La(NO3)3和Pr(NO3)3对高岭石脱羟基动力学的影响

doi:10.7503/cjcu20141004

摘要/Abstract

摘要：

采用热重和微商热重(TG/DTA)综合热分析技术在不同升温速率下研究了掺入La(NO₃)₃和Pr(NO₃)₃的高岭石的热分解过程, 利用Coats-Redfern积分法和Achar微分法对热分析实验数据进行动力学计算, 得到了高岭石脱羟基反应过程中的控制机理函数、活化能和指前因子等动力学参数; 分析了2种稀土掺入对高岭石脱羟基过程动力学参数的影响, 并用Ozawa法对活化能进行了验证. 结果表明, 未掺稀土和掺入Pr(NO₃)₃的高岭石的脱羟基反应过程均受化学反应模型F₃控制, 反应的活化能分别为307.94和282.86 kJ/mol, 指前因子lnA的值分别为47.8980和44.1718; 掺入La(NO₃)₃的高岭石脱羟基反应过程控制机理函数发生改变, 受化学反应模型F₂控制, 反应活化能为196.02 kJ/mol, 指前因子lnA的值为29.5551. 与未掺稀土的高岭石对比, 掺入Pr(NO₃)₃后活化能和指前因子略有降低; 而掺入La(NO₃)₃后则显著降低, 分别降低了36.34%和38.30%. 采用Ozawa法验证得到的活化能与Coats-Redfern积分法和Achar微分法结果一致.

关键词: La(NO3)3, Pr(NO3)3, 高岭石, 脱羟基过程, 活化能

Abstract:

The thermal decomposition processes of kaolinite mixed with La(NO₃)₃ and Pr(NO₃)₃ were investigated by thermogravimetric analysis/differential thermal analysis(TG/DTA) simultaneous thermal analysis technique under different heating rates. Thermal analysis data were used for dynamic analysis by the Coats-Redfern integral method and Achar differential method to calculate the kinetic model function, activation energy and pre-exponential factor of dehydroxylation process of kaolinite. The effects of two kinds of rare earth on kinetic parameters of dehydroxylation process of kaolinite were analyzed. The activation energy was validated by Ozawa method. The results show that dehydroxylation of kaolinite and the sample mixed with Pr(NO₃)₃ are controlled by the rate of third-order chemical reaction(F₃), the activation energies are 307.94 and 282.86 kJ/mol, respectively, and the values of pre-exponential factor lnA are 47.8980 and 44.1718, respectively; the kinetic model function of sample mixed with La(NO₃)₃ changes to the second-order chemical reaction(F₂), the activation energy is 196.02 kJ/mol, and the value of pre-exponential factor lnA is 29.5551. Compared with the kaolinite without rare earth, the activation energy and the pre-exponential factor lnA of the sample mixed with Pr(NO₃)₃ have slightly reduced, while those of the sample mixed with La(NO₃)₃ significantly decrease by 36.34% and 38.30%, respectively. The value of the activation energy obtained by Coats-Redfern and Achar method is consistent with the one obtained by Ozawa method.

Key words: La(NO3)3, Pr(NO3)3, Kaolinite, Dehydroxylation process, Activation energy

中图分类号:

O642
TQ170.1

TrendMD:

匡敬忠, 原伟泉, 徐力勇, 李琳, 黄震. La(NO₃)₃和Pr(NO₃)₃对高岭石脱羟基动力学的影响. 高等学校化学学报, 2015, 36(7): 1395.

KUANG Jingzhong, YUAN Weiquan, XU Liyong, LI Lin, HUANG Zhen. Effect of La(NO₃)₃ and Pr(NO₃)₃ on Kinetic of Dehydroxylation of Kaolinite^†. Chem. J. Chinese Universities, 2015, 36(7): 1395.

