Study on ammonia evaporation and hydration kinetics of microcrystalline magnesite

doi:10.11949/0438-1157.20221587

Abstract

Abstract:

In order to strengthen the further study of micrystalline magnesite, the microcrystalline MgO obtained from calcined microcrystalline magnesite and the light burned MgO from a factory in Liaoning are used as raw materials for steaming ammonia, precipitating magnesium and calcinating to obtain MgO, and conduct hydration experiment. The effect of MgO activity on ammonia evaporation kinetics was investigated by water method, and the effects of reaction temperature and solid-liquid ratio on particle size and hydration rate of products were investigated, the morphologies of products with different solid-liquid ratios were investigated, and hydration curves were analyzed to determine the hydration reaction control types of different magnesium sources. The results show that the evaporation of ammonia in both of them is controlled by diffusion. Under the conditions of 100℃ and 9 h, when the solid-liquid ratio is 1/5, the microcrystalline MgO hydration product has a complete hexagonal sheet structure, while the sheet structure of the lightly burned MgO hydration product is different in size and irregular. Both hydration reactions belong to the internal diffusion chemical reaction control type. This study provides a new idea for the utilization and development of micrystalline magnesite.

Key words: microcrystalline magnesite, powder technology, ammonia evaporation reaction, pyrolysis, kinetics

摘要：

为加强微晶菱镁矿的深入研究，分别以微晶菱镁矿经高温煅烧所得微晶MgO和辽宁某工厂轻烧MgO为原料进行蒸氨、沉镁、煅烧得到MgO，并进行水化实验。采用水合法考察了MgO活性对蒸氨动力学的影响，探究了反应温度、固液比对产品粒径及水化率的影响，考察了不同固液比所得产品形貌，并对水化曲线进行分析，确定了不同镁源的水化反应控制类型。结果表明：二者的蒸氨反应都受扩散控制；在100℃、9 h条件下，固液比为1/5时，微晶MgO水化产品呈完整的六方片状结构，而轻烧MgO水化产品的片状结构大小不一且不规整；二者水化反应均属于化学反应控制类型。此研究为微晶菱镁矿的利用发展提供了新思路。

关键词: 微晶菱镁矿, 粉体技术, 蒸氨反应, 热解, 动力学

CLC Number:

TQ 132.2

Simin YI, Yali MA, Weiqiang LIU, Jinshuai ZHANG, Yan YUE, Qiang ZHENG, Songyan JIA, Xue LI. Study on ammonia evaporation and hydration kinetics of microcrystalline magnesite[J]. CIESC Journal, 2023, 74(4): 1578-1586.

衣思敏, 马亚丽, 刘伟强, 张金帅, 岳岩, 郑强, 贾松岩, 李雪. 微晶菱镁矿蒸氨及水化动力学研究[J]. 化工学报, 2023, 74(4): 1578-1586.

Figures/Tables 12

Table 1 Main components of different MgO

成分	微晶MgO主要成分含量/%	轻烧MgO主要成分含量/%
MgO	96.15	75.83
CaO	1.55	7.21
SiO₂	0.24	10.25
Fe₂O₃	0.05	2.04

Table 2 Active MgO content in hydrated MgO obtained from different raw materials

样品编号	以微晶MgO为原料活性MgO含量/%	以轻烧MgO为原料活性MgO含量/%
1	75.15	56.14
2	76.52	56.35
3	76.47	54.77
平均值	76.05	55.75

Fig.1 Curve of leaching rate of Mg2+ from different raw materials

Fig.2 The fitting relation of ammonia evaporation reaction of different raw materials at different temperatures

Fig.3 lnk-1/T of ammonia of different raw materials

Fig.4 Effect of reaction temperature and solid-liquid ratio on particle size of product

Fig.5 Effect of reaction temperature and solid-liquid ratio on hydration rate

Fig.6 SEM images of hydration products at reaction temperature of 100℃ and reaction time of 3 h

Fig.7 XRD patterns of hydration products at reaction temperature of 100℃ and reaction time of 3 h

Fig.8 Hydration curves of different raw materials

Fig.9 The fitting relation of hydration reaction of different raw materials at different temperatures

