硅酸盐通报 ›› 2026, Vol. 45 ›› Issue (5): 1671-1681.DOI: 10.16552/j.cnki.issn1001-1625.2025.1025
任骏1(
), 晏云潇1, 李苗源2, 田镇赫3, 赵立兴4, 王大富1(
)
收稿日期:2025-10-22
修订日期:2025-12-09
出版日期:2026-05-15
发布日期:2026-06-10
通信作者:
王大富,博士,讲师。E-mail:wangdafu92@163.com作者简介:任 骏(1986—),男,博士,教授。主要从事水泥基材料的研究。E-mail:renjunking@aliyun.com
基金资助:
REN Jun1(
), YAN Yunxiao1, LI Miaoyuan2, TIAN Zhenhe3, ZHAO Lixing4, WANG Dafu1(
)
Received:2025-10-22
Revised:2025-12-09
Published:2026-05-15
Online:2026-06-10
摘要:
本文旨在探究不同改性方式处理的磷石膏对石膏矿渣水泥(SSC)性能的影响,阐明抗压强度提升机理及细菌在水化过程中的演化规律。在确定SSC最佳配合比(m(矿渣)∶m(磷石膏)∶m(水泥)=0.84∶0.13∶0.03)的基础上,系统研究了水洗、碱洗、微生物处理及协同处理对SSC性能的影响。通过标准稠度用水量、凝结时间及抗压强度测试,结合XRD与SEM分析水化产物和孔结构的演变。结果表明:微生物协同碱洗处理效果最优,与对照组相比,微生物处理使标准稠度用水量增加,终凝时间较处理前缩短30%左右,3 d抗压强度提升了298%~349%,28 d仍提升了40%~58%。微生物处理通过去除磷、氟杂质,提高水化体系pH值,借助细菌细胞壁提供成核位点和生物矿化等作用,促进C-S-H、钙矾石和碳酸钙等水化产物生成,优化孔结构。
中图分类号:
任骏, 晏云潇, 李苗源, 田镇赫, 赵立兴, 王大富. 微生物改性磷石膏对石膏矿渣水泥性能的影响[J]. 硅酸盐通报, 2026, 45(5): 1671-1681.
REN Jun, YAN Yunxiao, LI Miaoyuan, TIAN Zhenhe, ZHAO Lixing, WANG Dafu. Effect of Microbial-Modified Phosphogypsum on Properties of Supersulfated Cement[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(5): 1671-1681.
| Material | Mass fraction/% | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| Na2O | MgO | Al2O3 | SiO2 | P2O5 | CaO | TiO2 | Fe2O3 | SO3 | K2O | F | |
| RPG | 0.11 | 0.11 | 0.36 | 9.86 | 1.18 | 31.13 | 0.06 | 0.06 | 53.05 | — | 0.83 |
| Slag | 0.64 | 7.79 | 14.68 | 33.17 | — | 35.52 | — | 0.48 | 2.71 | 0.58 | — |
| Cement clinker | 0.40 | 3.21 | 5.21 | 21.06 | — | 63.46 | — | 3.82 | 0.58 | 0.65 | — |
表1 原材料的化学组成
Table 1 Chemical composition of raw materials
| Material | Mass fraction/% | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| Na2O | MgO | Al2O3 | SiO2 | P2O5 | CaO | TiO2 | Fe2O3 | SO3 | K2O | F | |
| RPG | 0.11 | 0.11 | 0.36 | 9.86 | 1.18 | 31.13 | 0.06 | 0.06 | 53.05 | — | 0.83 |
| Slag | 0.64 | 7.79 | 14.68 | 33.17 | — | 35.52 | — | 0.48 | 2.71 | 0.58 | — |
| Cement clinker | 0.40 | 3.21 | 5.21 | 21.06 | — | 63.46 | — | 3.82 | 0.58 | 0.65 | — |
| Code | RPG content/g | H2O content/mL | 0.5% NaOH content/mL | Washing liquid content/mL | Bacterial concentration content/(CFU·mL-1) |
|---|---|---|---|---|---|
| RPG | 1 | ||||
| WPG | 1 | 3 | |||
| ARPG | 1 | 3 | |||
| RPG-B1 | 1 | 3 | 3 | 3.3×106 | |
| WPG-B1 | 1 | 3 | 3 | 3.3×106 | |
| ARPG-B1 | 1 | 3 | 3 | 3.3×106 |
表2 微生物处理方案
Table 2 Microbial treatment scheme
| Code | RPG content/g | H2O content/mL | 0.5% NaOH content/mL | Washing liquid content/mL | Bacterial concentration content/(CFU·mL-1) |
|---|---|---|---|---|---|
| RPG | 1 | ||||
| WPG | 1 | 3 | |||
| ARPG | 1 | 3 | |||
| RPG-B1 | 1 | 3 | 3 | 3.3×106 | |
| WPG-B1 | 1 | 3 | 3 | 3.3×106 | |
| ARPG-B1 | 1 | 3 | 3 | 3.3×106 |
| Code | Slag | Phosphogypsum | Cement clinker | Mixing liquid |
|---|---|---|---|---|
| RPGC | 0.84 | 0.13 RPG | 0.03 | 0.33 |
| WPGC | 0.84 | 0.13 WPG | 0.03 | 0.33 |
