition of ammonium sulphate［J］.Nature，1944，154（3918）：706.
9	ZHU Zhenping， NIU Hongxian， LIU Zhenyu，et al.Decomposition and reactivity of NH₄HSO₄ on V₂O₅/AC catalysts used for NO reduction with ammonia［J］.Journal of Catalysis，2000，195（2）：268-278.
10	LI Jie， LI Yandong， DUAN Huamei，et al.Experimental and kinetic study of magnesium extraction and leaching from laterite nickel ore by roasting with ammonium sulfate［J］.Russian Journal of Non-Ferrous Metals，2018，59（6）：596-604.
11	WU Yan， XIN Haixia， XU Yujun，et al.Preparation of ultrafine α-Al₂O₃ powder from fly ash by ammonium sulfate roasting technology［J］.Journal of Physics：Conference Series，2019，1347（1）.Doi：10.1088/1742-6596/1347/1/012111.
12	ZHANG Xianghui， HE Chuan， WANG Ling，et al.Non-isothermal kinetic analysis of thermal dehydration of La₂（CO₃）₃·3.4H₂O in air［J］.Transactions of Nonferrous Metals Society of China，2014，24（10）：3378-3385.
13	LIAN Jingbao， LIU Fan， ZHANG Jing，et al.Template-free hydrothermal synthesis of Gd₂O₂SO₄：Eu³⁺ hollow spheres based on urea-ammonium sulfate （UAS） system［J］.Optik，2016，127（20）：8621-8628.
14	KIEFER W.Recent advances in linear and nonlinear Raman spectroscopy I［J］.Journal of Raman Spectroscopy，2007，38（12）：1538-1553.
15	ANTO P L， ANTO R J， VARGHESE H T，et al.FT-IR，FT-Raman and SERS spectra of anilinium sulfate［J］.Journal of Raman Spectroscopy，2009，40（12）：1810-1815.
16	ZAIRI I， GARCÍA-GRANDA S， LITAIEM H.Optical，thermal，vibrational and structural investigation to characterize phase transitions in the ammonium sulfate tellurate［J］.Journal of Molecular Structure，2021，1242.Doi：10.1016/J.MOLSTRUC.2021.130816.
17	JAYARAMAN K， KÖK M V， GÖKALP I.Combustion mechanism and model free kinetics of different origin coal samples：Thermal analysis approach［J］.Energy，2020，204.Doi：10.1016/j.energy.2020.117905.
18	ZHANG Wei， WANG Chang'an， LI Guangyu，et al.TG analysis and kinetic study of organic constituents in wastewater from coal-gasification process［J］.Asia-Pacific Journal of Chemical Engineering，2017，12（3）：406-414.
19	赵鹏达，倪珊梅，宋小文，等.可见光诱导8-氨基喹啉衍生物二氟烷基化反应［J］.精细化工，2020，37（8）：1678-1683.
	ZHAO Pengda， NI Shanmei， SONG Xiaowen，et al.Visible light induced difluoroalkylation of 8-aminoquinoline derivatives［J］.Fine Chemicals，2020，37（8）：1678-1683.
20	SBIRRAZZUOLI N.Determination of pre-exponential factor and reaction mechanism in a model-free way［J］.Thermochimica Acta，2020，691.Doi：10.1016/j.tca.2020.178707.
21	阎杰，谢军，宋丽华，等.煤与焦油、秸秆混合压球共热解的动力学［J］.煤炭学报，2018，43（7）：2052-2060.
	YAN Jie， XIE Jun， SONG Lihua，et al.Kinetics of co-pyrolysis of coal，tar and straw mixed briquette［J］.Journal of China Coal Society，2018，43（7）：2052-2060.
22	SINGH S， PATIL T， TEKADE S P，et al.Studies on individual pyrolysis and co-pyrolysis of corn cob and polyethylene：Thermal degradation behavior，possible synergism，kinetics，and thermodynamic analysis［J］.Science of the Total Environment，2021，783.Doi：10.1016/j.scitotenv.2021.147004.
23	ASHRAF A， SATTAR H， MUNIR S.A comparative applicability study of model-fitting and model-free kinetic analysis approaches to non-isothermal pyrolysis of coal and agricultural residues［J］.Fuel，2019，240：326-333.
24	HU Jinghui， GONG Li， HE Jiyu，et al.Studies on multistep thermal decomposition behavior of polytriazole polyethylene oxide-tetrahydrofuran elastomer［J］.Polymers for Advanced Technologies，2020，31（4）：749-758.
25	周绿山.硫酸铵与硫酸氢铵混合物催化热分解过程研究［D］.昆明：昆明理工大学，2014.

