某实际染整废水深度处理过程中无机组分与溶解性有机物的变化

宋铁红; 赵凯; 佟娟; 徐宇峰; 莫荣明; 莫东海; 夏建新; 魏源送

doi:10.7524/j.issn.0254-6108.2021112402

某实际染整废水深度处理过程中无机组分与溶解性有机物的变化

1.
吉林建筑大学，松辽流域水环境教育部重点实验室，长春，130118
2.
中国科学院生态环境研究中心环境模拟与污染控制国家重点联合实验室，北京，100085
3.
中国科学院生态环境研究中心水污染控制实验室，北京，100085
4.
中国科学院大学，北京，100049
5.
河北工程大学能源与环境工程学院，邯郸，056038
6.
浙江嘉名染整有限公司，嘉兴，314505

通讯作者: Tel: 13699271600, E-mail: hittj@ 163.com;

基金项目:
天津市重点研发计划项目（19YFSLQY00060）资助.

Variation of inorganic components and dissolved organic matter during advanced treatment of a full-scale dyeing wastewater treatment plant

1.
Key Laboratory of Water Environment in Songliao River Basin, Ministry of Education, Jilin Jianzhu University, Changchun, 130118, China
2.
State Key Joint Laboratory of Environmental Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China
3.
Laboratory of Water Pollution Control Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China
4.
University of Chinese Academy of Sciences, Beijing, 100049, China
5.
School of Energy and Environmental Engineering, Hebei University of Engineering, Handan，056038, China
6.
Zhejiang Charming Dyeing & Finishing CO., LTD, Jiaxing, 314505, China

Corresponding author: TONG Juan, hittj@163.com ;

Fund Project: the Key Research and Development Program of Tianjin（19YFSLQY00060）.

摘要: 近年来超滤（UF）-反渗透（RO）组合工艺逐渐在印染废水深度处理中得到推广应用，但目前对实际染整废水深度处理过程中无机与有机组分变化特征的研究仍有不足。研究考察了某实际染整废水的UF-RO深度处理工艺过程中无机离子、溶解性有机物（DOM）组分特征与来源解析。结果表明，实际染整废水深度处理工艺过程中，UF-RO工艺对常规污染物去除显著，但RO出水中仍存在有机氮；该工艺可显著去除染整废水中高芳香度、高分子量、疏水性的DOM，而陆源输入、腐殖化程度相对较低的DOM可透过RO膜。染整废水中主要阳离子为Na、Ca和K，阴离子为 ${\mathrm{C}\mathrm{l}}^{-}$ 、 ${\mathrm{S}\mathrm{O}}_{4}^{2-}$ 和 ${\mathrm{H}\mathrm{C}\mathrm{O}}_{3}^{-}$ ，RO单元对Fe、Si和Al的去除率为55.4%—83.6%，对K、Ca、Na、Mg的去除率达到96.3%—100%；RO膜对Mg的浓缩倍数最高，RO膜上 Fe和Al相比Ca和Si更难被洗脱。UF单元可显著截留富里酸类DOM，RO出水则仅存在色氨酸类（Ex/Em=235/335 nm）和酪氨酸类（Ex/Em=225/285 nm）荧光峰，其中Ex/Em=235/335 nm峰为染料相关的荧光峰。除RO出水外，其它水样DOM均以内源输入为主，RO出水则兼具自生源输入和陆源输入特征。这些研究结果可以为人们进一步了解实际染整废水深度处理过程中水质变化特征及RO膜性能提供参考价值。
- 染整废水 /
- 反渗透 /
- 无机离子 /
- 溶解性有机物 /
- 三维荧光光谱 /
- 平行因子分析
Abstract: The ultrafiltration (UF)-reverse osmosis (RO) process has gradually been applied in the advanced treatments of dyeing wastewater in recent years. However, there is still a gap in the characteristics of the inorganic and organic components of dyeing wastewater in the full-scale advanced treatment process. Therefore, the composition and occurrence of the inorganic ions and dissolved organic matter (DOM), and the source of DOM during a full-scale UF-RO advanced treatment process of dyeing wastewater were investigated in this study. Results show that the UF-RO process could significantly remove the conventional contaminants, while still with organic nitrogen in the RO permeate. The DOM with higher aromaticity, molecular weight and hydrophobic characters were significantly rejected during the advanced treatment, whereas the terrestrial input, lower humification DOM were permeable in the RO system. The dominant anions were Na, Ca and K, with ${\mathrm{C}\mathrm{l}}^{-}$ , ${\mathrm{S}\mathrm{O}}_{4}^{2-}$ and ${\mathrm{H}\mathrm{C}\mathrm{O}}_{3}^{-}$ as the main cations in the dyeing wastewater. The removal rates of Fe, Si and Al by the RO unit were 55.4%—83.6%, and 96.3%—100% for that of K, Ca, Na, Mg, respectively. The concentration factor of Mg was the highest for the RO system. Fe and Al were harder to be cleaned from the fouling RO membrane surface than Ca and Si. The fulvic acid-like DOM could be rejected perfectly by the UF unit, and only tryptophan protein-like (Ex/Em=235/335 nm) and tyrosine protein-like (Ex/Em=225/285 nm) DOM were detected in the RO product water. Moreover, DOM with fluorescence peak at Ex/Em=235/335 nm in the RO product water were related to dyestuffs. Endogenous derived DOM were dominant in the water samples other than RO product water, while both endogenous derived and terrestrial derived DOM were mainly in the RO product water. This research can provide a valuable reference for further understanding of the dyeing wastewater characteristics during the full-scale advanced treatment and the performance of the RO system.
- dyeing wastewater /
- reverse osmosis (RO) /
- inorganic ions /
- dissolved organic matter (DOM) /
- three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy /
- parallel factor analysis