| ARPGC | 0.84 | 0.13 ARPG | 0.03 | 0.33 |
| RPGC-B1 | 0.84 | 0.13 RPG-B1 | 0.03 | 0.33 |
| WPGC-B1 | 0.84 | 0.13 WPG-B1 | 0.03 | 0.33 |
| ARPGC-B1 | 0.84 | 0.13 ARPG-B1 | 0.03 | 0.33 |
表3 石膏矿渣水泥配合比
Table 3 Mix ratio of SSC
| Code | Slag | Phosphogypsum | Cement clinker | Mixing liquid |
|---|---|---|---|---|
| RPGC | 0.84 | 0.13 RPG | 0.03 | 0.33 |
| WPGC | 0.84 | 0.13 WPG | 0.03 | 0.33 |
| ARPGC | 0.84 | 0.13 ARPG | 0.03 | 0.33 |
| RPGC-B1 | 0.84 | 0.13 RPG-B1 | 0.03 | 0.33 |
| WPGC-B1 | 0.84 | 0.13 WPG-B1 | 0.03 | 0.33 |
| ARPGC-B1 | 0.84 | 0.13 ARPG-B1 | 0.03 | 0.33 |
图15 强度提升机理示意图:(a)细菌矿化生成MICP凝胶;(b)细胞壁提供成核位点;(c)细菌裂解提供成核点
Fig.15 Schematic diagram of mechanism of strength enhancement: (a) bacterial mineralization produces MICP gel;(b) cell wall provides nucleation sites; (c) bacterial lysis provides nucleation sites
| [1] | 孙正宁, 周 健, 慕 儒, 等. 新型超硫酸盐水泥水化硬化机理[J]. 硅酸盐通报, 2019, 38(8): 2362-2368. |
| SUN Z N, ZHOU J, MU R, et al. Hydration and hardening mechanisms of newly developed supersulfated cement[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(8): 2362-2368 (in Chinese). | |
| [2] | WU Q Y, XUE Q Z, YU Z Q. Research status of super sulfate cement[J]. Journal of Cleaner Production, 2021, 294: 126228. |
| [3] | ZOU M, HE Z Y, XIA Y H, et al. High-volume phosphogypsum cement stabilized road base: preparation methods and strength formation mechanism[J]. Materials, 2024, 17(24): 6201. |
| [4] | WU F H, REN Y, QU G F, et al. Utilization path of bulk industrial solid waste: a review on the multi-directional resource utilization path of phosphogypsum[J]. Journal of Environmental Management, 2022, 313: 114957. |
| [5] | 宋维相, 朱国飞, 徐韦洪, 等. 一种磷石膏基耐水路缘石及其制备方法: CN114685134A[P]. 2022-07-01. |
| SONG W X, ZHU G F, XU W H, et al. A phosphogypsum-based water-resistant curbstone and its preparation method: CN114685134A[P]. 2022-07-01 (in Chinese). | |
| [6] | 张兆锐, 单俊鸿, 王荣荣, 等. 磷建筑石膏基无砂自流平砂浆的制备与性能研究[J]. 硅酸盐通报, 2024, 43(4): 1455-1462. |
| ZHANG Z R, SHAN J H, WANG R R, et al. Preparation and performance of phosphorus building gypsum-based sandless self-leveling mortar[J]. Bulletin of the Chinese Ceramic Society, 2024, 43(4): 1455-1462 (in Chinese). | |
| [7] | 周 武, 李 杨, 冯伟光, 等. 磷石膏的综合利用及其在建筑材料领域的应用研究进展[J]. 硅酸盐通报, 2024, 43(2): 534-542. |
| ZHOU W, LI Y, FENG W G, et al. Research progress on comprehensive utilization of phosphogypsum and its application in the field of building materials[J]. Bulletin of the Chinese Ceramic Society, 2024, 43(2): 534-542 (in Chinese). | |
| [8] | ANDRADE NETO J S, BERSCH J D, SILVA T S M, et al. Influence of phosphogypsum purification with lime on the properties of cementitious matrices with and without plasticizer[J]. Construction and Building Materials, 2021, 299: 123935. |
| [9] | LIU S H, WANG L. Investigation on strength and pore structure of supersulfated cement paste[J]. Materials Science, 2018, 24(3): 319-326. |
