1.西安交通大学能源与动力工程学院,710049,西安
2.中国轻工业长沙工程有限公司,410114,长沙
3.制浆造纸污水循环回用与超低排放技术湖南省工程研究中心,410114,长沙
4.贵州鹏昇(集团)纸业有限责任公司,552401,贵州黔西南布依族苗族自治州
移动端阅览
李凡, 葛强, 周贤波, 等. 废纸造纸废水特征污染物对流化床结晶反应器除钙的影响[J/OL]. 默认刊物名称, 2025.
LI Fan, GE Qiang, ZHOU Xianbo, et al. Effects of key pollutants in Papermaking wastewater on Calcium removal in Fluidized Bed Crystallization Reactors[J/OL]. Moren Journal, 2025.
针对废纸造纸复杂水质对Ca
2+
去除的影响,系统研究了挥发性脂肪酸、纤维素、木质素3类特征污染物对流化床结晶反应器(FBCR)除钙性能的影响。通过pH-stat法测定污染物存在时碳酸钙的结晶速率,采用X射线能谱、红外光谱和热重分析对使用后晶种进行表征,探究其影响机制。结果表明:由于乙酸根离子在晶种表面的竞争性吸附及其与Ca
2+
的配位作用,挥发性脂肪酸抑制Ca
2+
的去除,当乙酸钠浓度为20 mmol·L
-1
时,Ca
2+
去除率由41.3%降至24.6%;微晶纤维素在不同质量浓度下与晶种表面的相互作用不同,所以对碳酸钙结晶的影响随质量浓度增加先促进后抑制,当微晶纤维素质量浓度为100 mg·L
-1
时,Ca
2+
去除率达到最大值56.8%;由于晶种表面活性位点的螯合以及溶液中游离Ca
2+
的配位作用,木质素显著抑制碳酸钙在晶种表面的生长,当木质素质量浓度为240 mg·L
-1
时,Ca
2+
去除率从38%下降到13.0%。该研究明晰了特征污染物对FBCR除钙过程的复杂机制,为实现更好的除钙效果,建议经预处理进入FBCR的废水中挥发性脂肪酸浓度小于2.5 mmol·L
-1
、纤维素质量浓度小于200 mg·L
-1
、木质素质量浓度小于15 mg·L
-1
。
To investigate the influence of complex water quality in waste paper pulping on Ca
2+
removal
this study systematically examined the effects of three key pollutants—Volatile fatty acids (VFAs)
cellulose
and lignin—on the Ca
2+
removal performance of the fluidized bed crystallization reactor (FBCR). The crystallization rate of CaCO
3
under these pollutant conditions was analyzed using the pH-stat method. Furthermore
spent seed crystals were characterized by X-ray energy spectroscopy
Fourier-transform infrared spectroscopy
and thermogravimetric analysis to elucidate the underlying mechanisms. The results showed that the competitive adsorption of acetate ions on the seed surface and their coordination with Ca
2+
resulted in the inhibition of Ca
2+
removal by VFAs When
the molar concentration of sodium acetate was 20 mmol·L
-1
the Ca
2+
removal rate decreased from 41.3% to 24.6%. In contrast
depending on its mass concentration
microcrystalline cellulose interacted differently with the crystal seed surface
initially promoting then inhibiting CaCO
3
crystallization as concentration increased. When the microcrystalline cellulose mass concentration was 100 mg·L
-1
the Ca
2+
removal rate reached a maximum of 56.8%. Moreover
due to the chelation of active sites on the seed crystal surface and the coordination of free Ca
2+
in the solution
lignin significantly inhibited the growth of CaCO
3
crystals on the seed crystal surface. At a mass concentration of 240 mg·L
-1
the Ca
2+
removal rate decreased from 38% to 13.0%. Therefore
in order to achieve better calcium removal efficiency
it is recommended that the molar concentration of volatile fatty acids in wastewater entering FBCR after pretreatment be less than 2.5 mmol·L
-1
the cellulose mass concentration be less than 200 mg·L
-1
and the lignin mass concentration be less than 15 mg·L
-1
.
2023中国造纸工业年度报告 [J ] . 中华纸业 , 2024 , 45 ( 05 ): 15 - 24 .
2023 China Paper Industry Annual Report [J ] . China Pulp & Paper Industry , 2024 , 45 ( 05 ): 15 - 24 .
崔明启 , 张弛 , 陈逸帆 , 等 . 造纸废水曝气池中钙的去除及迁移转化规律研究 [J ] . 环境科学学报 , 2020 , 40 ( 06 ): 2128 - 35 .