图/表 6

参考文献 34

[1]	Itagaki T., Matsumura A., Kato M., Usuki A., Kuroda K., J. Mater. Sci. Lett., 2001, 20, 1483—1484
[2]	Xu J. F., Liang Y. Y., Ma N., Chen L. K., Li Y., Du P. Y., Chinese J. Inorg. Chem., 2011, 27(6), 1121—1127
	(徐剑锋, 梁怡瑛, 马宁, 陈丽昆, 李勇, 杜丕一. 无机化学学报,2011, 27(6), 1121—1127)
[3]	Kuang J. Z., Qiu T. S., Shi F., Chinese J. Nonferrous Met., 2012, 22(1), 249—264
	(匡敬忠, 邱廷省, 施芳. 中国有色金属学报,2012, 22(1), 249—264)
[4]	He H. P., Hu C., Guo J. G., Zhang H. F., Chinese J. Geochem., 1995, 14(1), 78—82
[5]	Barreto Maia A. Á., Angélica R. S., Neves R. D. F., Pöllmann H., Straub C., Saalwächter K., Appl. Clay Sci., 2014, 87, 189—196
[6]	Liu Q. F., Ding S. L., Zhang T. J., Li P., J. China University Min. Techno., 2002, 12(2), 155—157
[7]	Franco F.,rez-Rodríguez J. L., J. Colloid Interf. Sci., 2004, 274, 107—117
[8]	Castelein O., Soulestin B., Bonnet J. P., Blanchart P., Ceram. Int., 2001, 27, 517—522
[9]	Chen Y. F., Wang M. Ch., Hon M. H., J. Eur. Ceram. Soc., 2004, 24, 2389—2397
[10]	Frost R.dey., Thermochim. Acta, 2003, 408, 103—113
[11]	Ding Z., Zhang D. C., Wang X. D., B. Chinese Ceram. Soc., 1997, 4, 57—62
	(丁铸, 张德成, 王向东.硅酸盐通报, 1997, 4, 57—62)
[12]	Ptek P., Kubátová D., Havlica J., Brandštetr J., Šoukal F., Opravil T., Thermochim. Acta, 2010, 501, 24—29
[13]	Ptek P., Šoukal F., Opravil T., Nosková M., Havlica J., Brandštetr J., Powder Techno., 2010, 203, 272—276
[14]	Ptek P., Šoukal F., Opravil T., Havlica J., Brandštetr J., Powder Techno., 2011, 208, 20—25
[15]	Ptek P. , Opravil T., Šoukal F., Brandštetr J., Havlica J., Msilko J., Appl. Clay Sci., 2014, 95, 146—149
[16]	Killingley J. S., Day S. J., Fuel, 1990, 69, 1145—1149
[17]	Gasparinia E., Tarantinoa S. C., Ghigna P., Riccardi M. P., Cedillo-González E. I., Siligardi C., Zema M., Appl. Clay Sci., 2013, 80/81, 417—425
[18]	Zhang A. H., He M. Z., Qin F. F., Yan H., J. Chinese Ceram. Soc., 2009, 37(10), 1678—1682
	(张爱华, 何明中, 秦芳芳, 严慧. 硅酸盐学报,2009, 37(10), 1678—1682)
[19]	Zhou J., He M. Z., Zhang A. H., Li L., Fu F. Y., Chinese J. Inorg. Chem., 2010, 26(7), 1279—1283
	(周佳, 何明中, 张爱华, 李淋, 傅凤英.无机化学学报, 2010, 26(7), 1279—1283)
[20]	Gao F., Zhao Z. L., Cui H., Zhang J. Y., Zhang B. J., J. Fuel Chem. Techno., 1998, 26(2), 135—139
	(高峰, 赵增立, 崔洪, 张济宇, 张碧江. 燃料化学学报,1998, 26(2), 135—139)
[21]	Liu Y., Yu L., Wei Z. G., Pan Z. C., Zou Y. D., Xie Y. H., Chem. J. Chinese Universities, 2013, 34(2), 434—440
	(刘月, 余林, 魏志钢, 潘湛昌, 邹燕娣, 谢英豪. 高等学校化学学报,2013, 34(2), 434—440)
[22]	Zhu L.C., Tang G. B., Shi Q., Yin J. H.,Polym. B., 2007, (3), 55—60
	(朱连超, 唐功本, 石强, 殷敬华. 高分子通报, 2007, (3), 55—60)
[23]	Chen Y., Li F. F., Li C. G., Pan Q. Z., Cui M. H., Chem. J. Chinese Universities, 2013, 34(4), 788—793
	(陈颖, 李菲菲, 李春光, 潘庆芝, 崔满华. 高等学校化学学报,2013, 34(4), 788—793)
[24]	Wang S. H., Hu H. Z., Chen C., Ma R. N., Zhang N., Chem. J. Chinese Universities, 2014, 35(10), 2055—2060
	(汪淑华, 胡汉珍, 陈超, 马润宁, 张宁. 高等学校化学学报,2014, 35(10), 2055—2060)
[25]	Li Y. T., Wu Y. L., Hu J. D., Hu C. Y., Li Y. X., Chinese J. Rare Met., 2007, 31(4), 526—532
	(黎毓婷, 吴燕利, 胡建东, 胡春燕, 李永绣. 稀有金属,2007, 31(4), 526—532)
[26]	Wu W. Y., Chen J., Sun S. C., Tu G. F., J. Northeast University(Nat. Sci.), 2004, 25(4), 378—381
	(吴文远, 陈杰, 孙树臣, 涂赣峰.东北大学学报(自然科学版), 2004, 25(4), 378—381)
[27]	Feng Y. J., Shi Y. Q., He D. M., Zou W. Q., Polym. Mater. Sci. Eng., 1991, 13, 30—34
	(冯仰婕, 史永强, 何东明, 邹文樵.高分子材料科学与工程, 1991, 13, 30—34)
[28]	Vlaev L., Nedelchev N., Gyurova K., Zagorcheva M., J. Anal. Appl. Pyrol., 2008, 81, 253—262
[29]	Coats A. W., Redfern J. P., Nature, 1964, 201, 68—69
[30]	Achar B. N., Brindley G. W., Sharp J. H., Proceedings of International Clay Conference, 1966, 1, 67
[31]	Ozawa T., B. Chem. Soc. JPN, 1965, 38, 1881—1886
[32]	Hu Z.R., Shi Q. Z., Thermal Analysis Kinetics, Science Press, Beijing, 2008, 81—82
	(胡祖荣, 史启祯.热分析动力学, 北京: 科学出版社, 2008, 81—82)
[33]	Ptek P., Kubtov D., Havlica J., Brandštetr J., Šoukal F., Opravil T., Power Techno., 2010, 204, 222—227
[34]	Traor K., Gridi-Bennadji F., Blanchart P., Thermochim. Acta, 2006, 451, 99—104

