基于自燃烧技术的铁铝酸钙固溶体低温制备与特性研究

doi:10.11988/ckyyb.20230823

长江科学院院报 ›› 2024, Vol. 41 ›› Issue (9): 146-152.DOI: 10.11988/ckyyb.20230823

基于自燃烧技术的铁铝酸钙固溶体低温制备与特性研究

汪健¹(), 雷金松², 方国宝³, 乔鑫位⁴, 李杨⁵(), 董芸⁵, 严建军⁵

¹ 安徽省引江济淮集团有限公司,合肥 231200
² 安徽水安建设集团股份有限公司,合肥 231200
³ 长江勘测设计集团有限公司,武汉 430010
⁴ 安徽省水利水电勘测规划设计研究院,合肥 231200
⁵ 长江科学院材料与结构研究所,武汉 430010

收稿日期:2023-07-31 修回日期:2023-12-11 出版日期:2024-09-01 发布日期:2024-09-01
通信作者:
李杨(1987-),男,河南驻马店人,高级工程师,博士,主要从事水泥基材料微观性能与调控的研究。E-mail:liyangzzu@126.com
作者简介:
汪健(1992-),男,安徽庐江人,工程师,硕士,主要从事水利水电工程建设及运营管理工作。E-mail:290445658@qq.com
基金资助:
中央级公益性科研院所基本科研业务费项目(CKSF2021456/CL); 国家自然科学基金项目(U2040222); 安徽省引江济淮集团有限公司科技项目(YJJH-ZT-ZX-20190823179)

High Efficiency Synthesis of Calcium Aluminoferrite at Low Temperature Based on Self-propagating Combustion Reaction

WANG Jian¹(), LEI Jin-song², FANG Guo-bao³, QIAO Xin-wei⁴, LI Yang⁵(), DONG Yun⁵, YAN Jian-jun⁵

¹ Anhui Provincial Group Limited for Yangtze-to-Huaihe River Water Diversion, Hefei 231200,China
² Anhui Shui’an Construction Group Co., Ltd., Hefei 231200,China
³ Changjiang Surveying, Planning andDesigin Institute, Wuhan 430010,China
⁴ Anhui Surveying and Design Institute of Water Resources andHydropower,Hefei 231200,China
⁵ Material and Structure Department, Changjiang River Scientific ResearchInstitute, Wuhan 430010,China

Received:2023-07-31 Revised:2023-12-11 Published:2024-09-01 Online:2024-09-01

摘要/Abstract

摘要：

熟料煅烧是影响硅酸盐水泥生产能耗的关键环节,而熟料矿物相的高效能低温制备是水泥工业研究的重点。以可溶性的金属硝酸盐和尿素为原料,借助自蔓延燃烧(SPCR)法在低温下制备出铁铝酸四钙(C₄AF),并借助X射线衍射(XRD)、傅里叶变换红外(FTIR)、扫描电子显微镜(SEM)和等温微量热技术,研究了合成C₄AF的矿物组成、结晶程度、颗粒形貌、水化特性等特性。结果表明:SPCR法能够在500 ℃恒温2 h制备出纯度和结晶程度均较好的C₄AF,优选的原材料质量比为 $m_{C a (N O_{3})_{2} \cdot 4 H_{2} O}$ ∶ $m_{A l (N O_{3})_{3} \cdot 9 H_{2} O}$ ∶ $m_{F e (N O_{3})_{3} \cdot 9 H_{2} O}$ ∶ $m_{C O (N H_{2})_{2}}$ =1.259∶1.0∶1.077∶2.664。CaCO₃是SPCR法制备C₄AF的过渡相,增加尿素用量有利于提高反应温度,改善C₄AF的结晶程度。合成C₄AF具有较高的水化活性,水化30 min内出现放热峰,水化过程中无休眠期出现,完全水化时的水化热为474 J/g。

关键词: 硅酸盐水泥, 熟料, 铁铝酸四钙, 自蔓延燃烧, 低温

Abstract:

Clinker calcination is a critical stage that influences the energy consumption in Portland cement production, and improving the efficiency of clinker manufacturing is a major concern in cement chemistry. This paper focuses on the synthesis of tetra-calcium aluminoferrite (C₄AF) at low temperatures with soluble metallic nitrate and urea as raw materials using the self-propagating combustion reaction (SPCR) method. We systematically analyze the mineral phase composition, crystallinity, particle morphology, and hydration behavior of the synthesized C₄AF using X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and isothermal microcalorimetry. Our findings demonstrate that high-purity C₄AF can be successfully synthesized via the SPCR method at 500 ℃ for 2 hours. The optimal raw material ratio by weight is $m_{C a (N O_{3})_{2} \cdot 4 H_{2} O}$ ∶ $m_{A l (N O_{3})_{3} \cdot 9 H_{2} O}$ ∶ $m_{F e (N O_{3})_{3} \cdot 9 H_{2} O}$ ∶ $m_{C O (N H_{2})_{2}}$ =1.259∶1.0∶1.077∶2.664. CaCO₃ is the only transient phase during the formation of C₄AF. Increasing the urea dosage effectively raises reaction temperature and enhances the crystallinity of the synthesized C₄AF. Additionally, the synthesized C₄AF exhibits high hydration activity with only one peak observed in the hydration heat release curve during the initial 30 minutes. No dormancy period is observed, and the calculated hydration heat at complete hydration is 474 J/g.

