菱镁矿浮选尾矿直接合成同时制备镁橄榄石和镁砂研究

doi:10.11949/0438-1157.20220143

摘要/Abstract

摘要：

为了有效利用菱镁矿浮选尾矿废弃物，提出以其为原料，在不添加任何物质、不经过高压压制成型的条件下直接烧制同时制备优质镁橄榄石和烧结镁砂的技术路线，并在高温管式炉中对其可行性进行了实验研究。通过对不同反应温度和时间条件下制备的样品进行XRD和SEM-EDS表征和分析，确认新技术路线不仅可行，并且还具有反应速度快、产品质量优等优势。当反应温度为1400℃及以上时，原料中的SiO₂在数分钟之内全部转化，产物镁橄榄石和烧结镁砂晶体发育良好。研究结果对进一步开发菱镁矿浮选尾矿废弃物高效利用新技术提供有力支持。

关键词: 菱镁矿浮选尾矿, 镁橄榄石, 烧结镁砂, 细颗粒, 高温固相反应

Abstract:

This paper proposed producing high-quality forsterite and sintered magnesia by high-temperature solid-state reactions of the waste magnesia ore directly without adding other materials and briquetting in order to realize the value-added utilization of magnesite flotation tailings. The experiments were carried out in a high-temperature tubular reactor at different reaction temperatures and times. The reaction products were characterized by XRD and SEM-EDS. The results confirmed that the proposed method was technically feasible and had noticeable advantages, including the fast reaction rate and high product quality. When the reaction temperature is 1400℃ and above, the SiO₂ in the raw material is completely converted within a few minutes, and the product forsterite and sintered magnesia crystals are well developed. The research results provide strong support for the further development of new technologies of efficient utilization of magnesite flotation tailings.

Key words: magnesite flotation tailings, forsterite, sintered magnesia, fine particle, high-temperature solid-state reactions

中图分类号:

TQ 028.8

李亚芾, 付亮亮, 白浩隆, 白丁荣, 许光文. 菱镁矿浮选尾矿直接合成同时制备镁橄榄石和镁砂研究[J]. 化工学报, 2022, 73(8): 3679-3687.

Yafu LI, Liangliang FU, Haolong BAI, Dingrong BAI, Guangwen XU. The simultaneous synthesis of high-quality forsterite and sintered magnesia from magnesite flotation tailings[J]. CIESC Journal, 2022, 73(8): 3679-3687.

图/表 14

表1 国内外有关人工合成镁橄榄石的基础研究

Table 1 Summary of literature research on forsterite synthesis

研究者	原料	试样样品形状或尺寸	反应温度和时间	主要结果
陈勇等^[13]	电熔镁砂细粉和二氧化硅微粉	Φ 40 mm×25 mm	1350/1400/1450/1500/1550/1600℃, 5 h	在最佳MgO和SiO₂配比下，仍有少量 SiO₂未完全转化；过量MgO阻碍了烧结的进行
Ando等^[14]	高纯硅粉和电熔镁砂	Φ 12 mm×6 mm	1400℃，2 h	未完全转化的SiO₂影响了产物作为超高频电介质的性能
丁达飞等^[15]	菱镁矿尾矿、硅石粉、硅灰、滑石及高纯镁砂	Φ 40 mm×130 mm	1580℃, 5 h	理论配比条件下仍有3%~10%的MgO未转化成镁橄榄石
陈少一等^[16]	氢氧化镁和二氧化硅	Φ 40 mm×50 mm	1400/1500/1600/1700℃, 3 h	1500℃及以下超过30%的SiO₂未转化成镁橄榄石
孟庆新等^[17]	菱镁矿细粉和天然硅石粉	圆柱试样（文中未提及具体尺寸）	1300/1400/1500/1600℃, 3 h	温度低于1400℃时，物相组成中含有未转化的SiO₂
Ren等^[18]	菱镁矿尾矿与硅废料	Φ 50×50 mm	1300/1400/1500/1600℃, 3 h	硅石对反应过程和产品质量具有较大影响
Liu等^[19]	SiO₂和Mg(OH)₂材料	Φ 50×50 mm Φ 25×50 mm	1500℃，3 h后，再1500/1600/1700℃, 3 h	在第一段烧结过程中，会生成顽火辉石相，并非全部转化成为镁橄榄石
Kullatham等^[20]	泰国滑石和菱镁矿	Φ 15 mm×20 mm	900/1000/1100/1200/1300℃，1 h	24 h球磨和5 h活化原料，烧结产物相对密度最高84.59%
Tan等^[2]	MgO粉末和 Mg₃Si₄O₁₀(OH)₂粉末	圆形球坯（文中未提及具体尺寸）	1200~1500℃，2 h	在1200℃反应2 h，再在1200~1500℃烧结2 h后，才生成产品

