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

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Table 1

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References 25

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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

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Inorganic Acid-Base-Salt Committee of CIESC

Study on decomposition process and thermal decomposition kinetics of ammonium sulfate

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