微型流化床内菱镁矿轻烧反应特性及动力学

doi:10.11949/0438-1157.20190411

化工学报 ›› 2019, Vol. 70 ›› Issue (8): 2928-2937.DOI: 10.11949/0438-1157.20190411

微型流化床内菱镁矿轻烧反应特性及动力学

姜微微¹(),郝文倩¹,刘雪景¹(),韩振南¹,岳君容²,许光文^1,²()

1. 沈阳化工大学能源与化工产业技术研究院，资源化工与材料教育部重点实验室，辽宁沈阳 110142
2. 中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190

收稿日期:2019-04-18 修回日期:2019-07-01 出版日期:2019-08-05 发布日期:2019-08-05
通讯作者: 刘雪景,许光文
作者简介:姜微微（1994—），女，硕士研究生,814265991@qq.com
基金资助:
辽宁省教育厅重点项目(LZ2017001);辽宁省高水平创新团队国（境）外培养项目(2018LNGXGJWPY-ZD002)

Characteristic and kinetics of light calcination of magnesite in micro fluidized bed reaction analyzer

Weiwei JIANG¹(),Wenqian HAO¹,Xuejing LIU¹(),Zhennan HAN¹,Junrong YUE²,Guangwen XU^1,²()

1. Institute of Industrial Chemistry and Energy Technology, Laboratory on Resources Chemicals and Materials of Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
2. State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2019-04-18 Revised:2019-07-01 Online:2019-08-05 Published:2019-08-05
Contact: Xuejing LIU,Guangwen XU

摘要/Abstract

摘要：

通过微型流化床反应分析仪（MFBRA）和热重分析仪（TGA）对比研究了菱镁矿粉在氮气和空气气氛中的煅烧反应特性和反应动力学特性。结果表明：菱镁矿在氮气和空气中测得的表观活化能相似，说明空气中的氧气对菱镁矿的煅烧没有影响。MFBRA中菱镁矿粉在800℃以上完全分解的时间只有短短数秒，显著少于在TGA中完全分解的时间，揭示了TGA和MFBRA在测定反应动力学方面的差异。MFBRA测定菱镁矿在空气和氮气气氛中分解的表观活化能（约125 kJ/mol）和指前因子（10⁵ s^-1）显著低于TGA所得结果（约200 kJ/mol，10¹⁵ s^-1），进一步测试表明这与TGA中的反应受气氛抑制有关。即菱镁矿在TGA坩埚内分解产生的CO₂不能及时随气流排出，抑制了轻烧反应的进行，而MFBRA可有效降低外扩散对反应的影响。但两种仪器测试的反应均遵循成核与生长控制模型。对于流化床反应，证明了MFBRA测试结果具有更高的准确性，为有气体生成的煅烧或分解反应（如菱镁矿轻烧）提供了可靠的反应测试方法和仪器。

关键词: 流化床, 动力学, 菱镁矿, 轻烧, 扩散

Abstract:

The calcination reaction characteristics and reaction kinetics of magnesite powder in nitrogen and air atmosphere were studied by microfluidic bed reaction analyzer (MFBRA) and thermogravimetric analyzer (TGA). It was shown that the activation energy of magnesite calcination measured in nitrogen and air was quite similar, indicating that the oxygen in the air had little effect on the calcination of magnesite. The time for complete decomposition of magnesite in MFBRA was short as a few seconds in MFBRA at temperatures above 800℃, showing its reaction rate much quicker than that in TGA，which revealed the difference between TGA and MFBRA in measuring the reaction kinetics. Both activation energy and pre-exponential factor are significantly lower in MFBRA (about 125 kJ/mol, 10⁵ s^-1) than in TGA (about 200 kJ/mol，10¹⁵ s^-1). The gas product CO₂ produced by magnesite decomposition is difficult to fully flow out from the crucible of TGA and thus inhibits the decomposition reaction of magnesite. For MFBRA, it can effectively reduce the inhibition effect from the formed CO₂ that easily flows into the main gas flow surrounding the particles. It is also found that the magnesite decomposition reaction follows the nucleation and growth control model in both MFBRA and TGA. Overall, for the reaction in fluidized beds, the study verifies that MFBRA provides a reliable secure of the reaction rate and kinetic parameters for the gas-formation calcination or decomposition reactions like tested light calcination of magnesite.

Key words: fluidized bed, kinetics, magnesite, light calcination, diffusion

中图分类号:

TQ 028.8

姜微微, 郝文倩, 刘雪景, 韩振南, 岳君容, 许光文. 微型流化床内菱镁矿轻烧反应特性及动力学[J]. 化工学报, 2019, 70(8): 2928-2937.

Weiwei JIANG, Wenqian HAO, Xuejing LIU, Zhennan HAN, Junrong YUE, Guangwen XU. Characteristic and kinetics of light calcination of magnesite in micro fluidized bed reaction analyzer[J]. CIESC Journal, 2019, 70(8): 2928-2937.