Fig.10 lnk-1/T curves of hydration of different raw materials

References 34

1	李志勋, 冯润棠, 田晓利,等. 水化方式对微晶菱镁矿制备高纯氢氧化镁的影响[J]. 耐火材料, 2018, 52(3):213-216.
	Li Z X, Feng R T, Tian X L, et al. Effect of hydration process on preparation of high purity magnesium hydroxide from microcrystalline magnesite[J]. Refractories, 2018, 52(3):213-216.
2	田晓利, 李志勋, 冯润棠,等. 煅烧制度对微晶菱镁矿制备高致密度烧结镁砂性能的影响[J]. 耐火材料, 2022, 56(5):400-406.
	Tian X L, Li Z X, Feng R T, et al. Effect of calcination schedule on properties of high density sintered magnesia prepared from microcrystalline magnesite[J]. Refractories, 2022, 56(5):400-406.
3	王刚, 夏志豪, 李希艳,等. 不同气氛下流化床菱镁矿轻烧产物特性研究[J]. 化工学报, 2022, 73(8):3699-3707.
	Wang G, Xia Z H, Li X Y, et al. Effect of atmosphere on active performance of light-burned magnesium oxides from calcined magnesite in fluidized bed[J]. CIESC Journal, 2022, 73(8):3699-3707.
4	杨翠杰, 赵华, 徐恺,等. (NH₄)₂SO₄浸取轻烧粉的控制过程[J]. 矿产综合利用, 2016(5):66-68, 42.
	Yang C J, Zhao H, Xu K, et al. Study on controlling process of (NH₄)₂SO₄ leaching of light-calcined powder[J]. Multipurpose Utilization of Mineral Resources, 2016(5):66-68, 42.
5	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 magnesit[J]. Conservation and Utilization of Mineral Resources, 2017(1):84-89.
6	范天博, 姜宇, 陈思,等. TRIZ理论在轻烧粉氨气法制备氢氧化镁过程中的应用研究[J]. 无机盐工业, 2019, 51(5):23-27, 44.
	Fan T B, Jiang Y, Chen S, et al. Application of TRIZ theory in preparation of magnesium hydroxide by light burning ammonia[J]. Inorganic Chemicals Industry, 2019, 51(5): 23-27, 44.
7	吴易梅, 孙玉柱, 路贵民,等. 结晶-水热法制备六角片状氢氧化镁[J]. 高校化学工程学报, 2019, 33(2):425-434.
	Wu Y M, Sun Y Z, Lu G M, et al. Preparation of hexagonal sheet magnesium hydroxide flake by a crystallization-hydrothermal method[J]. Journal of Chemical Engineering of Chinese Universities, 2019, 33(2):425-434.
8	赵丽, 王立艳, 肖姗姗,等.氢氧化镁阻燃剂制备研究进展[J]. 无机盐工业, 2018, 50(3):16-19.
	Zhao L, Wang L Y, Xiao S S, et al. Research progress in preparation of magnesium hydroxide flame retardant[J]. Inorganic Chemicals Industry, 2018, 50(3):16-19.
9	李雪, 程沛, 侯睿,等. 轻烧粉氨气法制备氢氧化镁阻燃剂的研究[J]. 无机盐工业, 2016, 48(11):21-24.
	Li X, Cheng P, Hou R, et al. Preparation of Mg(OH)₂ with caustic calcined magnesia through ammonium circulation[J]. Inorganic Chemicals Industry, 2016, 48(11):21-24.
10	姚建平, 范天博, 王健,等. 氨状态对氨法制备氢氧化镁颗粒性质的影响[J]. 化工学报, 2012, 63(1):314-319.
	Yao J P, Fan T B, Wang J, et al. Influence of ammonia state on particle characterization of magnesium hydroxide prepared via ammonia method[J]. CIESC Journal, 2012, 63(1):314-319.
11	孙晓君, 丁珂, 仇龙,等. 以轻烧粉制备六方片状氢氧化镁[J]. 硅酸盐学报, 2019, 47(4):538-544.
	Sun X J, Ding K, Qiu L, et al. Preparation of hexagonal-sheet magnesium hydroxide by surfactant free method[J]. Journal of the Chinese Ceramic Society, 2019, 47(4):538-544.
12	吴丹, 张琦, 王玉琪,等. 轻烧粉在氯化铵体系中的萃取实验研究[J]. 应用化工, 2021, 50(2):415-418.
	Wu D, Zhang Q, Wang Y Q, et al. Experimental study on extraction of light burning powder in ammonium chloride system[J]. Applied Chemical Industry, 2021, 50(2):415-418.
13	丁珂, 孙晓君, 李会杰,等. 氧化镁蒸氨反应的动力学和机理研究[J]. 无机盐工业, 2019, 51(11):31-35.
	Ding K, Sun X J, Li H J, et al. Study on kinetics and mechanism of ammonia evaporation reaction of magnesium oxide[J]. Inorganic Chemicals Industry, 2019, 51(11):31-35.
14	朱云, 王善忠, 胡建锋. 水热法制备阻燃剂氢氧化镁[J]. 有色金属, 2007(3): 30-32, 36.
	Zhu Y, Wang S Z, Hu J F. Hydrothermal preparation of flame retardant Mg(OH)₂ [J]. Nonferrous Metals, 2007(3): 30-32, 36.
15	梁晓正, 马玉新, 李鸣铎,等. 外力环境对氧化镁水化产物性能的影响[J]. 有色金属工程, 2020, 10(6):1-8.
	Liang X Z, Ma Y X, Li M D, et al. Effect of external force on properties of products prepared from hydration of MgO[J]. Nonferrous Metals Engineering, 2020, 10(6): 1-8.
16	白丽梅, 邢智博, 张俊,等. 氧化镁常压水合法制备氢氧化镁的过程分析[J]. 非金属矿, 2017, 40(4):1-3.
	Bai L M, Xing Z B, Zhang J, et al. The process analysis of hydrating magnesium oxide to prepare magnesium hydroxide under the ordinary pressure[J]. Non-Metallic Mines, 2017, 40(4):1-3.