我国铅锌工业总规模大，常年位于世界第一，仅2018年，精Zn产量达5.68×10⁶ t，约占全球总量的40%，我国Zn冶炼主流工艺为“焙烧—浸出—电积”，其生产过程中产生大量含Zn、Cd和As等的冶炼废渣，统计表明，平均生产1 t Zn，产生0.96 t废渣^[1]，废渣历史积存量和年新增量大，难以得到有效的消纳利用，通常采用无害化填埋、堆置储存等方式进行处置。在长期的堆置过程中，受风蚀、淋溶和浸蚀等作用影响，废渣中的重金属释放，对周边人群健康和土壤、地下水等生态环境造成严重威胁^[2]。

稳定化是废渣常见的无害化处理方式，通过加入稳定剂降低重金属的迁移性，而稳定剂的选择是关键。目前，常用稳定剂一般包括有机、无机和生物质型3种^[3]。其中，无机型药剂因对重金属稳定效果好而广被应用^[4-6]，其对重金属主要是通过化学键合、物理包容、吸附或形成惰性沉淀物等作用进行稳定^[7-8]。目前，研究应用多以含硫、磷、铁、钙、镁等药剂为主^[7-11]，但多集中在Zn、Pb等个别污染指标，而针对废渣中As、Cd等其他多污染物共存的系统化研究还较为欠缺，特别是个别稳定剂对废渣中As反而存在活化作用则较少关注，受介质类型、污染程度、稳定剂种类、投加量、配伍等因素的影响，不同药剂实际稳定化效果还须进行综合比对和考证。

本研究以湖南某大型冶炼企业渣场堆存的铅锌冶炼废渣为研究对象，采用Na₂S·9H₂O、(NH₄)₂HPO₄、Na₃PO₄·12H₂O、CaO、MgO为稳定化药剂，并进行了药剂配伍研究，以水浸提法^[12]模拟废渣堆存过程的浸蚀淋溶影响，考察了不同药剂对Zn、Cd、Cu、As的综合稳定化效果及其对环境的影响，以期为国内铅锌冶炼废渣的无害化处置提供参考。

1. 材料与方法

1.1 供试材料

本研究所用工业废渣取自湖南某大型冶炼企业典型渣堆场。将堆场上性状明显类似的废渣进行现场机械开挖和预混，运至具防渗结构的预存场进行自然风干、人工除杂、混匀、磨碎后，过4 mm筛，取筛下物于小型卧式搅拌机中再次混匀后，用于稳定化实验。