图1 原料A（a）和原料B（b）的粒度分布图

Fig.1 The particle size distributions of samples A(a) and B(b)

图2 原料A（a）和原料B（b）的XRD谱图

Fig.2 XRD spectra of samples A (a) and B (b)

图3 原料A（a）和原料B（b）的SEM-EDS检测结果

Fig.3 SEM-EDS spectra of samples A (a) and B (b)

表2 原料A和B的物质组成

Table 2 Material compositions of samples A and B

项目		MgCO₃	MgO	SiO₂	Al₂O₃	Fe₂O₃	CaO
原料A	%(mol)	68.12	—	29.63	1.19	0.46	0.60
原料A	%(mass)	74.09	—	22.96	1.56	0.96	0.43
原料B	%(mol)	—	74.34	23.01	1.29	0.25	1.11
原料B	%(mass)	—	64.96	29.97	2.86	0.86	1.35

图4 实验装置及方法示意图

Fig.4 Schematic illustrations of the experimental apparatus and sample analysis methods

图5 在1500℃反应120 min生成的样品XRD谱图和SEM照片

Fig.5 XRD patterns and SEM image of the sample produced at 1500℃ and 120 min reaction conditions

图6 原料A在1500℃反应120 min前（a）、后（b）Mg和Si元素的分布对比

Fig.6 Comparison of Mg and Si element distributions in the raw materials (a) and sample produced at 1500℃ and 120 min (b)

图7 反应温度对样品特性的影响（反应时间10 min）

Fig.7 Influence of the reaction temperature on the product quality at a constant reaction time of 10 min

图8 反应温度对制得样品中MgO和Mg2SiO4晶粒尺寸的影响（反应时间10 min）

Fig.8 Influence of the reaction temperature on the grain sizes of MgO and Mg2SiO4 at a constant reaction time of 10 min

图9 在反应温度为1500和1600℃时反应时间对制得样品特性的影响

Fig.9 Influence of the reaction time on the products at 1500℃ and 1600℃

图10 在反应温度1500和1600℃时反应时间对样品中MgO和Mg2SiO4晶粒尺寸的影响

Fig.10 Influence of the reaction time on the grain sizes of MgO and Mg2SiO4 at 1500℃ and 1600℃

图11 反应温度1500℃（a）和1600℃（b）时不同反应时间所得样品的形貌特征

Fig.11 SEM images of samples obtained with different reaction times at 1500℃ and 1600℃

图12 制得样品成分与反应温度和时间的关系

Fig.12 Variation of the product chemical composition with the reaction temperature and time