CUI M , ZHANG C , CHEN Y , et al . Study on the removal, migration and transformation of calcium in the aeration tank of paper mill wastewater [J ] . Acta Scientiae Circumstantiae , 2020 , 40 ( 06 ): 2128 - 35 .
NIE X , WANG Z , WAN J , et al . Competition between homogeneous and heterogeneous crystallization of CaCO 3 during water softening [J ] . Water Research , 2024 , 250 : 121061 .
GUI L , YANG H , HUANG H , et al . Liquid solid fluidized bed crystallization granulation technology: Development, applications, properties, and prospects [J ] . Journal of Water Process Engineering , 2022 , 45 : 102513 .
贺延龄 . 废纸制浆造纸废水的封闭循环和零排放 [J ] . 中华纸业 , 2001 , ( 02 ): 13 - 6 .
HE Y . The closed circulation and zero discharge of waste water of pulpand paper making from waste paper [J ] . China Pulp & Paper Industry , 2001 , ( 02 ): 13 - 6
REDDY M M , HOCH A R . Calcite Crystal Growth Rate Inhibition by Polycarboxylic Acids [J ] . Journal of Colloid and Interface Science , 2001 , 235 ( 2 ): 365 - 70 .
TAI C Y , HON M J , CHEN P-C . A comparison of growth behavior between CaCO3 and CaF2 crystals in a constant-composition environment [J ] . Journal of the Taiwan Institute of Chemical Engineers , 2011 , 42 ( 3 ): 435 - 40 .
宋清丝 . 废纸造纸废水复杂水质环境中条件下碳酸钙的诱导结晶研究 [D ] . 西安 : 西安交通大学 , 2024 : 19 - 46 .
SONG Q . Induced crystallization of calcium carbonate in complex water-quality constituentditions of paper recycling wastewater [D ] . Xi'an ; Xi'an Jiaotong University , 2024 : 19 - 46 .
SONG Q , GE Q , ZHOU X , et al . CaCO3 accumulation in the wastewater treatment system of a recycled paper mill with zero‐liquid discharge [J ] . Water Environment Research , 2025 , 97 ( 6 ).
环境保护部 . 制浆造纸工业污染防治可行技术指南 : HJ 2302—2018 [S ] . 北京 : 中国环境科学出版社 , 2018 .
Ministry of Environmental Protection . Guideline for Available Techniques of Pollution Prevention and Control for Pulp and Paper Industry : HJ 2302—2018 [S ] . Beijing : China Environmental Science Press , 2018 .
汪雨佳 . 基于流化床结晶反应器的废纸造纸废水除钙研究 [D ] . 西安 : 西安交通大学 , 2025 : 19 - 31 .
WANG Y . Study on Calcium Removal from Wastepaper Recyclinged Papermaking Wastewater Using a Fluidized Bed Crystallization Reactor [D ] . Xi'an ; Xi'an Jiaotong University , 2025 : 19 - 31 .
TAI C Y , CHIEN W C , CHEN C Y . Crystal growth kinetics of calcite in a dense fluidized-bed crystallizer [J ] . Aiche Journal , 1999 , 45 ( 8 ): 1605 - 14 .
贺延龄 . 废水的厌氧生物处理 [M ] . 废水的厌氧生物处理 , 1998 .
HE Y . Anaerobic biological treatment of wastewater [M ] . China Light Industry Press , 1998 .
HACHT B . Complex Formation of Acetic Acid with Ca(II) and Mg(II) Under Physiological Conditions [J ] . Journal of Solution Chemistry , 2008 , 37 ( 2 ): 155 - 63 .
陆洲 , 聂小保 , 余志 , 等 . 高硬水软化中Fe 3 O 4 诱导结晶对微晶形成的控制 [J ] . 环境工程学报 , 2021 , 15 ( 02 ): 563 - 71 .
LU Z , NIE X , XU Z , et al . Control of the microcrystal formation during high-hardness water softening with Fe 3 O 4 induced-crystallization [J ] . Chinese Journal of Environmental Engineering , 2021 , 15 ( 02 ): 563 - 71 .
孟浩江 , 张蕾 , 张祎 , 等 . 微晶纤维素基碳酸钙复合材料对Cd 2+ 和Pb 2+ 的捕集与回收研究 [J ] . 应用化工 , 2024 , 53 ( 04 ): 832 - 7 .
MENG H , ZHANG L , ZHANG Y , et al . Trapping and recovery of Pb 2+ and Cd 2+ by microcrystalline cellulose-based calcium carbonate composites [J ] . Applied Chemical Industry , 2024 , 53 ( 04 ): 832 - 7
ABUSHAMMALA H , MAO J . Impact of the Surface Properties of Cellulose Nanocrystals on the Crystallization Kinetics of Poly(Butylene Succinate) [J ] . Crystals , 2020 , 10 ( 3 ): 196 .