图/表 13

图1 微型流化床反应分析仪流程

Fig.1 Schematic diagram of used MFBRA

图2 MFBRA中菱镁矿粉轻烧的CO2生成质谱检测曲线

Fig.2 CO2 formation curve of magnesite calcination in MFBRA detected using process mass spectrometry

图3 不同温度下MFBRA中菱镁矿粉轻烧转化率随时间的变化

Fig.3 Variation of conversion with time for magnesite calcination in MFBRA at different preset temperatures

图4 MFBRA中菱镁矿轻烧反应速率随转化率的变化关系

Fig.4 Reaction rate varying with conversion for magnesite calcination corresponding to Fig.3

图5 TGA中菱镁矿粉轻烧转化率随时间的变化曲线

Fig.5 Variation of conversion with time for magnesite calcination in TGA at different heating rates.

图6 MFBRA中菱镁矿粉轻烧反应的ln(dx/dt)与1/T拟合曲线

Fig.6 Fitting curve of ln(dx/dt) versus 1/T for magnesite calcination reaction in MFBRA

表1 依据MFBRA测试空气和氮气气氛中菱镁矿粉轻烧数据计算的等温模型法表观活化能

Table 1 Activation energy of magnesite calcination reaction calculated according to isothermal model for MFBRA-measured data in N2 and air atmospheres

模型	N₂			Air
模型	E/ (kJ/mol)	lgA	R ²	E/ (kJ/mol)	lgA	R ²
G(x)= -ln(1-x)	124.45	5.61	0.997	125.09	5.69	0.996
G(x)=1-(1-x)^1/3	128.67	5.36	0.997	129.32	5.39	0.996
G(x)=1-(1-x)^1/2	123.25	5.30	0.998	121.08	5.08	0.998

图7 不同升温速率下TGA中菱镁矿粉轻烧反应转化率随温度的变化关系

Fig.7 Variation of conversion with temperature measured in TGA at different heating rates

图8 TGA中菱镁矿粉轻烧反应的lgβ与1/T的线性拟合关系

Fig.8 Relationship of lgβ with 1/T for light calcination of magnesite power from tests in TGA

图9 TGA中菱镁矿粉煅烧反应中活化能与转化率的拟合关系

Fig.9 Relationship of activation energy with conversion for magnesite power calcination in TGA

表2 利用Coats-Redfern公式根据文献报道的机理模型拟合TGA测试数据的结果

Table 2 Fitting results using Coats-Redfern formula for literature-reported mechanism models based on TGA data

模型		β→0	β=1℃/min		β=5℃/min		β=10℃/min
模型		E/(kJ/mol)	E/(kJ/mol)	r	E/(kJ/mol)	r	E/(kJ/mol)	r
N₂	G(x)= -ln(1-x)	201.72	187.88	0.994	224.46	0.997	224.81	0.997
	G(x)=1- (1-x)^1/2	191.02	187.88	0.994	224.48	0.997	224.84	0.997
	G(x)=1- (1-x)^1/3	228.12	166.02	0.993	198.53	0.997	202.75	0.996
air	G(x)= -ln(1-x)	236.76	225.72	0.997	224.79	0.997	224.61	0.997
	G(x)=1-(1-x)^1/2	197.21	187.14	0.995	186.82	0.996	186.59	0.995
	G(x)=1-(1-x)^1/3	209.74	199.72	0.997	198.83	0.997	198.62	0.997

表3 利用TGA和MFBRA测定的氮气和空气气氛中的菱镁矿粉轻烧动力学参数

Table 3 Kinetic parameters of magnesite calcination in N2 and air atmospheres measured using TGA and MFBRA

Analyzer	E/(kJ/mol)	lgA	G(x)
TGA (N₂)	205.94	15.68	-ln(1-x)
TGA (air)	236.60	15.81	-ln(1-x)
MFBRA (N₂)	125.74	5.61	-ln(1-x)
MFBRA (air)	124.16	5.69	-ln(1-x)

图10 TGA中N2和CO2气氛中不同坩埚条件下菱镁矿粉的热分解曲线

Fig.10 Curves of magnesite decomposition under different crucibles in N2 and CO2 atmospheres in TGA