| [10] | 康雪儿, 黄 赟, 刘 刚, 等. 可溶性磷对大掺量磷石膏胶凝材料水化过程的影响[J]. 硅酸盐通报, 2024, 43(9): 3303-3312. |
| KANG X E, HUANG Y, LIU G, et al. Effect of soluble phosphorus on hydration process of high content phosphogypsum cementitious materials[J]. Bulletin of the Chinese Ceramic Society, 2024, 43(9): 3303-3312 (in Chinese). | |
| [11] | 李义胜, 吕 伟, 吴赤球, 等. 高掺量磷石膏胶凝材料硬化体制备及其性能调节[J]. 硅酸盐通报, 2025, 44(8): 2944-2954. |
| LI Y S, LYU W, WU C Q, et al. Hardened body preparation and performance adjustment of high content phosphogypsum cementitious materials[J]. Bulletin of the Chinese Ceramic Society, 2025, 44(8): 2944-2954 (in Chinese). | |
| [12] | XIANG J C, QIU J P, ZHENG P K, et al. Usage of biowashing to remove impurities and heavy metals in raw phosphogypsum and calcined phosphogypsum for cement paste preparation[J]. Chemical Engineering Journal, 2023, 451: 138594. |
| [13] | ANAND K, GOYAL S, REDDY M S. Long-term viable SF immobilized bacterial cells as sustainable solution for crack healing in concrete[J]. Structures, 2022, 43: 1342-1355. |
| [14] | DHAMI N K, MUKHERJEE A, REDDY M S. Micrographical, minerological and nano-mechanical characterisation of microbial carbonates from urease and carbonic anhydrase producing bacteria[J]. Ecological Engineering, 2016, 94: 443-454. |
| [15] | WANG Z, SU J F, HU X F, et al. Isolation of biosynthetic crystals by microbially induced calcium carbonate precipitation and their utilization for fluoride removal from groundwater[J]. Journal of Hazardous Materials, 2021, 406: 124748. |
| [16] | LIU S H, FANG P P, REN J, et al. Application of lime neutralised phosphogypsum in supersulfated cement[J]. Journal of Cleaner Production, 2020, 272: 122660. |
| [17] | SHI Y, CHEN H Y, WANG J, et al. Preliminary investigation on the pozzolanic activity of superfine steel slag[J]. Construction and Building Materials, 2015, 82: 227-234. |
| [18] | 裴 迪, 刘志明, 胡碧茹, 等. 巴氏芽孢杆菌矿化作用机理及应用研究进展[J]. 生物化学与生物物理进展, 2020, 47(6): 467-482. |
| PEI D, LIU Z M, HU B R, et al. Progress on mineralization mechanism and application research of sporosarcina pasteurii[J]. Progress in Biochemistry and Biophysics, 2020, 47(6): 467-482 (in Chinese). | |
| [19] | DING S, SHUI Z H, CHEN W, et al. Properties of supersulphated phosphogysumslag cement (SSC) concrete[J]. Journal of Wuhan University of Technology-Mater Sci Ed, 2014, 29(1): 109-113. |
| [20] | ERDEM E, ÖLMEZ H. The mechanical properties of supersulphated cement containing phosphogypsum[J]. Cement and Concrete Research, 1993, 23(1): 115-121. |
| [21] | CUI Y, WANG H, WANG D Q, et al. Effects of Ca(OH)2 on the early hydration, macro-performance and environmental risks of the calcined phosphogypsum[J]. Construction and Building Materials, 2022, 324: 126590. |
| [22] | 陈 宇, 季军荣, 周 洲, 等. 超硫酸盐水泥早期强度影响因素及提高途径[J]. 硅酸盐通报, 2021, 40(5): 1413-1419. |