废渣污染特性如表1所示，与《污水综合排放标准》(GB 8978-1996) ^[13]1级最高允许排放浓度相比，废渣H₂O浸出Zn、Cd和Cu超标，分别超标6.60、10.10、1.76倍，废渣pH为2.40，呈强酸性。

表 1 供试废渣污染特性

Table 1. Pollution characteristics of waste slag

供试废渣	总量/(mg·kg⁻¹)	H₂O浸出/(mg·L⁻¹)	GB 8978-1996 I级/(mg·L⁻¹)
Zn	4 631	38	5.0
Cd	2 188	1.11	0.1
Cu	1 572	5.51	2.0
As	1 442	0.25	0.5
Pd	4 752	0.02	1.0
Cr	106	0.05	1.5

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DownLoad: CSV

稳定化药剂包括Na₂S·9H₂O、(NH₄)₂HPO₄、Na₃PO₄·12H₂O、CaO、MgO，均为分析纯。

1.2 实验方法与分析方法

称量1 000.00 g(干质量)废渣置于敞口玻璃容器中，将Na₂S·9H₂O、(NH₄)₂HPO₄和Na₃PO₄·12H₂O 分别配成200 mL的水剂，按废渣Zn、Cd、Cu、As等的理论水浸出量计算药剂添加量，药剂与元素浸出摩尔比设计为2∶1、4∶1、8∶1、16∶1，对应药剂投加质量分数如表2所示，边加药剂边充分混匀搅拌，搅拌时间20 min，CaO和MgO按粉剂添加，根据前期Zn、Cd稳定化实验结果，3种药剂复配配方按质量比Na₂S·9H₂O∶(NH₄)₂HPO₄∶Na₃PO₄·12H₂O=2∶1∶3进行药剂配伍，设置空白对照(CK)，每处理设3次重复，控制水∶渣(质量比)=1:4左右，室温养护7 d后，进行废渣pH、毒性浸出测试。

表 2 稳定化实验设计

Table 2. Design of heavy metals stabilization experiment %

实验处理	Na₂S·9H₂O	(NH₄)₂HPO₄	Na₃PO₄·12H₂O	CaO	MgO
1	0.30	—	—	—	—
2	0.60	—	—	—	—
3	1.21	—	—	—	—
4	2.42	—	—	—	—
5	—	0.16	—	—	—
6	—	0.32	—	—	—
7	—	0.64	—	—	—
8	—	1.28	—	—	—
9	—	—	0.46	—	—
10	—	—	0.92	—	—
11	—	—	1.84	—	—
12	—	—	3.68	—	—
13	—	—	—	0.40	—
14	—	—	—	0.60	—
15	—	—	—	1.00	—
16	—	—	—	—	0.40
17	—	—	—	—	0.60
18	—	—	—	—	1.00
19	0.60	—	—	0.40	—
20	1.21	—	—	0.40	—
21	2.42	—	—	0.40	—
22	—	0.32	—	0.40	—
23	—	0.64	—	0.40	—
24	—	1.28	—	0.40	—
25	0.40	0.20	0.60	—	—
26	0.80	0.40	1.20	—	—
27	1.60	0.80	2.40	—	—
空白对照	—	—	—	—	—
注：“—”表示未添加，配伍药剂添加时先加CaO。

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使用酸度计(pHs-3C型，上海仪电科学仪器股份有限公司)测定供试废渣的pH，测定方法采用《固体废物腐蚀性测定玻璃电极法》(GB/T 15555.12-1995)^[14]；重金属总量测试的前处理采用石墨炉三酸(体积比为HNO₃∶HF∶HClO₄=3∶2∶2)消解法；毒性浸出采用水浸法^[12]；消解液和水浸出液中重金属含量采用电感耦合等离子体发射光谱仪(ICP-MS 7500，美国Agilent公司)测定。

修复效果评估根据式(1)~式(3)进行计算。

$\eta \left( {\rm{M}} \right) = \left( {{C_0}-{C_t}} \right)/{C_0} \times 100\%$

$(1)$

$\eta \left( {{\rm{Zn}},\;{\rm{Cd}}} \right) = \left( {\eta \left( {{\rm{Zn}}} \right) + \eta \left( {{\rm{Cd}}} \right)} \right)/2$