参考文献 35

1	Zhao Y , Zhu G . Thermal decomposition kinetics and mechanism of magnesium bicarbonate aqueous solution[J]. Hydrometallurgy, 2007, 89(3): 217-223.
2	Demir F , Dönmez B . Optimization of the dissolution of magnesite in citric acid solutions[J]. International Journal of Mineral Processing, 2008, 87(1/2): 60-64.
3	巴浩静, 白丽梅, 赵文青, 等 . 轻烧镁制备及深加工研究进展[J]. 矿产保护与利用, 2017, 1: 84-89.
	Ba H J , Bai L M , Zhao W Q , et al . Review on preparation and processing of caustic calcined magnesite[J]. Conservation and Utilization of Mineral Resources, 2017, 1: 84-89
4	Tian L , Tahmasebi A , Yu J . An experimental study on thermal decomposition behavior of magnesite[J]. Journal of Thermal Analysis and Calorimetry, 2014, 118(3): 1577-1584.
5	Liu X W , Feng Y L , Li H R , et al . Thermal decomposition kinetics of magnesite from thermogravimetric data[J]. Journal of Thermal Analysis and Calorimetry, 2011, 107(1): 407-412.
6	Demir F , Dönmez B , Okur H , et al . Calcination kinetic of magnesite from thermogravimetric data[J]. Chemical Engineering Research and Design, 2003, 81(6): 618-622.
7	Bai L , Deng Y , Li X , et al . Research on decomposition kinetics of fine grained magnesite[J]. Non-metallic Mines, 2016, 39(5): 7-9.
8	刘欣伟, 冯雅丽, 李浩然 . 菱镁矿热分解微分方程的建立[J]. 无机盐工业, 2011, 43(11): 15-18.
	Liu X W , Feng Y L , Li H R . Establishment of differential equations of magnesite thermal decomposition[J]. Inorganic Chemicals Industry, 2011, 43(11): 15-18.
9	张强, 何宏平, 陶奇 . 基于热重分析的菱镁矿分解动力学解析[J]. 岩石矿物学杂志, 2016, 33(2): 391-396.
	Zhang Q , He H P , Tao Q . Decomposition kinetics of magnesite deduced from thermogravimetric analysis[J]. Acta Petrologica Et Mineralodica, 2016, 33(2): 391-396.
10	彭强, 郭玉香, 曲殿利 . 菱镁矿热分解的动力学研究[J]. 硅酸盐通报, 2017, 36(6): 1886-1890.
	Peng Q , Guo Y X , Qu D L . Thermal decomposition kinetics analysis of magnesite[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(6): 1886-1890.
11	Yu J , Yue J , Liu Z , et al . Kinetics and mechanism of solid reactions in a micro fluidized bed reactor[J]. AIChE Journal, 2010, 56(11): 2905-2912.
12	Yu J , Yao C , Zeng X , et al . Biomass pyrolysis in a micro-fluidized bed reactor: characterization and kinetics[J]. Chemical Engineering Journal, 2011, 168(2): 839-847.
13	周宝余, 李志坚, 吴锋, 等 . 块状菱镁矿热分解机理及动力学方程的建立[J]. 人工晶体学报, 2014, 43(7): 1823-1828.
	Zhou B Y , Li Z J , Wu F , et al . Thermal decomposition mechanism and establishment of kinetic equations of block magnesite[J]. Journal of Synthetic Crystals, 2014, 43(7): 1823-1828.
14	Liu X , Xu G , Gao S . Micro fluidized beds: wall effect and operability[J]. Chemical Engineering Journal, 2008, 137(2): 302-307.
15	Wang F , Zeng X , Geng S , et al . Distinctive hydrodynamics of a micro fluidized bed and its application to gas-solid reaction analysis[J]. Energy & Fuels, 2018, 32(4): 4096-4106.
16	Guo Y , Zhao Y , Meng S , et al . Development of a multistage in situ reaction analyzer based on a micro fluidized bed and its suitability for rapid gas-solid reactions[J]. Energy & Fuels, 2016, 30(7): 6021-6033.
17	杨旭, 刘雅宁, 余剑, 等 . 微型流化床内混合特性的数值模拟[J]. 化工学报, 2014, 65(9): 3323-3330.
	Yang X , Liu Y N , Yu J , et al . Numerical simulation of mixing characteristics of trace sample and bed material in micro fluidized bed reaction analyzer[J]. CIESC Journal, 2014, 65(9): 3323-3330.
18	季颖, 曾玺, 余剑, 等 . 微型流化床反应分析仪中煤半焦水蒸气气化反应特性[J]. 化工学报, 2014, 65(9): 3447-3456.
	Ji Y , Zeng X , Yu J , et al . Steam gasification characteristics of coal char in micro-fluidized bed reaction analyzer[J]. CIESC Journal, 2014, 65(9): 3447-3456.
19	Geng S , Han Z , Hu Y , et al . Methane decomposition kinetics over Fe₂O₃ catalyst in micro fluidized bed reaction analyzer[J]. Industrial & Engineering Chemistry Research, 2018, 57(25): 8413-8423.
20	Fang Y , Zou R , Luo G , et al . Kinetic study on coal char combustion in a micro fluidized bed[J]. Energy & Fuels, 2017, 31(3): 3243-3252.
21	Guo Y , Zhao Y , Gao D , et al . Kinetics of steam gasification of in-situ chars in a micro fluidized bed[J]. International Journal of Hydrogen Energy, 2016, 41(34): 15187-15198.
