原料粒径对石灰石热分解反应动力学影响

doi:10.19964/j.issn.1006-4990.2022-0232

Abstract

Abstract:

The thermal decomposition characteristics of four limestones with different particle sizes were investigated by using thermal synchronous analyzer under pure carbon dioxide atmosphere with heating rate of 10~30 K/min.A modified double extrapolation method was used to solve the kinetic parameters of the thermal decomposition reaction of limestone.The results of data analysis showed that：the limestone particle size was proportional to the activation energy required for its decomposition，the smaller the particle size，the smaller the activation energy required，and vice versa.The faster the heating rate，the higher the corresponding reaction temperature，and the shorter the time required to reach the same conversion rate，indicating the faster the reaction process.The thermal decomposition of limestone with four different particle sizes under pure carbon dioxide atmosphere was followed the random nucleation and subsequent growth model，and different the reaction rate of limestone thermal decomposition under different heating rates was different，and reaction order range was 1/2~2.The thermal decomposition reaction rate of limestone was different at different heating rates，the thermal decomposition reaction rates of limestone with particle size of 38~250 μm were controlled by interfacial chemical reaction.

Key words: limestone, particle size, pyrolysis reaction kinetics, improved double extrapolation method

CLC Number:

P619.26

ZHANG Xing,XU Jie,WANG Zibing,HOU Peng,HE Long,LIU Huan. Effect of feedstock particle size on kinetics of limestone thermal decomposition reaction[J]. Inorganic Chemicals Industry, 2023, 55(2): 79-84.

Figures/Tables 10

Table 1

Table 2

Fig.1

Table 3

Corresponding Starink differential equations underdifferent conversion rates"

$α$ /%	ln $β / T 1.8 ~ 1 / T$
20	ln $β / T 1.8 = - 152 ? 175 / T + 115.21$
25	ln $β / T 1.8 = - 140 ? 625 / T + 105.56$
30	ln $β / T 1.8 = - 132 ? 514 / T + 98.76$
35	ln $β / T 1.8 = - 125 ? 203 / T + 92.63$
40	ln $β / T 1.8 = - 118 ? 188 / T + 86.76$
45	ln $β / T 1.8 = - 112 ? 344 / T + 81.86$
50	ln $β / T 1.8 = - 107 ? 427 / T + 77.72$
55	ln $β / T 1.8 = - 102 ? 280 / T + 73.41$
60	ln $β / T 1.8 = - 982 ? 19 / T + 69.98$
65	ln $β / T 1.8 = - 948 ? 96 / T + 67.16$
70	ln $β / T 1.8 = - 904 ? 34 / T + 63.42$
75	ln $β / T 1.8 = - 867 ? 98 / T + 60.34$
80	ln $β / T 1.8 = - 834 ? 82 / T + 57.52$
85	ln $β / T 1.8 = - 800 ? 74 / T + 54.61$
90	ln $β / T 1.8 = - 753 ? 50 ? / T + 50.62$

Table 3

Table 4

Apparent activation energies of samples at different conversion ratios"

$α$ /%	E/（kJ·mol^-1）	$α$ /%	E/（kJ·mol^-1）	$α$ /%	E/（kJ·mol^-1）
90	624.2	60	813.6	30	1 097.7
85	663.3	55	847.3	25	1 164.9
80	691.6	50	889.9	20	1 260.6
75	719.0	45	930.6	$→$ 0	1 713.0
70	749.1	40	979.1
65	789.1	35	1 037.2

Table 4

Fig.2

Table 5

Apparent activation energies and correlation coefficients corresponding to linear optimalmechanism functions at different heating rates"

