Impact of Characteristic Pollutants in Waste Paper Pulping Wastewater on Calcium Removal by Fluidized Bed Crystallization Reactor

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

doi:10.7652/xjtuxb202602013

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Impact of Characteristic Pollutants in Waste Paper Pulping Wastewater on Calcium Removal by Fluidized Bed Crystallization Reactor

Special Topic Pollution Control and Resource Utilization in the "Dual Carbon" Context | 更新时间：2026-02-09

- Impact of Characteristic Pollutants in Waste Paper Pulping Wastewater on Calcium Removal by Fluidized Bed Crystallization Reactor
- Journal of Xi'an Jiaotong University Vol. 60, Issue 2, Pages: 136-146(2026)
- 作者机构：
  
  西安交通大学能源与动力工程学院，710049，西安
  中国轻工业长沙工程有限公司，410114，长沙
  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
  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：10.7652/xjtuxb202602013
  CLC： X703
- Received：30 May 2025，
  
  Published：10 February 2026
- 稿件说明：
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LI Fan, GE Qiang, ZHOU Xianbo, et al. Impact of Characteristic Pollutants in Waste Paper Pulping Wastewater on Calcium Removal by Fluidized Bed Crystallization Reactor[J]. Journal of Xi'an Jiaotong University, 2026, 60(2): 136-146.
DOI：

LI Fan, GE Qiang, ZHOU Xianbo, et al. Impact of Characteristic Pollutants in Waste Paper Pulping Wastewater on Calcium Removal by Fluidized Bed Crystallization Reactor[J]. Journal of Xi'an Jiaotong University, 2026, 60(2): 136-146. DOI： 10.7652/xjtuxb202602013.

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，采用能谱仪、红外光谱和热质量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，当乙酸钠的浓度为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，当微晶纤维素的质量浓度为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38.0%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

The influence of complex water quality in waste paper pulping on Ca

removal was systematically investigated，focusing on the effects of three characteristic pollutants—volatile fatty acids，cellulose，and lignin—on the calcium removal performance of a fluidized bed crystallization reactor（FBCR）.The crystallization rate of calcium carbonate in the presence of these pollutants was measured using the pH-stat method，and spent seed crystals were characterized by energy dispersive spectroscopy，infrared spectroscopy，and thermogravimetric analysis to explore the underlying mechanisms.The results show that volatile fatty acids inhibit Ca

removal due to competitive adsorption of acetate ions on the seed crystal surface and their complexation with Ca

.When sodium acetate concentration reached 20 mmol·L

-1

，the Ca

removal rate decreased from 41.3% to 24.6%.Microcrystalline cellulose interacted differently w

ith seed crystal surfaces at varying mass concentrations，leading to a concentration-dependent effect on calcium carbonate crystallization：promotion at lower levels and inhibition at higher levels.At a microcrystalline cellulose concentration of 100 mg·L

-1

，the Ca

removal rate reached a maximum of 56.8%.Lignin significantly inhibited calcium carbonate growth on seed crystals due to chelation of active surface sites and complexation with free Ca

in solution.At a lignin concentration of 240 mg·L

-1

，the Ca

removal rate dropped from 38.0% to 13.0%.This study clarifies the complex mechanisms by which characteristic pollutants influence the FBCR calcium removal process. To achieve improved calcium removal，it is recommended that pretreated wastewater entering the FBCR contain volatile fatty acids below 2.5 mmol·L

-1

，cellulose below 200 mg·L

-1

，and lignin below 15 mg·L

-1

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Keywords

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