阶段	反应方程	质量损失率/%
阶段	反应方程	实验值	理论值
1	（NH₄）₂SO₄=NH₄HSO₄+NH₃（g）	14.20	12.87
2	2NH₄HSO₄=（NH₄）₂S₂O₇+H₂O（g）	5.78	6.82
3	3（NH₄）₂S₂O₇=2NH₃+2N₂+6SO₂+9H₂O	80.02	80.30

阶段	升温速率/ （K·min^-1）	温度/K
阶段	升温速率/ （K·min^-1）	α=0.1	α=0.2	α=0.3	α=0.4	α=0.5	α=0.6	α=0.7	α=0.8	α=0.9
1	4	527.074	536.61	541.416	547.311	551.469	555.173	558.648	562.221	566.363
	6	536.434	546.635	553.46	559.256	563.611	567.533	571.397	575.303	579.806
	8	539.245	549.356	556.176	561.854	566.718	571.328	575.467	579.908	584.906
	10	542.169	552.4	560.069	566.104	570.973	575.3	579.448	583.701	588.262
	12	545.182	555.169	562.435	568.201	572.901	577.243	581.326	585.999	591.967
2	4	571.221	573.195	575.226	577.926	579.499	581.697	583.919	586.057	588.006
	6	586.375	587.962	589.539	591.219	593.028	594.827	596.744	598.551	600.986
	8	592.578	594.517	596.464	598.429	600.327	602.248	603.649	605.421	607.225
	10	596.481	598.699	600.689	602.729	604.527	606.545	608.567	610.501	612.446
	12	600.525	602.713	604.619	606.705	608.786	611.074	613.12	615.337	617.551
3	4	607.216	618.543	628.022	635.468	641.61	646.693	651.16	655.139	658.714
	6	629.151	642.269	651.483	658.467	664.278	669.326	673.73	677.603	681.234
	8	629.781	642.085	650.9	657.726	663.193	668.549	673.045	677.251	681.123
	10	637.448	650.501	659.913	667.121	675.548	678.58	683.357	687.656	691.561
	12	641.613	654.517	664.004	671.574	678.076	684.014	689.832	693.736	697.537

机理函数	第一阶段		第二阶段		第三阶段
机理函数	E/（kJ·mol^-1）	R²	E/（kJ·mol^-1）	R²	E/（kJ·mol^-1）	R²
α²	237.411	0.94	749.528	0.89	278.720	0.99
α+（1-α）ln（1-α）	277.369	0.99	834.992	0.92	308.109	0.99
［1-（1-α）^1/3］²	125.218	0.99	22.54	0.98	23.095	0.99
1-2/3α-（1-α）^2/3	288.660	0.99	871.099	0.93	320.438	0.99
［-ln（1-α）］^1/4	35.472	0.99	110.214	0.99	38.650	0.98
［-ln（1-α）］^1/3	50.399	0.99	168.997	0.96	55.168	0.98
［-ln（1-α）］^1/2	80.25	0.99	258.461	0.96	88.203	0.98
［-ln（1-α）］^2/3	110.108	0.99	347.925	0.96	121.238	0.98
-ln（1-α）	170.081	0.99	526.884	0.97	187.308	0.98
α^1/2	55.580	0.97	179.873	0.89	97.706	0.99
1-（1-α）^1/3	151.229	0.99	467.396	0.94	176.256	0.99
1-（1-α）^1/2	142.761	0.99	440.415	0.93	158.099	0.99
（1-α）^-1	108.929	0.76	327.614	0.87	116.467	0.69
（1-α）^-2	27.048	0.77	120.788	0.89	243.835	0.71