参考文献 25

1	陈英春, 周佳芬, 路贵民, 等. 高纯镁砂及氧化镁陶瓷研究进展[J]. 化工进展, 2019, 38(1): 505-515.
	Chen Y C, Zhou J F, Lu G M, et al. A review on the production technologies of high-purity magnesia and magnesium oxide ceramics[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 505-515.
2	Tan C Y, Singh R, Teh Y C, et al. Sinterability of forsterite prepared via solid-state reaction[J]. International Journal of Applied Ceramic Technology, 2015, 12(2): 437-442.
3	Guo Z Q, Ma Y, Rigaud M. Sinterability of macrocrystalline and cryptocrystalline magnesite to refractory magnesia[J]. International Journal of Ceramic Engineering & Science, 2020, 2(6): 303-309.
4	王汇平, 崔妍, 曲殿利. 添加La₂O₃对菱镁矿制备烧结镁砂性能的影响[J]. 耐火材料, 2021, 55(1): 61-63, 68.
	Wang H P, Cui Y, Qu D L. Effect of La₂O₃ addition on properties of sintered magnesia prepared from magnesite[J]. Refractories, 2021, 55(1): 61-63, 68.
5	连娜. 利用菱镁矿原矿制备烟气脱硫剂的研究[D]. 鞍山: 辽宁科技大学, 2014.
	Lian N. The use of magnesite in the wet flue gas desulfurization[D]. Anshan: University of Science and Technology Liaoning, 2014.
6	刘永杰, 孙杰璟, 孟庆凤. 利用菱镁矿尾矿制备镁硅酸盐水泥的研究[J]. 硅酸盐通报, 2013, 32(6): 1126-1130.
	Liu Y J, Sun J J, Meng Q F. Study on magnesite tailing for preparing magnesium silicate cement[J]. Bulletin of the Chinese Ceramic Society, 2013, 32(6): 1126-1130.
7	袁广亮. 镁橄榄石轻质隔热耐火材料制备工艺研究[D]. 西安: 西安建筑科技大学, 2010.
	Yuan G L. Preparation of lightweight refractories of forsterite[D]. Xi'an: Xi'an University of Architecture and Technology, 2010.
8	Douy A. Aqueous syntheses of forsterite (Mg₂SiO₄) and enstatite (MgSiO₃)[J]. Journal of Sol-Gel Science and Technology, 2002, 24(3): 221-228.
9	Brindley G W, Hayami R. Kinetics and mechanism of formation of forsterite (Mg₂SiO₄) by solid state reaction of MgO and SiO₂ [J]. Philosophical Magazine, 1965, 12(117): 505-514.
10	Lin L, Yin M, Shi C S, et al. Luminescence properties of a new red long-lasting phosphor: Mg₂SiO₄: Dy³⁺, Mn²⁺ [J]. Journal of Alloys and Compounds, 2008, 455(1/2): 327-330.
11	Othman A G M, Khalil N M. Sintering of magnesia refractories through the formation of periclase-forsterite-spinel phases[J]. Ceramics International, 2005, 31(8): 1117-1121.
12	祁欣, 罗旭东, 李振, 等. 高硅菱镁矿的选矿提纯与应用研究进展[J]. 硅酸盐通报, 2021, 40(2): 485-492.
	Qi X, Luo X D, Li Z, et al. Research progress on purification and application of high-silicon magnesite[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(2): 485-492.
13	陈勇, 于景坤, 高杰. 烧结温度对合成镁橄榄石性能的影响[J]. 硅酸盐通报, 2012, 31(3): 622-625.
	Chen Y, Yu J K, Gao J. Effect of sinterring temperature on the properties of synthetic forsterite[J]. Bulletin of the Chinese Ceramic Society, 2012, 31(3): 622-625.
14	Ando M, Ohsato H, Kagomiya I, et al. Quality factor of forsterite for ultrahigh frequency dielectrics depending on synthesis process[J]. Japanese Journal of Applied Physics, 2008, 47(9): 7729-7731.
15	丁达飞, 李志坚, 栾旭. 用菱镁矿尾矿合成高纯镁橄榄石[C]//2015耐火材料综合学术年会. 论文集( 3). 2015:156-158.
	Ding D F, Li Z J, Luan X. Synthesis of high purity magnesium olivine from magnesite tailings [C]//2015 Refractory Comprehensive Academic Conference. Proceedings ( 3). 2015: 156-158.
16	陈少一, 刘浩, 王周福, 等. 温度及组成对镁橄榄石合成过程的影响[J]. 陶瓷学报, 2017, 38(5): 621-625.
	Chen S Y, Liu H, Wang Z F, et al. Effects of temperature and composition on the synthesis process of forsterite[J]. Journal of Ceramics, 2017, 38(5): 621-625.
17	孟庆新, 周宁生, 刘昭, 等. 高纯镁橄榄石质轻质微孔原料的制备[J]. 耐火材料, 2020, 54(1): 56-60.
	Meng Q X, Zhou N S, Liu Z, et al. Preparation of high-purity forsterite light-weight micropore starting materials[J]. Refractories, 2020, 54(1): 56-60.
18	Ren X M, Ma B Y, Fu G F, et al. Facile synthesis of MgO-Mg₂SiO₄ composite ceramics with high strength and low thermal conductivity[J]. Ceramics International, 2021, 47(14): 19959-19969.
19	Liu H, Jie C, Ma Y, et al. Synthesis and processing effects on microstructure and mechanical properties of forsterite ceramics[J]. Transactions of the Indian Ceramic Society, 2020, 79(2): 83-87.
20	Kullatham S, Synthesis Thiansem S., characterization and properties of forsterite refractory produced from Thai talc and magnesite[J]. Materials Science Forum, 2018, 940: 46-50.
21	Chung F H. Quantitative interpretation of X-ray diffraction patterns of mixtures(Ⅰ): Matrix-Flushing method for quantitative multicomponent analysis[J]. Journal of Applied Crystallography, 1974, 7(6): 519-525.
22	Chung F H. Quantitative interpretation of X-ray diffraction patterns of mixtures(Ⅱ): Adiabatic principle of X-ray diffraction analysis of mixtures[J]. Journal of Applied Crystallography, 1974, 7(6): 526-531.
23	单小兵, 张其土, 李玉华. X射线K值法在水泥物相中的应用[J]. 理化检验(物理分册), 2002, 38(8): 342-345.
	Shan X B, Zhang Q T, Li Y H. Application of XRD K value method in cement[J]. Physical Testing and Chemical Analysis Parta Physical Testing, 2002, 38(8): 342-345.
24	范国宁, 韩萍. X射线衍射K值法测定加氢催化剂及载体中二氧化钛的含量[J]. 化学工程师, 2014, 28(11): 20-22, 64.
	Fan G N, Han P. Determination of TiO₂ content in hydrogenation catalyst and its carrier using K value method of X-ray diffraction[J]. Chemical Engineer, 2014, 28(11): 20-22, 64.
25	王雷雷, 王勤隆, 李晶, 等. X射线衍射法测定纳米氧化铝的平均晶粒尺寸[J]. 无机盐工业, 2021, 53(4): 86-89.
	Wang L L, Wang Q L, Li J, et al. Determination of average grain size of nano-alumina by X-ray diffraction method[J]. Inorganic Chemicals Industry, 2021, 53(4): 86-89.