$(2)$

$\eta = \left( {\eta \left( {{\rm{Zn}}} \right) + \eta \left( {{\rm{Cd}}} \right) + \eta \left( {{\rm{Cu}}} \right) + \eta \left( {{\rm{As}}} \right)} \right)/4$

$(3)$

式中：η(M)为M元素的稳定率；C₀、C_t分别为废渣在稳定化前和稳定化后的元素水浸出浓度，mg·L⁻¹；η(Zn, Cd)为Zn和Cd这2种重金属的稳定率均值；η为Zn、Cd、Cu、As 4种元素的综合稳定率均值。

2. 结果与讨论

2.1 单一稳定剂

Na₂S·9H₂O、(NH₄)₂HPO₄、Na₃PO₄·12H₂O均能明显降低4种金属元素的水浸出浓度(图1~图3)。如图1所示，随Na₂S·9H₂O投加量的增加，各金属元素浸出均呈降低的趋势，Zn、Cd和Cu的稳定率分别为27.63%~88.97%、70.08%~98.05%、99.52%~99.85%。其中，药剂与4种金属元素浸出总量的摩尔比为8 (投加1.21%)时，Cd的浸出浓度由CK的1.11 mg·L⁻¹降至0.02 mg·L⁻¹，达到GB 8978-1996中Cd (0.1 mg·L⁻¹)限标；摩尔比16(投加2.42%)时，Zn浸出才达标，由CK的38 mg·L⁻¹降至4.19 mg·L⁻¹，此时η(Zn)为88.97%、η(Cd)为97.35%，η(Zn, Cd)为93.16%，Na₂S·9H₂O对3种重金属稳定效果突出，总体稳定效应大小依次为Cu>Cd>Zn，这与其提供的S^2-与Zn²⁺、Cd²⁺和Cu²⁺形成金属硫化物沉淀有关^[15]。这种难溶物溶解度很低，形成沉淀的先后顺序一般为CuS>CdS>ZnS^[16]，随投加量的增加，其水解过程中产生的OH⁻也有利于重金属的稳定。此外，各处理使As浸出降低了90.24%~99.11%，说明其与As形成的惰性沉淀物在应对水浸滤风险能力方面也很显著，但在稳定化过程中有少许H₂S逸出。

图 1 Na₂S·9H₂O对废渣中Zn、Cd、Cu和As水浸出浓度的影响

Figure 1. Effect of Na₂S·9H₂O on the H₂O leaching concentration of Zn, Cd, Cu and As in waste slag

下载: 全尺寸图片幻灯片

图 3 Na₃PO₄·12H₂O对废渣中Zn、Cd、Cu和As水浸出浓度的影响

Figure 3. Effect of Na₃HPO₄·12H₂O on the H₂O leaching concentration of Zn, Cd, Cu and As in waste slag

下载: 全尺寸图片幻灯片

(NH₄)₂HPO₄可明显降低重金属的水浸出毒性。如图2所示，随(NH₄)₂HPO₄投加量的增加，Zn、Cd和Cu浸出浓度均呈不断降低的趋势，稳定率分别为59.52%~99.46%、57.97~99.23%、98.85~99.93%，而As浸出则呈现先降低后回升的趋势，药剂摩尔比≥8后，As浸出浓度开始升高并被活化，药剂摩尔比升高至16时，As浸出浓度被活化1.74倍，浓度为0.68 mg·L⁻¹，超出0.5 mg·L⁻¹限标的36%，药剂摩尔比为4时，As浸出降至最低0.016 mg·L⁻¹，η(As)高达93.52%，但此时Zn和Cd浸出分别降至8.47 mg·L⁻¹和0.23 mg·L⁻¹，并未达标。直到药剂摩尔比为8(投加量为0.64%)时，才使以上4种金属元素均达标，Zn和Cd分别降至0.224 mg·L⁻¹和0.01 mg·L⁻¹，η(Zn)和η(Cd)分别为99.41%和99.08%，η(Zn, Cd)为99.25%，4种元素综合稳定率η达到最高值，为87.42%。因此，0.64%的(NH₄)₂HPO₄投加量综合稳定效果最好，但须控制投加剂量，以免高量添加对As过度活化。