[1]	HU Dian, GUO Ze, ZHANG Hanquan, LU Manman. Research on effects of roasting process and typical impurities on reduction and decomposition process of phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(7): 88-95.
[2]	QI Xingzhao, WANG Feng, WU Jie, ZHANG Qi, TANG Zhongfeng. Study on pyrolysis behavior and mechanism of calcium carbide slag/magnesium carbonate system [J]. Inorganic Chemicals Industry, 2024, 56(10): 118-126.
[3]	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.
[4]	WANG Song, WANG Jiawei, GOU Bibo, YANG Pan, HE Yue, YANG Chunyuan, WANG Haifeng. Study on distribution law of magnesium in leaching solution of rhodochrosite by complex salt crystallization method [J]. Inorganic Chemicals Industry, 2023, 55(4): 65-71.
[5]	ZHOU Qiang, WU Bin, CHEN Kui, JI Lijun, WU Yanyang. Study on thermal decomposition kinetic mechanism and calcination process of phosphorus tailings [J]. Inorganic Chemicals Industry, 2023, 55(3): 47-54.
[6]	TIAN Xiaoli, LI Zhixun, FENG Runtang, ZHANG Jie, ZHENG Quanfu, SHI Xuwu, DU Yongbin. Study on thermal decomposition behavior of Tibetan Kamado microcrystalline magnesite [J]. Inorganic Chemicals Industry, 2023, 55(3): 60-65.
[7]	PAN Sicheng,XU Hongbin,ZHANG Hongling,DONG Yuming,ZHANG Hongjun,LOU Taiping. Study on preparation of metatitanic acid by hydrolysis of leaching solution of roasted mixture of red mud and ammonium sulfate [J]. Inorganic Chemicals Industry, 2023, 55(2): 85-91.
[8]	YANG Han,DENG Fuli,DING Yao,LONG Bingwen. Experimental study on comprehensive utilization of citric acid soluble phosphorus sludge [J]. Inorganic Chemicals Industry, 2022, 54(12): 87-91.
[9]	QI Yuanhao,WU Jinxiu,LIU Zhaogang,HU Yanhong,FENG Fushan,LI Jianfei,WANG Xin,LIU Conglin. Preparation and characterization of anhydrous calcium sulfate whisker [J]. Inorganic Chemicals Industry, 2022, 54(10): 109-115.
[10]	Hu Min,Gong Hanzhang,Wu Huadong,Guo Jia,Zhang Linfeng,Zhou Yuxin. Preparation of battery-grade lithium carbonate from lithium-containing industrial waste [J]. Inorganic Chemicals Industry, 2020, 52(3): 80-84.
[11]	Liu Yuelong,Wang Linlin,Liu Gousheng. Extraction of rubidium and cerium salts from lithium tail liquid of medium and low grade lithium clay by ammonium sulfate process [J]. Inorganic Chemicals Industry, 2020, 52(11): 60-63.
[12]	Liu Gousheng,Wang Linlin,Liu Yuelong. Preparation of lithium carbonate from medium-and low-grade lithium clay by ammonium sulfate process [J]. Inorganic Chemicals Industry, 2020, 52(10): 125-129.
[13]	Su Xiaoli,Qin Fengting,Cai Tiancong,Ma Chunyu,Tang Changqing. Preparation of nano-sized zinc oxide by thermal decomposition with different carbonate precipitates [J]. Inorganic Chemicals Industry, 2019, 51(9): 36-39.
[14]	Cheng Jialin1，Chi Yongqing1，Jia Panfeng2，Lü Yazhen1，Wang Yuanyang1. A new process for producing potassium sulfate by conversion method of ammonium chloride purified by inducing ammonia [J]. Inorganic Chemicals Industry, 2019, 51(10): 56-59.
[15]	Tian Sen1，2，3，Ye Xuemei1，2，3，Feng Haitao1，2，Dong Yaping1，2，Li Wu1，2，Zhang Bo1，2，Li Bo1，2. Effect of temperature on preparation of chromium oxide by thermal decomposition of ammonium dichromate [J]. Inorganic Chemicals Industry, 2019, 51(10): 60-63.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on decomposition process and thermal decomposition kinetics of ammonium sulfate

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 25

Related Articles 15

Metrics

Comments

Recommended 0