退浆废水预氧化-絮凝一体化处理及资源化技术

doi:10.13475/j.fzxb.20250201801

摘要/Abstract

摘要： 聚乙烯醇(PVA)的高聚合度、电中性和强分子内/间氢键,导致其难降解也难脱稳沉淀。为此,提出一种基于Fe²⁺/CaO₂体系的一体化“预氧化-絮凝沉淀”处理技术,利用CaO₂水解释放H₂O₂,在Fe²⁺催化下生成氧化活性物种,强化PVA的可絮凝性并通过生成的Fe³⁺和Ca²⁺实现高效絮凝沉淀。通过药剂Fe与Ca的量比、反应pH值及处理时间等关键影响因素的调控,结合X射线光电子能谱、扫描电子显微镜等表征技术手段,对Fe²⁺/CaO₂体系处理含PVA退浆废水的效能、机制以及污泥资源化潜力进行研究。结果表明:Fe²⁺投加量为20 mmol/L、CaO₂投加量为2 mmol/L时,对于PVA质量浓度为0.5 ~ 2 g/L的退浆废水,其PVA和COD去除率分别可达97.1%和92.2%以上,且对含有改性淀粉等其它高聚物的实际退浆废水COD去除率也可达90%以上;处理过程中产生的污泥富含铁有机络合物及铁氧体,具有良好的吸附和催化性能,投加氧化剂30 min内对10 mg/L活性黑5模拟废水的去除率可达94.29%。

关键词: 退浆废水, 聚乙烯醇, Fe²⁺/CaO₂体系, 废水一体化处理, 预氧化, 絮凝沉淀, 污泥资源化

Abstract:

Objective In China, over 20% of polyvinyl alcohol (PVA) is utilized as a sizing reagent in the textile industry, with virtually all of it being discharged into wastewater during the desizing process in fabric printing and dyeing. Traditional PVA wastewater treatment methods face significant challenges due to PVA's high degree of polymerization, electrical neutrality, and strong intramolecular/intermolecular hydrogen bonds, which collectively impede degradation and precipitation. These characteristics typically necessitate substantial chemical inputs and complex treatment processes. Therefore, developing an integrated technology that combines pre-oxidation and flocculation processes is particularly crucial for efficient PVA wastewater treatment.

Method A "pre-oxidation flocculation precipitation" technology based on Fe²⁺/CaO₂ was developed. The system releases H₂O₂ through CaO₂ hydrolysis, generates oxidative species under Fe²⁺ catalysis, enhances PVA flocculability, and achieves precipitation via Fe³⁺ and Ca²⁺ ions. Effects of reagent dosage, pH value, initial PVA concentration, and reaction time were investigated. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques were used to analyze precipitates for mechanism elucidation. The sludge was evaluated as an adsorbent and catalyst for Reactive Black 5 degradation.

Results The integrated treatment of PVA technology has been successfully achieved. The optimal conditions were determined to be 20 mmol/L Fe²⁺ and 2 mmol/L CaO₂, with a pH value of 3 for the pre-oxidation stage, pH value of 10 for the flocculation for sedimentation stage, and a pre-oxidation time of 60 minutes. When treating PVA within a concentration range of 0.5-2 g/L, the removal rates for PVA and chemical oxygen demand (COD) reached over 97.1% and 92.2%. The process also demonstrated effective treatment of actual desizing wastewater containing modified starch, achieving over 90% removal efficiency. XPS C1s spectra showed an increase in C—O bond proportion after treatment, with O—C═O bonds shifting to higher binding energy (289.3 eV) and the emergence of a new ketone (C═O) peak at 288.1 eV, indicating PVA chain breakage and oxidation to form oxygen-containing groups that improved flocculation. SEM revealed that precipitates consisted of irregularly stacked nanoparticles with compact structures, while EDS mapping showed Fe and Ca atomic percentages of 24.65% and 75.35%, respectively. TEM images displayed typical amorphous flocculent structures with localized lattice fringes, confirming the formation of CaFe₅O₅ ferrite complexes. Additionally, the integrated treatment technology produces sludge containing a significant amount of iron/calcium organic complexes and ferrites. This sludge can be repurposed for the treatment of difficult-to-degrade pollutants in wastewater. Specifically, when 0.10 g of sludge was added to 100 mL of wastewater containing 10 mg/L of Reactive Black 5, a removal rate exceeding 94.3% was achieved after 30 min.

Conclusion This study developed an Fe²⁺/CaO₂ system for treating PVA-containing desizing wastewater and investigated the resource utilization of generated sludge. The system functions by producing H₂O₂ through CaO₂ hydrolysis, generating oxidative species under Fe²⁺ catalysis, while Fe³⁺ and Ca²⁺ ions act as flocculants. Optimal conditions (20 mmol/L Fe²⁺, 2 mmol/L CaO₂, pH value 3 for pre-oxidation, pH value 10 for flocculation, 60 min reaction time) achieved removal efficiencies exceeding 97.1% for PVA and 92.2% for COD in 0.5-2 g/L PVA concentrations. The resulting sludge, rich in iron/calcium-organic complexes and ferrites (CaFe₅O₇), demonstrated exceptional value for treating recalcitrant pollutants, achieving 94.29% removal of Reactive Black 5 within 30 min.

Key words: desizing wastewater, polyvinyl alcohol, Fe²⁺/CaO₂ system, integrated wastewater treatment, pre-oxidation, flocculation precipitation, sludge utilization

中图分类号:

X703.1

沈忱思, 王欣悦, 李方. 退浆废水预氧化-絮凝一体化处理及资源化技术[J]. 纺织学报, 2025, 46(08): 173-182.

SHEN Chensi, WANG Xinyue, LI Fang. Integrated treatment and resource recovery technology of desizing wastewater through pre-oxidation and flocculation[J]. Journal of Textile Research, 2025, 46(08): 173-182.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20250201801

http://www.fzxb.org.cn/CN/Y2025/V46/I08/173

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