| CHEN Y, JI J R, ZHOU Z, et al. Influencing factors and enhancement methods of early strength of supersulfated cement[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(5): 1413-1419 (in Chinese). | |
| [23] | BISWAS M, MAJUMDAR S, CHOWDHURY T, et al. Bioremediase a unique protein from a novel bacterium BKH1, ushering a new hope in concrete technology[J]. Enzyme and Microbial Technology, 2010, 46(7): 581-587. |
| [24] | 林宗寿, 黄 赟. 碱度对磷石膏基免煅烧水泥性能的影响[J]. 武汉理工大学学报, 2009, 31(4): 132-135. |
| LIN Z S, HUANG Y. Effect of alkalinity on phosphogypsum-base non-calcined cement[J]. Journal of Wuhan University of Technology, 2009, 31(4): 132-135 (in Chinese). | |
| [25] | XIAO X, LI J, YANG S, et al. Effect of phosphorus impurities on sulfoaluminate cement-modified gypsum-based self-leveling mortar and improvement method[J]. Construction and Building Materials, 442. |
| [26] | NAIN N, SURABHI R, YATHISH N V, et al. Enhancement in strength parameters of concrete by application of Bacillus bacteria[J]. Construction and Building Materials, 2019, 202: 904-908. |
| [27] | 黄浩然, 廖宜顺, 江国喜, 等. 磷建筑石膏对硫铝酸盐水泥熟料收缩特性的影响[J]. 建筑材料学报, 2022, 25(9): 893-900. |
| HUANG H R, LIAO Y S, JIANG G X, et al. Effect of phosphorous calcined gypsum on shrinkage characteristics of calcium sulfoaluminate cement clinker[J]. Journal of Building Materials, 2022, 25(9): 893-900 (in Chinese). | |
| [28] | SAJEDI F, RAZAK H A. The effect of chemical activators on early strength of ordinary Portland cement-slag mortars[J]. Construction and Building Materials, 2010, 24(10): 1944-1951. |
| [29] | LIAO Y S, YAO J X, DENG F, et al. Hydration behavior and strength development of supersulfated cement prepared by calcined phosphogypsum and slaked lime[J]. Journal of Building Engineering, 2023, 80: 108075. |
| [30] | MUN K J, HYOUNG W K, LEE C W, et al. Basic properties of non-sintering cement using phosphogypsum and waste lime as activator[J]. Construction and Building Materials, 2007, 21(6): 1342-1350. |
| [31] | ZHAO J H, WANG D M, YAN P Y. Design and experimental study of a ternary blended cement containing high volume steel slag and blast-furnace slag based on Fuller distribution model[J]. Construction and Building Materials, 2017, 140: 248-256. |
| [32] | 赵德强, 张昺榴, 沈卫国, 等. 磷石膏对微膨胀水泥孔隙液及水化产物的影响[J]. 建筑材料学报, 2020, 23(6): 1273-1281. |
| ZHAO D Q, ZHANG B L, SHEN W G, et al. Effect of phosphogypsum on pore solution and hydration products of slight-expansive cement[J]. Journal of Building Materials, 2020, 23(6): 1273-1281 (in Chinese). | |
| [33] | 吴开振, 李 瑞, 李育彪, 等. 磷石膏常压制备二水硫酸钙晶须机理研究[J]. 硅酸盐通报, 2024, 43(12): 4461-4470. |
| WU K Z, LI R, LI Y B, et al. Mechanism of preparing calcium sulfate dihydrate whiskers from phosphogypsum under atmospheric[J]. Bulletin of the Chinese Ceramic Society, 2024, 43(12): 4461-4470 (in Chinese). | |
| [34] | BIZZOZERO J, SCRIVENER K L. Limestone reaction in calcium aluminate cement-calcium sulfate systems[J]. Cement and Concrete Research, 2015, 76: 159-169. |
