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黄金科学技术 ›› 2020, Vol. 28 ›› Issue (5): 658-668.doi: 10.11872/j.issn.1005-2518.2020.05.127

• 绿色胶凝材料专栏 • 上一篇    下一篇

铝硅酸盐固废胶凝材料制备及其性能

叶智远1,2(),王倩倩1,2()   

  1. 1.南京工业大学材料科学与工程学院，江苏 南京 211816
    2.南京工业大学材料化学工程国家重点实验室，江苏 南京 211816
  • 收稿日期:2020-07-16 修回日期:2020-08-18 出版日期:2020-10-31 发布日期:2020-11-05
  • 通讯作者: 王倩倩 E-mail:201861203117@njtech.edu.cn;qqwang@njtech.edu.cn
  • 作者简介:叶智远（1995-），男，江苏扬州人，硕士研究生，从事固废胶凝材料研究工作。201861203117@njtech.edu.cn
  • 基金资助:
    国家自然科学基金青年基金项目“硅酸钙矿物水化反应位点计算、表征及活性调控研究”(51602148);国家自然科学基金—山东联合基金“高耐久海工混凝土组成结构设计和关键技术及其应用基础研究”(U1806222);江苏高校优势学科建设工程项目

Preparation and Performance of Aluminosilicate Based Solid Waste Cemen-titious Materials

Zhiyuan YE1,2(),Qianqian WANG1,2()   

  1. 1.College of Materials Science and Engineering，Nanjing Tech University，Nanjing 211816，Jiangsu，China
    2.State Key Laboratory of Materials-Oriented Chemical Engineering，Nanjing Tech University，Nanjing 211816，Jiangsu，China
  • Received:2020-07-16 Revised:2020-08-18 Online:2020-10-31 Published:2020-11-05
  • Contact: Qianqian WANG E-mail:201861203117@njtech.edu.cn;qqwang@njtech.edu.cn

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摘要：

通过调控赤泥和煤矸石的不同质量配比，采用热活化与复合钙基激发剂活化相结合的方式，制备赤泥和煤矸石总掺量达65%的铝硅酸盐固废胶凝材料。采用X射线衍射（XRD）、热重—差热分析（TG-DSC）和傅里叶红外光谱分析等表征手段对不同龄期硬化浆体进行分析，并研究其物相发展。研究结果表明：赤泥和煤矸石的配比对胶凝材料抗压强度和水化产物的形成及发展具有重要影响。赤泥与煤矸石在固废胶凝材料中掺量（质量分数）分别为39%和26%时，胶凝材料综合性能最佳。XRD图谱表明：赤泥—煤矸石基固废热活化后的铝酸盐，与石膏、Ca（OH）2和碳酸盐等反应，形成钙钒石（AFt）、单斜型水化硫铝酸钙（AFm）和半碳型水化铝酸钙（Hc）等水化产物；TG-DSC分析表明不同样品生成的C-A-S-H凝胶和AFt含量不同。适当配比的赤泥和煤矸石在热活化和复合钙基激发剂活化过程中都体现了协同活化作用，一方面促进了活性铝酸盐和硅酸盐离子的释放，另一方面促进了火山灰反应及水化产物的形成，使得浆体早期和后期抗压强度提升。该研究为赤泥和煤矸石等含较高铝硅质组分的大宗工业固废在矿山胶结充填、路基材料和墙体砌块材料等方面的应用提供理论指导。

关键词: 赤泥, 煤矸石, 热活化, 钙基激发, 钙钒石, 火山灰反应, 固废胶凝材料

Abstract:

The metallurgical and coal power industries produce a large amount of solid wastes，such as red mud and coal gangue，etc.The main elemental composition of this solid waste is Si，Al，Fe，Ca，Na and O，etc.It has the potential to prepare cementitious materials in terms of chemical composition and phase composition.The preparation of industrial solid waste into low cost cementitious material is an effective way to realize the large utilization of solid waste as well as energy conservation and emission reduction.Solid waste cementitious materials with 65% of red mud and coal gangue were prepared.Different mass ratios between red mud and coal gangue was considered.The recombination method of thermal activation and compound activation methods were used to improve their cementitious properties.X-ray diffraction（XRD），thermogravimetric-differential thermal analysis（TG-DSC） and Fourier infrared spectroscopy analysis were used to analyze the hydration products at different ages.The results show that the mass ratio of red mud to coal gangue has an important influence on the compressive strength of the hardened pastes，as well as the formation and development of hydration products.When the addition of red mud and coal gangue in the solid waste cementitious materials are 39% and 26% respectively，the compressive strength is the highest on the 3rd day，up to 13.28 MPa.When the addition of red mud and coal gangue in the solid waste cementitious materials are 13% and 52% respectively，the compressive strength on the 28 days is the highest，up to 31.62 MPa.The XRD patterns show that the red mud and coal gangue composites after thermal activated can react with gypsum，calcium hydroxide and carbonate to form ettringite （AFt），monosulfoaluminate hydrate （AFm），Hemicarbonate （Hc），and so on.TG-DSC analysis show that the content of C-A-S-H gel and AFt produced by different mass ratios of red mud and coal gangue is different.The pozzolanic reaction of the samples with higher coal gangue content is stronger at 28 days，resulting into the higher consumption of the calcium hydroxide in the activator，which is the main reason for the rapid development of the compressive strength of the red mud-coal gangue based solid waste cementitious materials at 28 days.A synergistic effect between red mud and coal gangue was determined by the heat activation and the addition of calcium based activators，i.e.， the release of active aluminate and silicate ions was promoted and the pozzolanic reaction was activited with more hydration products formed.Thus，it is conducive to the improvement of the compressive strength of sample in the early and late stages.This research provides theoretical guidance for the application of red mud and coal gangue-based bulk industrial solid wastes with higher aluminum and silicate components in the preparation of pavement base materials，wall building blocks and mine filling materials.

Key words: red mud, coal gangue, thermal activation, calcium based activation, ettringite, pozzolanic reaction, solid waste cementitious materials

中图分类号: 

  • TQ177

表1

X射线荧光分析法（XRF）分析得到的试验原料化学组成"

原料名称SiO2Al2O3Fe2O3CaONa2OTiO2MgOK2OSO3LOI

赤泥

煤矸石

熟料

石膏

13.76

57.05

18.80

10.96

22.90

23.21

4.10

3.97

32.35

3.61

3.90

1.30

3.30

0.52

64.80

24.72

9.37

0.45

0.10

0.44

3.68

0.80

0.00

0.14

0.25

0.61

0.70

2.26

0.13

1.59

0.70

0.75

0.43

0.12

2.90

33.84

12.99

11.72

3.20

21.20

图1

试验原料XRD分析图谱"

表 2

原料的配合比设计"

样品编号RM∶CG煤矸石+赤泥/%熟料/%石膏/%石灰/%

S1

S2

S3

S4

S5

S6

S7

S8

S9

1∶9

2∶8

3∶7

4∶6

5∶5

6∶4

7∶3

8∶2

9∶1

65

65

65

65

65

65

65

65

65

15

15

15

15

15

15

15

15

15

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

图2

不同配比赤泥煤矸石基固废胶凝材料粒径分布图注：S1 D50：24.18为S1样品（其D50为24.18 mm）的结果，其他依此类推"

图3

不同配比赤泥煤矸石基固废胶凝材料相应龄期抗压强度"

图4

不同养护龄期净浆XRD衍射图谱分析"

图5

不同养护龄期水化样的TG-DSC分析图注：S1-3 d表示S1样品3 d水化样的结果，其他依此类推"

图6

不同养护龄期水化样的红外图谱注：S1-3 d表示S1样品3 d水化样的结果，其他依此类推"

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[1] 张雷,郭利杰,李文臣. 基于铜镍冶炼渣制备充填胶凝材料试验研究[J]. 黄金科学技术, 2020, 28(5): 669 -677 .
[2] 张婷婷,周子钰,郭利杰,武震林,韩俊南. 矿物掺合料改性铜镍渣胶凝材料的性能研究[J]. 黄金科学技术, 2020, 28(5): 678 -687 .

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