图 2 (NH₄)₂HPO₄对废渣中Zn、Cd、Cu和As水浸出浓度的影响

Figure 2. Effect of (NH₄)₂HPO₄ on the H₂O leaching concentration of Zn, Cd, Cu and As in waste slag

下载: 全尺寸图片幻灯片

如图3所示，Na₃PO₄·12H₂O稳定化效果突出，最低药剂摩尔比为2 (投加量为0.46%)时，可使4种元素均能达标，Zn、Cd、Cu和As浸出分别降至0.446、0.014、0.004、0.169 mg·L⁻¹，稳定率分别为98.83%、98.70%、99.93%、31.58%，4元素综合稳定率η可达82.26%。其中，η(Zn)和η(Cd)分别为98.83%和98.70%，η(Zn, Cd)为98.76%，稳定率均高于同摩尔比条件下的(NH₄)₂HPO₄(η(Zn) 59.52%，η(Cd) 57.97%，η(Zn, Cd) 58.94%)和Na₂S·9H₂O(η(Zn)27.63%，η(Cd) 70.08%，η(Zn, Cd) 48.85%)，在Na₃PO₄·12H₂O的各处理组中，η(As)均可稳定在34.92%左右。磷酸盐对Cd、Cu等的固定主要是通过与金属发生表面络合吸附和共沉淀等作用所致^[8]，对Zn主要以诱导或直接吸附^[8]以及少量溶解性无定形沉淀反应^[17]为主，并可促进Zn的可氧化态向残渣态转变^[18]。而P与As化学性质相似，一般认为， ${\rm{PO}}_4^{3 - }$ 和 ${\rm{HPO}}_4^{2 - }$ 会与 ${\rm{AsO}}_4^{3 - }$ 形成竞争吸附，使As的流动性增强，但本研究采用单一Na₃PO₄·12H₂O处理强酸性废渣，并未对As产生明显的活化作用，其具体原因尚须进一步的深入研究。

由图1~图3可知，对Zn的稳定化效果顺序依次为Na₃PO₄·12H₂O>(NH₄)₂HPO₄>Na₂S·9H₂O，对Cd和Cu的稳定化效果依次为Na₃PO₄·12H₂O>Na₂S·9H₂O>(NH₄)₂HPO₄，对As的稳定化效果依次为Na₂S·9H₂O>(0.16~0.32)% (NH₄)₂HPO₄>Na₃PO₄·12H₂O。其中，(NH₄)₂HPO₄易对As产生活化作用，从药剂投加量角度来看，使4种金属元素同时达标的综合稳定效应依次为0.46% Na₃PO₄·12H₂O(摩尔比为2，η=82.26%)>0.64% (NH₄)₂HPO₄(摩尔比为8，η=87.42%)>2.42% Na₂S·9H₂O (摩尔比为16，η=96.36%)，因此，Na₃PO₄·12H₂O对Zn和Cd稳定效果均最为突出，对As活化效果不明显，且低剂量添加不易导致溶解P过量，因此，在3种药剂中，Na₃PO₄·12H₂O最适合单独处理强酸性废渣。

如图4(a)所示，(0.4~1)% CaO处理后，废渣中Zn、Cd、Cu、As的浸出浓度分别降至<10、<0.50、<25、<220 μg·L⁻¹，远低于GB 8978-1996最高限值。其中，Zn、Cd、Cu稳定率均高于96%，这与CaO提高废渣pH、重金属氢氧化物沉淀增多、黏土物质等对重金属吸附性增强^[19]、提供的钙离子与金属离子发生同晶替代^[20]等作用有关。η(As)则为10.93%~74.09%，低量CaO更有利于As的稳定，CaO对As的稳定作用主要与强氧化性和适当pH条件下易形成CaHAsO₄和Ca₃(AsO₄)₂沉淀^[21]有关。但本研究表明，当CaO≤1%，随CaO量的增加，As浸出浓度逐渐升高，这可能由于随着OH⁻浓度增高，负电荷对As的竞争吸附作用逐渐加强，最终导致As的迁移性有所增强^[22]。