Key words: portland cement, clinker, tetra-calcium aluminoferrite, self-propagating combustion reaction, low temperature

中图分类号:

TV431水工混凝土

汪健, 雷金松, 方国宝, 乔鑫位, 李杨, 董芸, 严建军. 基于自燃烧技术的铁铝酸钙固溶体低温制备与特性研究[J]. 长江科学院院报, 2024, 41(9): 146-152.

WANG Jian, LEI Jin-song, FANG Guo-bao, QIAO Xin-wei, LI Yang, DONG Yun, YAN Jian-jun. High Efficiency Synthesis of Calcium Aluminoferrite at Low Temperature Based on Self-propagating Combustion Reaction[J]. Journal of Changjiang River Scientific Research Institute, 2024, 41(9): 146-152.

图/表 11

图1 C4AF制备过程

Fig.1 Synthesis procedures of C4AF

表1 金属硝酸盐和尿素的化学平衡价

Table 1 Equivalent valencies of metallic nitrate and urea

物质	各元素化合价							化学平衡价	作用
物质	Ca	Fe	Al	H	O	C	N	化学平衡价	作用
Ca(NO₃)₂·4H₂O	+2			+1	-2		0	-10	氧化剂
Al(NO₃)₃·9H₂O			+3	+1	-2		0	-15	氧化剂
Fe(NO₃)₃·9H₂O		+3					0	-15	氧化剂
CO(NH₂)₂					-2	+4	0	+6	还原剂

图2 尿素和金属硝酸盐摩尔比对反应温度的影响

Fig.2 Influence of molar ratio of urea to metallic nitrate on reaction temperature

表2 合成C4AF晶格参数

Table 2 Crystal parameters of synthesized C4AF

原子	位置	x	y	z
Ca	8c 1	0.025 9	0.108 6	0.491
Fe(oct)	4a 2	0	0	0
Fe(tet)	4b m	0.926 1	1/4	0.959 5
Al(oct)	4a 2	0	0	0
Al(tet)	4b m	=Fe(tet)	1/4	=Fe(tet)
O (1)	8c 1	0.253 1	0.987 3	0.243 5
O(2)	8c 1	0.069 4	0.144 3	0.028 9
O(3)	4b m	0.86	1/4	0.611

图3 尿素用量对合成C4AF制备效果的影响

Fig.3 Influence of urea dosage on synthesized C4AF

图4 合成C4AF的结晶情况

Fig.4 Crystallinity of synthesized C4AF

图5 合成C4AF的FTIR图谱和去卷积分峰结果

Fig.5 FTIR spectrum and deconvolution results of synthesized C4AF

表3 合成C4AF的FTIR图谱上信号峰的归属情况

Table 3 Signal attribution of synthesized C4AF FTIR spectrum

波数/cm^-1	归属
343 9	υ O-H (H₂O)
1 631	δO-H (H₂O)
2 919、2 584	Al₂O₃中的Al-O 或是Fe₃O₄中的Fe-O
2 375	υC-O (CO₂)
2 325	δC-O (CO₂)
2 515、575、486	不明确
1 469	υ₃ C-O ( ${CO}_{3}^{2 -}$ )
1 423	υ₃C-O ( ${CO}_{3}^{2 -}$ )
874	υ₂C-O ( ${CO}_{3}^{2 -}$ )
418	δCa-O (CaO)

表3 合成C4AF的FTIR图谱上信号峰的归属情况

Table 3 Signal attribution of synthesized C4AF FTIR spectrum

波数/cm^-1	归属
343 9	υ O-H (H₂O)
1 631	δO-H (H₂O)
2 919、2 584	Al₂O₃中的Al-O 或是Fe₃O₄中的Fe-O
2 375	υC-O (CO₂)
2 325	δC-O (CO₂)
2 515、575、486	不明确
1 469	υ₃ C-O ( ${CO}_{3}^{2 -}$ )
1 423	υ₃C-O ( ${CO}_{3}^{2 -}$ )
874	υ₂C-O ( ${CO}_{3}^{2 -}$ )
418	δCa-O (CaO)

图6 合成C4AF颗粒形貌的SEM照片

Fig.6 SEM image of particle morphology of synthesized C4AF

图7 合成C4AF的水化放热特性曲线

Fig.7 Characteristic curves of hydration heat release of synthesized C4AF

图8 合成C4AF完全水化放热量计算

Fig.8 Calculation result of complete hydration heat of synthesized C4AF

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基于自燃烧技术的铁铝酸钙固溶体低温制备与特性研究

High Efficiency Synthesis of Calcium Aluminoferrite at Low Temperature Based on Self-propagating Combustion Reaction

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