Heating rate/ (℃·min^-1)	Coats-Redfern method			Achar method
Heating rate/ (℃·min^-1)	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃
10	275.39	190.76	269.03	303.32	215.27	304.52
15	293.78	183.91	254.02	329.33	189.71	281.76
20	277.98	187.42	255.49	324.06	204.34	295.88
25	284.87	187.68	277.09	334.58	208.44	302.43
30	310.90	185.57	271.24	345.18	207.08	317.18
Average	288.58	187.07	265.37	327.29	204.97	300.35

Heating rate/ (℃·min^-1)	Coats-Redfern method			Achar method
Heating rate/ (℃·min^-1)	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃
10	275.39	190.76	269.03	303.32	215.27	304.52
15	293.78	183.91	254.02	329.33	189.71	281.76
20	277.98	187.42	255.49	324.06	204.34	295.88
25	284.87	187.68	277.09	334.58	208.44	302.43
30	310.90	185.57	271.24	345.18	207.08	317.18
Average	288.58	187.07	265.37	327.29	204.97	300.35

Heating rate/ (℃·min^-1)	Coats-Redfern method			Achar method
Heating rate/ (℃·min^-1)	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃
10	43.4691	28.6730	41.9935	47.8400	32.5472	47.5556
15	45.6960	27.6883	39.6585	51.1239	28.6523	44.0226
20	43.4219	28.1997	40.1881	50.4558	30.8576	46.4083
25	44.3856	28.2342	43.3183	51.9198	31.4627	47.2162
30	47.7643	27.9504	42.2074	52.9029	31.2854	49.1495
Average	44.9474	28.1491	41.4732	50.8485	30.9610	46.8704

Heating rate/ (℃·min^-1)	Coats-Redfern method			Achar method
Heating rate/ (℃·min^-1)	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃	Kaolinite	Kaolinite+ La(NO₃)₃	Kaolinite+ Pr(NO₃)₃
10	43.4691	28.6730	41.9935	47.8400	32.5472	47.5556
15	45.6960	27.6883	39.6585	51.1239	28.6523	44.0226
20	43.4219	28.1997	40.1881	50.4558	30.8576	46.4083
25	44.3856	28.2342	43.3183	51.9198	31.4627	47.2162
30	47.7643	27.9504	42.2074	52.9029	31.2854	49.1495
Average	44.9474	28.1491	41.4732	50.8485	30.9610	46.8704

Sample	Ozawa method		Average value(E_a) of Coats-Redfern and Achar method
Sample	E_a/(kJ·mol^-1)		R²
Kaolinite	301.94	0.9908	307.94
Kaolinite+La(NO₃)₃	212.86	0.9987	196.02
Kaolinite+Pr(NO₃)₃	284.23	0.9966	282.86

La(NO₃)₃和Pr(NO₃)₃对高岭石脱羟基动力学的影响

Effect of La(NO₃)₃ and Pr(NO₃)₃ on Kinetic of Dehydroxylation of Kaolinite^†

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