BRODIN F W , GREGERSEN Ø W , SYVERUD K . Cellulose nanofibrils: Challenges and possibilities as a paper additive or coating material – A review [J ] . Nordic Pulp & Paper Research Journal , 2014 , 29 ( 1 ): 156 - 66 .
张桐荣 , 宋立新 , 李明昊 , 等 . 木质素-Ca 2+ 络合物微粒的制备及其改性聚乙烯醇薄膜的研究 [J ] 塑料科技 . 2024 , 52 ( 02 ): 64 - 8 .
ZHANG T , SONG L , LI M , et al . Preparation of lignin-Ca 2+ complex microparticles and study on their modification of polyvinyl alcohol films [J ] . Plastics Science and Technology 2024 , 52 ( 02 ): 64 - 8 .
韩跃新 , 陈经华 , 王泽红 , 等 . 纳米碳酸钙表面改性研究 [J ] . 矿冶 , 2003 , ( 01 ): 48 - 51 .
HAN Y , CHEN J , WANG Z , et al . Study on surface modification of nanometer calcium carbonate [J ] . Mining and Metallurgy , 2003 , ( 01 ): 48 - 51 .
赵瑾 , 李彦军 , 成国祥 . 羟丙基甲基纤维素凝胶模板合成碳酸钙晶体 [J ] . 科学通报 , 2007 , ( 04 ): 394 - 8 .
ZHAO J , LI Y , CHENG G . Synthesis of calcium carbonate crystal using hydroxypropyl methyl cellulose as template [J ] . Chinese Science Bulletin , 2007 , ( 04 ): 394 - 8 .
DALAS E , KLEPETSANIS P G , KOUTSOUKOS P G . Calcium Carbonate Deposition on Cellulose [J ] . Journal of Colloid and Interface Science , 2000 , 224 ( 1 ): 56 - 62 .
MATAHWA H , RAMIAH V , SANDERSON R D . Calcium carbonate crystallization in the presence of modified polysaccharides and linear polymeric additives [J ] . Journal of Crystal Growth , 2008 , 310 ( 21 ): 4561 - 9 .
ZHANG F , YANG X , TIAN F . Calcium carbonate growth in the presence of water soluble cellulose ethers [J ] . Materials Science and Engineering: C , 2009 , 29 ( 8 ): 2530 - 8 .
SáENZ EZQUERRO C , LASPALAS M , GARCíA AZNAR J M , et al . Monitoring interactions through molecular dynamics simulations: effect of calcium carbonate on the mechanical properties of cellulose composites [J ] . Cellulose , 2023 , 30 ( 2 ): 705 - 26 .
ZHANG Y , CUI S , LIAO H , et al . Poly(butylene succinate)/cellulose composite monofilaments with microelastic response based on interfacial bonding [J ] . Carbohydrate Polymers , 2023 , 302 : 120387 .
LAVOINE N , DESLOGES I , DUFRESNE A , et al . Microfibrillated cellulose – Its barrier properties and applications in cellulosic materials: A review [J ] . Carbohydrate Polymers , 2012 , 90 ( 2 ): 735 - 64 .
竹文坤 , 罗学刚 , 贺攀 , 等 . 木质素对碳酸钙结晶行为的影响 [J ] . 林产化学与工业 , 2010 , 30 ( 06 ): 7 - 12 .
ZHU W , LUO X , HE P , et al . Effects of ligninon crystallization of calcium carconate [J ] . Chemistry and Industry of Forest Production , 2010 , 30 ( 06 ): 7 - 12 .
谢燕 , 曾祥钦 . 羧酸型磺化木质素的阻垢性能及机理研究 [J ] . 工业水处理 , 2006 , ( 05 ): 24 - 6 .
XIE Y , ZENG X . Research on the property and mechanism of scale inhibition of carboxylic lignosulfonate [J ] . Industrial Water Treatment , 2006 , ( 05 ): 24 - 6 .
LIU H-J , SUN D-Y , YANG L , et al . Pretreatment of enzymatic hydrolysis lignin based on deep eutectic solvent containing a reversibly-soluble base [J ] . International Journal of Biological Macromolecules , 2025 , 301 : 140452 .
PANG T , WANG G , SUI W , et al . Lignin-based support for metal catalysts: Synthetic strategies, performance boost, and application advances [J ] . Coordination Chemistry Reviews , 2025 , 528 : 216426 .
0
浏览量
3
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010802024621