$G α$	$→$ 0 K/min			10 K/min		15 K/min		20 K/min			25 K/min		30 K/min
$G α$	$E β → 0 ?$ / （kJ·mol^-1）	R²		E/ （kJ·mol^-1）	R²	E/ （kJ·mol^-1）	R²	E/ （kJ·mol^-1）	R²		E/ （kJ·mol^-1）	R²	E/ （kJ·mol^-1）	R²
$- l n 1 - α 1 / 4$	410.6	0.996 2	287.7		0.961 2	257.2	0.970 4	228.9	0.973 6	215.5		0.967 3	191.5	0.974 8
$- l n 1 - α 1 / 3$	554.3	0.996 2	390.3		0.962 5	349.8	0.971 5	311.9	0.974 7	294.1		0.968 8	262.2	0.976 1
$- l n 1 - α 2 / 5$	669.1	0.996 2	472.4		0.963 1	423.8	0.972 0	378.4	0.975 3	357.0		0.969 5	318.8	0.976 7
$- l n 1 - α 1 / 2$	841.3	0.996 2	595.6		0.963 8	534.8	0.972 6	478.1	0.975 8	451.4		0.970 2	403.6	0.977 3
$- l n 1 - α 2 / 3$	1 128	0.996 2	800.9		0.964 3	719.8	0.973 1	644.3	0.976 3	608.6		0.970 8	544.9	0.977 8
$- l n 1 - α 3 / 4$	1 272	0.996 2	903.5		0.964 5	812.3	0.973 2	727.4	0.976 5	687.3		0.971 1	615.6	0.978 0
$- l n 1 - α$	1 703	0.996 2	1 211		0.964 9	1 090	0.973 6	976.6	0.976 8	923.2		0.971 5	827.7	0.978 4
$- l n 1 - α 3 / 2$	2 565	0.996 2	1 827		0.965 3	1 645	0.973 9	1 475	0.977 1	1 395		0.971 9	1 252	0.978 7

Table 5

Table 6

Activation energy，correlation coefficient，mechanism function and reaction order of thermal decomposition reaction of limestone with different average particle sizes"

平均粒径/ μm	$E α → 0$ / （kJ·mol^-1）	R²	$G α$	n
200	1 825	0.997 4	$- l n 1 - α 2$	2
112	1 713	0.999 7	$- l n 1 - α$	1
60	1 382	0.999 4	$- l n 1 - α 2 / 3$	2/3
42	1 289	0.999 9	$- l n 1 - α 1 / 2$	1/2

Table 6

Table 7

Reaction time from 20% to 90% conversion oflimestone with different average particle sizesat different heating rates"

$β$ /（K·min^-1）	平均粒径/μm	$T α = 20 %$ /K	$T α = 90 %$ /K	t/min
10	200	1 212	1 240	2.862
	112	1 212	1 235	2.273
	60	1 210	1 230	2.000
	42	1 211	1 228	1.671
15	200	1 214	1 245	2.069
	112	1 214	1 239	1.700
	60	1 214	1 238	1.567
	42	1 212	1 232	1.320
20	200	1 217	1 252	1.730
	112	1 217	1 245	1.450
	60	1 216	1 242	1.300
	42	1 217	1 240	1.150
25	200	1 220	1 260	1.483
	112	1 219	1 250	1.200
	60	1 218	1 246	1.134
	42	1 220	1 246	1.028
30	200	1 222	1 268	1.224
	112	1 222	1 256	1.111
	60	1 222	1 251	0.989
	42	1 222	1 251	0.932

Table 7

Fig.3

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转化率/%	反应温度/K
转化率/%	10 K·min^-1	15 K·min^-1	20 K·min^-1	25 K·min^-1	30 K·min^-1
20	1 211.7	1 213.9	1 217.0	1 218.8	1 222.1
25	1 212.9	1 215.3	1 218.6	1 220.5	1 224.2
30	1 214.2	1 216.7	1 220.3	1 222.2	1 226.2
35	1 215.4	1 218.2	1 221.9	1 223.9	1 228.2
40	1 216.6	1 219.6	1 223.5	1 225.6	1 230.2
45	1 217.8	1 221.1	1 225.2	1 227.3	1 232.2
50	1 219.1	1 222.6	1 226.9	1 229.1	1 234.2
55	1 220.4	1 224.1	1 228.6	1 230.9	1 236.3
60	1 221.8	1 225.7	1 230.5	1 232.8	1 238.4
65	1 223.4	1 227.4	1 232.4	1 234.8	1 240.6
70	1 225.0	1 229.2	1 234.4	1 236.9	1 243.1
75	1 226.8	1 231.2	1 236.7	1 239.3	1 245.7
80	1 228.8	1 233.4	1 239.2	1 241.9	1 248.5
85	1 231.4	1 236.1	1 242.3	1 244.8	1 252.0
90	1 234.7	1 239.4	1 245.2	1 249.6	1 256.4

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Effect of feedstock particle size on kinetics of limestone thermal decomposition reaction

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