[1]	熊桂龙, 谢静雯, 杨林军. 粗糙度对水汽在细颗粒表面异质核化影响的数值模拟[J]. 化工学报, 2021, 72(8): 4304-4313.
[2]	余廷芳, 高巨, 熊桂龙, 李水清, 姚强. 基于分子运动学的水汽在细颗粒表面异质核化的数值模拟[J]. 化工学报, 2020, 71(7): 3071-3079.
[3]	王健,潘伶,王帅,张昊. 工程相变凝并器内超细颗粒长大与脱除性能分析[J]. 化工学报, 2020, 71(11): 5090-5098.
[4]	吴建东, 刘乔, 王昊. 带绕流板的湍流管道内细颗粒物沉积实验[J]. 化工学报, 2018, 69(S1): 15-19.
[5]	侯大伟, 潘丹萍, 周心澄, 黄荣廷, 沈凯, 杨林军. 石灰石-石膏法脱硫过程中浆液雾化夹带与细颗粒排放的关系[J]. 化工学报, 2018, 69(4): 1714-1722.
[6]	刘道银, 王远保, 王铮, 陈晓平. 超细颗粒聚团流化的临界流化速度[J]. 化工学报, 2017, 68(11): 4105-4111.
[7]	郑建祥, 许帅, 王京阳, 史梦燚, 汪龙. 基于微分代数积分矩量法的聚并器超细颗粒聚团研究[J]. 化工学报, 2017, 68(1): 119-128.
[8]	孙伟, 刘小伟, 徐义书, 陈栋, 张宇, 崔江, 徐明厚. 两种改性高岭土减排超细颗粒物的对比分析[J]. 化工学报, 2016, 67(4): 1179-1185.
[9]	潘丹萍, 郭彦鹏, 黄荣廷, 盛溢, 杨林军. 石灰石-石膏法烟气脱硫过程中细颗粒物形成特性[J]. 化工学报, 2015, 66(11): 4618-4625.
[10]	颜金培, 陈立奇, 杨林军. 燃煤细颗粒在过饱和氛围下声波团聚脱除的实验研究[J]. 化工学报, 2014, 65(8): 3243-3249.
[11]	沙焱, 杨林军, 陈浩, 瞿如敏. 燃煤烟气中细颗粒物与共存气态组分对膜吸收CO₂的影响[J]. 化工学报, 2013, 64(4): 1293-1299.
[12]	张明俊，凡凤仙. 细颗粒物的声凝并数值模拟研究进展[J]. 化工进展, 2012, 31(08): 1671-1676.
[13]	沙焱，杨林军. 燃煤烟气杂质影响膜法捕集CO2的研究进展 [J]. CIESC Journal, 2011, 30(9): 2069-.
[14]	耿俊峰, 宋士娟, 鲍静静, 杨林军. 应用润湿剂促进WFGD系统脱除细颗粒物的性能 [J]. 化工学报, 2011, 62(4): 1084-1090.
[15]	李林，董勇，崔琳，张立强，马春元. 荷电水雾脱除超细颗粒物的研究进展 [J]. CIESC Journal, 2010, 29(6): 1143-.