22	Zhang Y , Yao M , Gao S , et al . Reactivity and kinetics for steam gasification of petroleum coke blended with black liquor in a micro fluidized bed[J]. Applied Energy, 2015, 160: 820-828.
23	Wang F , Zeng X , Shao R , et al . Isothermal gasification of in situ/ex situ coal char with CO₂ in a micro fluidized bed reaction analyzer[J]. Energy & Fuels, 2015, 29(8): 4795-4802.
24	Guo F , Dong Y , Lv Z , et al . Kinetic behavior of biomass under oxidative atmosphere using a micro-fluidized bed reactor[J]. Energy Conversion and Management, 2016, 108: 210-218.
25	Zeng X , Wang F , Wang Y , et al . Characterization of char gasification in a micro fluidized bed reaction analyzer[J]. Energy & Fuels, 2014, 28(3): 1838-1845.
26	王芳, 曾玺, 韩江则, 等 . 微型流化床与热重测定煤焦- CO₂气化反应动力学的对比研究[J]. 燃料化学学报, 2013, 41(4): 407-413.
	Wang F , Zeng X , Han J Z , et al . Comparation of char gasification kinetics studied by micro fluidized bed and by thermogravimetric analyzer[J]. Journal of Fuel Chemistry and Technology, 2013, 41(4): 407-413.
27	Yu J , Zeng X , Zhang J , et al . Isothermal differential characteristics of gas-solid reaction in micro-fluidized bed reactor[J]. Fuel, 2013, 103: 29-36.
28	Chen H , Zheng Z , Shi W . Investigation on the kinetics of iron ore fines reduction by CO in a micro-fluidized bed[J]. Procedia Engineering, 2015, 102: 1726-1735.
29	王芳, 曾玺, 王永刚, 等 . 微型流化床与热重测定煤焦非等温气化反应动力学对比[J]. 化工学报, 2015, 66(5): 1716-1722.
	Wang F , Zeng X , Wang Y G , et al . Comparation of non-isothermal coal char gasification in micro fluidized bed and thermogravimetric analyzer[J]. CIESC Journal, 2015, 66(5): 1716-1722.
30	Criado J M , Morales J . Thermal decomposition reactions of solids controlled by diffusion and phase-boundary processes: possible misinterpretation of the mechanism from thermogravimetric data[J]. Thermochimica Acta, 1977, 19(3): 305-317.
31	Criado J M , Ortega A , Gotor F . Correlation between the shape of controlled-rate thermal analysis curves and the kinetics of solid-state reactions[J]. Thermochimica Acta, 1990, 157(1): 171-179.
32	Maitra S , Mukherjee S , Saha N , et al . Non-isothermal decomposition kinetics of magnesite[J]. Cerâmica, 2007, 53(327): 284-287.
33	余剑, 朱剑虹, 岳君容, 等 . 微型流化床反应动力学分析仪的研制与应用[J]. 化工学报, 2009, 60(10): 2669-2674.
	Yu J , Zhu J H , Yue J R , et al . Development and application of micro kinetic analyzer for fluidized bed gas-solid reactions[J]. CIESC Journal, 2009, 60(10): 2669-2674.
34	郑瑛, 宋侃, 池保华, 等 . 二氧化碳气氛下碳酸钙热分解动力学研究[J]. 华中科技大学学报, 2007, 35(8): 87-89.
	Zheng Y , Song K , Chi B H , et al . Decomposition kinetics of CaCO₃ in CO₂ atmosphere[J]. Journal of Huazhong University of Science and Technology, 2007, 35(8): 87-89.
35	Vyazovkin S , Wight C A . Kinetics in solids [J]. Annu. Rev. Phys. Chem. , 1997, (48): 125-149.

[1]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[2]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[3]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[4]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[5]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[6]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[7]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[8]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[9]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[10]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[11]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[12]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[13]	何宣志, 何永清, 闻桂叶, 焦凤. 磁液液滴颈部自相似破裂行为[J]. 化工学报, 2023, 74(7): 2889-2897.
[14]	周继鹏, 何文军, 李涛. 异形催化剂上乙烯催化氧化失活动力学反应工程计算[J]. 化工学报, 2023, 74(6): 2416-2426.
[15]	杨峥豪, 何臻, 常玉龙, 靳紫恒, 江霞. 生物质快速热解下行式流化床反应器研究进展[J]. 化工学报, 2023, 74(6): 2249-2263.

微型流化床内菱镁矿轻烧反应特性及动力学

Characteristic and kinetics of light calcination of magnesite in micro fluidized bed reaction analyzer

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 35

相关文章 15

编辑推荐

Metrics

本文评价