Effects of key pollutants in Papermaking wastewater on Calcium removal in Fluidized Bed Crystallization Reactors

LI Fan; GE Qiang; ZHOU Xianbo; WANG Yujia; ZHU Congyun; LIU Hefang; LIU Guifang; LIU Kuanyong; YANG Shucheng

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Effects of key pollutants in Papermaking wastewater on Calcium removal in Fluidized Bed Crystallization Reactors

更新时间：2025-07-08

- Effects of key pollutants in Papermaking wastewater on Calcium removal in Fluidized Bed Crystallization Reactors
- Moren Journal (2025)
- 作者机构：
  
  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
- 作者简介：
- 基金信息：
- DOI：
  CLC： X703
- 稿件说明：
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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.
DOI：

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. DOI：

摘要

针对废纸造纸复杂水质对Ca

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

的配位作用，挥发性脂肪酸抑制Ca

的去除，当乙酸钠浓度为20 mmol·L

-1

时，Ca

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

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

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

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

。

Abstract

To investigate the influence of complex water quality in waste paper pulping on Ca

removal

this study systematically examined the effects of three key pollutants—Volatile fatty acids (VFAs)

cellulose

and lignin—on the Ca

removal performance of the fluidized bed crystallization reactor (FBCR). The crystallization rate of CaCO

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

resulted in the inhibition of Ca

removal by VFAs When

the molar concentration of sodium acetate was 20 mmol·L

-1

the Ca

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

crystallization as concentration increased. When the microcrystalline cellulose mass concentration was 100 mg·L

-1

the Ca

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

in the solution

lignin significantly inhibited the growth of CaCO

crystals on the seed crystal surface. At a mass concentration of 240 mg·L

-1

the Ca

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

关键词

Keywords

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