磷石膏-氨-水固碳反应体系氨浓度对石膏颗粒溶解速率的影响

doi:10.11949/0438-1157.20200200

摘要/Abstract

摘要：

磷石膏-氨-水固碳反应体系中石膏颗粒的溶解，是三相流化矿化反应系统的控制性步骤。在氨水溶液中石膏颗粒能与氨分子形成N—H…O氢键，导致石膏溶解速率受氨浓度影响。基于已知粒度分布的石膏颗粒群在不同氨浓度下的溶解实验数据，采用种群平衡模型与物料衡算相结合的方法，探究了氨浓度对石膏颗粒群溶解特性的影响规律。结果表明：氨浓度的增加会降低石膏溶解速率，随着溶解的进行，氨对溶解的抑制作用会减弱。此外，随着氨浓度的增大，增加单位氨浓度石膏溶解速率的降幅将变小。结合实验数据拟合关联溶解动力学参数，构建了氨浓度影响下石膏的溶解速率模型，预测了三相流化矿化反应系统中两个串联回路石膏料浆所需的停留时间，为磷石膏-氨-水固碳反应体系矿化烟气CO₂的放大设计提供了理论依据。

关键词: 氨, 石膏, 种群平衡, 溶解, 速率模型

Abstract:

The dissolution of gypsum particles in the phosphogypsum-ammonia-water carbon fixation reaction system is a controlling step of the three-phase fluidized mineralization reaction system. The macroscopic dissolution rate was infected by ammonia concentrations because the N—H···O hydrogen bonds between the gypsum surface and ammonia molecules were formed in the ammonia solution. Dissolution data of gypsum particle group with certain particle size distribution were experimentally determined under different ammonia concentrations. The influence regulations of ammonia concentration on gypsum particle group dissolution characteristics were investigated combining with the population equilibrium model and the material balance method. The results indicated that the dissolution rate of gypsum reduced with increase of ammonia concentration. As the gypsum dissolution processing, the dissolution inhibition of gypsum by ammonia has been weakened. Besides, the decrease of gypsum dissolution rate would be smaller with the increase of ammonia concentration. The dissolution rate model of gypsum under different ammonia concentration were established by fit the dissolution dynamics parameters based on experimental data，and to predict the residence time required in two series loops in the TFMS, which provides theoretical support for scale up design of the phosphogypsum - ammonia - water carbon fixation system mineralizing flue gas CO₂.

Key words: ammonia, gypsum, population balance, dissolution, rate model

中图分类号:

TQ 021.4

吴林, 李季, 朱家骅, 宫源, 葛敬. 磷石膏-氨-水固碳反应体系氨浓度对石膏颗粒溶解速率的影响[J]. 化工学报, 2020, 71(8): 3575-3584.

Lin WU, Ji LI, Jiahua ZHU, Yuan GONG, Jing GE. Effect of ammonia concentration on dissolution rate of gypsum particles in phosphogypsum-ammonia-water reaction system for carbon sequestration[J]. CIESC Journal, 2020, 71(8): 3575-3584.

图/表 11

图1 磷石膏-氨-水固碳体系三相流化矿化反应系统[6]

Fig.1 The three-phase fluidized mineralization reaction system in the phosphogypsum-ammonia-water system for carbon sequestration

图2 氨抑制CaSO4·2H2O溶解机理

Fig.2 Mechanism of dissolution inhibition of gypsum by ammonia

图3 溶解种群平衡方程求解框图

Fig.3 Calculation flow chart of dissolved population equilibrium equation

图4 石膏颗粒初始粒度分布

Fig.4 The initial size distribution of gypsum particles

图5 不同搅拌转数下液相cCa2+随t的变化

Fig.5 Variation of concentration of Ca2+versus time with different stirring revolutions

图6 实验装置图

Fig.6 Schematic diagram of experiments

图7 不同T和ω下cCa2+随t的变化

Fig.7 cCa2+versust under different T and ω

表1 溶解动力学参数及Ca2+浓度实验值与模型计算值对比(T=25℃)

Table 1 Dissolution kinetics parameters and comparisons between experimental results and model calculations of Ca2+ concentrations (T=25℃)

ω/%	时间/s	$c C a 2 +, c a l$ / (mol·L^-1)	$c C a 2 +, e x p$ / (mol·L^-1)	$c C a 2 +, e x p - ? c C a 2 +, c a l c C a 2 +, e x p / %$	k/ (mol·m^-2·s^-1)	n
0	120	0.010	0.0101	9.0	1.73×10^-4	1.10
	240	0.0129	0.0126	5.4
	360	0.0141	0.0142	2.8
	480	0.0146	0.0146	2.1
	600	0.0148	0.0145	0.7
2	120	0.0075	0.0077	2.6	1.01×10^-4	1.12
	240	0.0110	0.0109	0.9
	360	0.0128	0.0126	1.6
	480	0.0137	0.0136	0.7
	600	0.0144	0.0143	0.7
4	120	0.0059	0.0067	11.9	0.70×10^-4	1.13
	240	0.0091	0.0096	5.2
	360	0.0111	0.0107	3.7
	480	0.0124	0.0120	3.3
	600	0.0133	0.0127	4.7
6	120	0.0046	0.0051	9.8	0.46×10^-4	1.12
	240	0.0071	0.0073	2.7
	360	0.0091	0.0095	4.2
	480	0.0105	0.0104	1.0
	600	0.0116	0.0110	5.5

表1 溶解动力学参数及Ca2+浓度实验值与模型计算值对比(T=25℃)

Table 1 Dissolution kinetics parameters and comparisons between experimental results and model calculations of Ca2+ concentrations (T=25℃)

ω/%	时间/s	$c C a 2 +, c a l$ / (mol·L^-1)	$c C a 2 +, e x p$ / (mol·L^-1)	$c C a 2 +, e x p - ? c C a 2 +, c a l c C a 2 +, e x p / %$	k/ (mol·m^-2·s^-1)	n
0	120	0.010	0.0101	9.0	1.73×10^-4	1.10
	240	0.0129	0.0126	5.4
	360	0.0141	0.0142	2.8
	480	0.0146	0.0146	2.1
	600	0.0148	0.0145	0.7
2	120	0.0075	0.0077	2.6	1.01×10^-4	1.12
	240	0.0110	0.0109	0.9
	360	0.0128	0.0126	1.6
	480	0.0137	0.0136	0.7
	600	0.0144	0.0143	0.7
4	120	0.0059	0.0067	11.9	0.70×10^-4	1.13
	240	0.0091	0.0096	5.2
	360	0.0111	0.0107	3.7
	480	0.0124	0.0120	3.3
	600	0.0133	0.0127	4.7
6	120	0.0046	0.0051	9.8	0.46×10^-4	1.12
	240	0.0071	0.0073	2.7
	360	0.0091	0.0095	4.2
	480	0.0105	0.0104	1.0
	600	0.0116	0.0110	5.5

图8 ra 实验值与拟合方程计算值的对比

Fig.8 Comparisons of ra between experimental values and calculating results

图9 不同粒径颗粒 w随t 的变化

Fig.9 Variation of w versustwith different particle size

图10 w随t 的变化A—w=7%，t=11 min；B—w=7%，t=9 min；C—w=96%，t=86 min；D—w=24%，t=11 min

Fig.10 Variation of w versust

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