17	黄娜娜, 李会杰, 仇龙,等. 菱镁矿氨法制备氢氧化镁及活性氧化镁水化动力学研究[J]. 盐科学与化工, 2020, 49(2):29-32.
	Huang N N, Li H J, Qiu L, et al. Study on hydration kinetics of magnesium hydroxide and active magnesium oxide prepared by magnesite ammonia process[J]. Journal of Salt Science and Chemical Industry, 2020, 49(2):29-32.
18	刘欣伟, 冯雅丽, 李浩然,等. 菱镁矿制备轻烧氧化镁及其水化动力学研究[J]. 中南大学学报(自然科学版), 2011, 42(12):3912-3917.
	Liu X W, Feng Y L, Li H R, et al. Preparation of light-burned magnesia from magnesite and its hydration kinetics[J]. Journal of Central South University (Science and Technology), 2011, 42(12):3912-3917.
19	王利莎. 氧化镁水合法制备阻燃级氢氧化镁研究[D]. 天津: 天津科技大学, 2012.
	Wang L S. Research on hydration preparation of fire-retardant level magnesium hydrate from magnesium oxide[D]. Tianjin: Tianjin University of Science & Technology, 2012.
20	白炳华. 微晶菱镁矿制备高纯轻质氧化镁研究[D]. 西安: 西安建筑科技大学, 2021.
	Bai B H. Research of preparation of high purity light magnesium oxide from microcrystalline magnesite[D]. Xi'an: Xi'an University of Architecture and Technology, 2021.
21	张诗英. 菱镁粉MgO活性测定方法研究: Cl^－测定法[J]. 武汉工业大学学报, 1994, 16(3): 114-117.
	Zhang S Y. The study of determination method in magnisia activity[J]. Journal of Wuhan University of Technology, 1994, 16(3): 114-117.
22	王素平. 高活性氧化镁的制备与吸附性能的研究[D]. 天津: 天津大学, 2015.
	Wang S P. Study on the synthesis and adsorption properties of high active MgO[D]. Tianjin: Tianjin University, 2015.
23	孙世清, 谢维章. 用热分析方法研究MgO的活性[J]. 硅酸盐学报, 1986, 14(2): 226-232.
	Sun S Q, Xie W Z. Study on the activity of MgO by thermal analysis[J]. Journal of the Chinese Ceramic Society, 1986, 14(2): 226-232.
24	李广垠, 李志坚, 徐娜,等. 轻烧氧化镁活性对烧结镁砂性能的影响[J]. 硅酸盐通报, 2018, 37(5):1699-1703.
	Li G Y, Li Z J, Xu N, et al. Effect of light burned magnesia activity on properties of sintered magnesia[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(5):1699-1703.
25	董金美, 余红发, 张立明. 水合法测定活性MgO含量的试验条件研究[J]. 盐湖研究, 2010, 18(1):38-41.
	Dong J M, Yu H F, Zhang L M. Study on experimental conditions of hydration methods of determining active magnesium oxide content[J]. Journal of Salt Lake Research, 2010, 18(1):38-41.
26	He G X, Zhao Z W, Wang X B, et al. Leaching kinetics of scheelite in hydrochloric acid solution containing hydrogen peroxide as complexing agent[J]. Hydrometallurgy, 2014, 144/145: 140-147.
27	肖永丰, 陈爱国, 张雨薇,等. 粉煤灰提铝硅渣碱溶脱硅反应及其动力学[J]. 硅酸盐通报, 2021, 40(2):542-547.
	Xiao Y F, Chen A G, Zhang Y W, et al. Desilication reaction and kinetics of aluminum-extracting silicon slag in NaOH solution[J]. Bulletin of the Chinese Ceramic Society, 2021,40(2):542-547.
28	Zheng Y J, Chen K K. Leaching kinetics of selenium from selenium-tellurium-rich materials in sodium sulfite solutions[J]. Transactions of Nonferrous Metals Society of China, 2014, 24(2):536-543.
29	Amaral L F, Oliveira I R, Salomão R, et al. Temperature and common-ion effect on magnesium oxide (MgO) hydration[J]. Ceramics International, 2010, 36(3):1047-1054.
30	Kato Y, Yamashita N, Kobayashi K, et al. Kinetic study of the hydration of magnesium oxide for a chemical heat pump [J]. Applied Thermal Engineering, 1996, 16(11):853-862.
31	Birchal V S, Rocha S D F, Mansur M B, et al. A simplified mechanistic analysis of the hydration of magnesia [J]. The Canadian Journal of Chemical Engineering, 2001, 79(4):507-511.
32	郭杰, 刘百宽, 田晓利,等. 微晶菱镁矿制备高纯氢氧化镁水化工艺研究[J]. 非金属矿, 2019, 42(5):45-48.
	Guo J, Liu B K, Tian X L, et al. Study on hydration process of preparing high purity magnesium hydroxide from microcrystalline magnesite[J]. Non-Metallic Mines, 2019, 42(5):45-48.
33	孔会民, 邹来禧, 刘远,等. 以轻烧氧化镁制备六角片状氢氧化镁的研究[J]. 无机盐工业, 2022, 54(1):39-44.
	Kong H M, Zou L X, Liu Y, et al. Study on preparation of hexagonal plates of magnesium hydroxide by light-burned magnesium oxide[J]. Inorganic Chemicals Industry, 2022, 54(1):39-44.
34	翟学良, 杨永社. 活性氧化镁水化动力学研究[J]. 无机盐工业, 2000, 32(4): 16-18.
	Zhai X L, Yang Y S. Study of hydrolization kinetics of activated MgO[J]. Inorganic Chemicals Industry, 2000, 32(4): 16-18.