| [35] | HARGIS C W, TELESCA A, MONTEIRO P J M. Calcium sulfoaluminate (ye’elimite) hydration in the presence of gypsum, calcite, and vaterite[J]. Cement and Concrete Research, 2014, 65: 15-20. |
| [36] | SINGH M, GARG M. Making of anhydrite cement from waste gypsum[J]. Cement and Concrete Research, 2000, 30(4): 571-577. |
| [37] | WANG Q, YANG J W, YAN P Y. Influence of initial alkalinity on the hydration of steel slag[J]. Science China Technological Sciences, 2012, 55(12): 3378-3387. |
| [38] | DE OLIVEIRA A M, OLIVEIRA A P, VIEIRA J D, et al. Study of the development of hydration of ternary cement pastes using X-ray computed microtomography, XRD-Rietveld method, TG/DTG, DSC, calorimetry and FTIR techniques[J]. Journal of Building Engineering, 2023, 64: 105616. |
| [39] | WANG J, BECKER U. Structure and carbonate orientation of vaterite (CaCO3)[J]. American Mineralogist, 2009, 94(2/3): 380-386. |
| [40] | RAMSTEDT M, LEONE L, PERSSON P, et al. Cell wall composition of Bacillus subtilis changes as a function of pH and Zn2+ exposure: insights from cryo-XPS measurements[J]. Langmuir, 2014, 30(15): 4367-4374. |
| [41] | VIJAY K, MURMU M, DEO S V. Bacteria based self healing concrete: a review[J]. Construction and Building Materials, 2017, 152: 1008-1014. |
| [42] | SANTHOSH K. RAMACHANDRAN V R, SOOKIE S B. Remediation of concrete using microorganisms[J]. ACI Materials Journal, 2001, 98(1): 3-5. |
| [1] | 张蕴哲, 陈敏孙, 王洪磊, 周新贵, 余金山. 陶瓷基复合材料的激光烧蚀行为及发展趋势[J]. 硅酸盐通报, 2026, 45(5): 1727-1740. |
| [2] | 宿辉, 张林康, 白延杰, 吕佳鑫, 张鑫, 南博文, 皮浩军. FeSO4·H2O协同DTPA改性氯氧镁水泥的作用机理[J]. 硅酸盐通报, 2026, 45(5): 1491-1500. |
| [3] | 任骏, 庹珉泰, 毛江鸿, 陈昌雨, 曾根生, 刘翔云, 李钟. 冷冻法制备PVA-ECC增强增韧单元的力学性能试验研究[J]. 硅酸盐通报, 2026, 45(5): 1513-1526. |
| [4] | 孔硕, 耿永娟, 刘彦岑, 李绍纯. 二氧化硅改性环氧涂层的制备及其对钢筋的防护性能研究[J]. 硅酸盐通报, 2026, 45(5): 1580-1590. |
| [5] | 李有, 王雪琪, 赵玉霞, 郑木莲, 黄洁, 卢川, 李宜锋. 骨架密实型水泥稳定碎石-钢渣混合料收缩补偿机理与性能研究[J]. 硅酸盐通报, 2026, 45(5): 1823-1837. |
| [6] | 谢祥兵, 贾亚鹏, 李程, 侯博研, 张雁翔, 万赈民, 邵景干. 微纳米气泡水对水泥稳定碎石物理力学性能影响及机理研究[J]. 硅酸盐通报, 2026, 45(5): 1838-1850. |
| [7] | 杨泰华, 王公略, 罗旭峰, 周哲, 屠名, 刘滨, 刘学伟. 纳米材料与纤维改性洞渣混凝土力学性能研究[J]. 硅酸盐通报, 2026, 45(5): 1559-1570. |
| [8] | 杨雪滢, 王开元, 王耀城, 占宝剑, 邢锋. 自然风化作用下碳化养护水泥基材料的力学性能劣化机制[J]. 硅酸盐通报, 2026, 45(4): 1132-1141. |
| [9] | 洪川海, 梁瑞庆, 梁振升, 张伯涛, 唐雪梅, 阮国威, 林嘉祥. 海水珊瑚砂粉工程水泥基复合材料高温暴露后的性能研究[J]. 硅酸盐通报, 2026, 45(4): 1151-1159. |
| [10] | 李顺凯, 陈荣辉, 董勋, 窦华康, 孙凤品. 促凝早强剂对喷射混凝土性能的影响[J]. 硅酸盐通报, 2026, 45(4): 1184-1192. |
| [11] | 朱世栋, 陈纨年, 李忠慧, 张宇, 张云升, 李王鑫. 振动搅拌对粉煤灰混凝土性能与碳排放的影响[J]. 硅酸盐通报, 2026, 45(4): 1193-1207. |
| [12] | 林明智, 陈旸, 陈波. 浅水海砂骨料矿物特征及物理力学性能研究[J]. 硅酸盐通报, 2026, 45(4): 1240-1247. |
| [13] | 邹仁华, 胡小龙, 冯泽平, 牛高辉, 邱继生. 煤矸石混合砂混凝土宏观力学性能及微观机理研究[J]. 硅酸盐通报, 2026, 45(4): 1266-1281. |
| [14] | 郭阳光, 秦拥军, 罗玲, 谌君诚, 李琦, 程昊. 硅灰-玻璃纤维全再生粗骨料混凝土力学性能研究[J]. 硅酸盐通报, 2026, 45(4): 1296-1303. |
| [15] | 谌君诚, 罗玲, 秦拥军, 郭阳光, 李琦, 程昊. 硅灰-聚甲醛纤维再生水工混凝土力学和耐水性能研究[J]. 硅酸盐通报, 2026, 45(4): 1304-1314. |
| 阅读次数 | ||||||
|
全文 |
|
|||||
|
摘要 |
|
|||||