[1]	Cheng CHENG, Zhongdi DUAN, Haoran SUN, Haitao HU, Hongxiang XUE. Lattice Boltzmann simulation of surface microstructure effect on crystallization fouling [J]. CIESC Journal, 2023, 74(S1): 74-86.
[2]	Lei WU, Jiao LIU, Changcong LI, Jun ZHOU, Gan YE, Tiantian LIU, Ruiyu ZHU, Qiuli ZHANG, Yonghui SONG. Catalytic microwave pyrolysis of low-rank pulverized coal for preparation of high value-added modified bluecoke powders containing carbon nanotubes [J]. CIESC Journal, 2023, 74(9): 3956-3967.
[3]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[4]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[5]	Zhenghao YANG, Zhen HE, Yulong CHANG, Ziheng JIN, Xia JIANG. Research progress in downer fluidized bed reactor for biomass fast pyrolysis [J]. CIESC Journal, 2023, 74(6): 2249-2263.
[6]	Guangyu WANG, Kai ZHANG, Kaihua ZHANG, Dongke ZHANG. Heat and mass transfer and energy consumption for microwave drying of coal slime [J]. CIESC Journal, 2023, 74(6): 2382-2390.
[7]	Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts [J]. CIESC Journal, 2023, 74(6): 2416-2426.
[8]	Quanbi ZHANG, Yijin YANG, Xujing GUO. Catalytic degradation of dissolved organic matter in rifampicin pharmaceutical wastewater by Fenton oxidation process [J]. CIESC Journal, 2023, 74(5): 2217-2227.
[9]	Jin YU, Binbin YU, Xinsheng JIANG. Study on quantification methodology and analysis of chemical effects of combustion control based on fictitious species [J]. CIESC Journal, 2023, 74(3): 1303-1312.
[10]	Qingyun YANG, Qingsong LI, Zeming CHEN, Jing DENG, Yuying LI, Fan YANG, Guoyuan CHEN, Guoxin LI. Degradation of methylparaben by UV/PMS, UV/PDS and UV/SPC process [J]. CIESC Journal, 2023, 74(3): 1322-1331.
[11]	Ruizhe CHEN, Leilei CHENG, Jing GU, Haoran YUAN, Yong CHEN. Research progress in chemical recovery technology of fiber-reinforced polymer composites [J]. CIESC Journal, 2023, 74(3): 981-994.
[12]	Lingxin ZU, Rongting HU, Xin LI, Yudao CHEN, Guanglin CHEN. Carbon release products and denitrification bioavailability from chemical components of woody biomass [J]. CIESC Journal, 2023, 74(3): 1332-1342.
[13]	Han HU, Liang YANG, Chunxiao LI, Daoping LIU. Kinetics of methane storage in the natural tobacco leaching filtrate in the hydrate form [J]. CIESC Journal, 2023, 74(3): 1313-1321.
[14]	Jieyuan ZHENG, Xianwei ZHANG, Jintao WAN, Hong FAN. Synthesis and curing kinetic analysis of eugenol-based siloxane epoxy resin [J]. CIESC Journal, 2023, 74(2): 924-932.
[15]	Xianxian RAO, Miao DU, Guorong SHAN, Pengju PAN. Effect of different metal salt demulsifiers on vulcanization behavior of isobutylene isoprene rubber [J]. CIESC Journal, 2023, 74(2): 756-765.