图 4 CaO和MgO对废渣中Zn、Cd、Cu和As浸出浓度的影响

Figure 4. Effect of CaO and MgO on the leaching concentration of Zn, Cd, Cu and As in waste slag

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如图4(b)所示，MgO使废渣中Zn、Cd、Cu、As的浸出浓度分别降至≤15、<3、<5、≤10 μg·L⁻¹，η均高于98%，其中η(As)均高于95%，明显优于CaO，这可能与MgO比表面积大，表面具有镁氧基(Mg―O)活泼反应基团，对重金属的吸附、沉淀等作用更强有关^[23]。

由图4可知，CaO、MgO均可作为高效稳定剂，Ca²⁺、Mg²⁺虽均会与砷酸根离子形成复杂的络合沉淀物，但CaO的添加会使As浸出反升，4种元素综合稳定效应为0.4% MgO(η=98.90%)>0.4% CaO(η=93.48%)。

2.2 无机-无机组合处理

硫钙、磷钙和硫磷组合处理结果如图5所示。各类组合对废渣中的Zn、Cd和Cu的稳定化效果均较为明显，稳定率均高于95%，硫化物的添加有助于As的稳定，磷酸盐过量则对As的稳定化效果产生一定的拮抗作用。由图5(a)可知，0.4% CaO与3种不同投加比的Na₂S·9H₂O组合处理后，4种元素浸出浓度均达标，Zn、Cd和Cu的稳定率均高于99%，Zn浸出浓度均低于0.07 mg·L⁻¹，Cd和Cu浸出浓度均低于0.01 mg·L⁻¹，随Na₂S·9H₂O投加量的增加，η(As)明显增强。与单一Na₂S·9H₂O相比，各处理的硫钙组合均提高了Zn和Cd的稳定效果，其中，η(Zn)从45.53%~88.97%升至99.80%以上，说明CaO的加入有助于增强阳离子金属的稳定效果，协同增效作用明显，但同时一定程度上降低了As的稳定效果，η(As)从96.36%~99.11%降至41.70%~97.17%。在Na₂S·9H₂O组合比为0.61%和1.21%时，As的稳定化效果反而不如2种药剂单独使用时的效果，不仅未达到协同稳定As的效应，反而弱化了As的稳定效果，这与王浩等^[3]的研究结果类似。但CaO与最高投加比(2.42%)Na₂S·9H₂O组合时，稳定As的能力依次为Na₂S·9H₂O>硫钙组合>CaO，组合处理对4种元素的综合稳定率η高达99.08%，这也说明硫钙组合稳定As的效果优于CaO，究其原因主要为2个方面：一方面，低量CaO利于降低As的浸出；另一方面，存在碱性条件使As流动性增强的风险^[24-25]，而硫钙组合对As的稳定化水平则随Na₂S·9H₂O投加量的增加而增强，在控制低剂量CaO防止因过量而活化As的同时，可使As₂S₃等更稳定的沉淀作用逐渐占优，As的稳定性增强。综上所述，硫钙组合有利于增强单一Na₂S·9H₂O对Zn的稳定效果，高剂量时对As的稳定效果优于单一CaO，且对4种元素的综合稳定效果均强于单一处理时的效果，组合处理中先加CaO也大大减少了H₂S的逸出，有助于环境友好性，因此，与CaO和Na₂S·9H₂O单一处理相比，硫钙组合更占优势。

图 5 组合药剂对废渣中Zn、Cd、Cu和As的稳定效果

Figure 5. Stabilization effect of Zn, Cd, Cu and As in waste slag by complex stabilizers

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由图5(b)可知，低剂量的0.4% CaO+0.32% (NH₄)₂HPO₄使4种金属元素的稳定率均高于95%，η高达98.13%，优于单一CaO(η 93.48%)和单一(NH₄)₂HPO₄(η 87.42%)，与单一(NH₄)₂HPO₄相比，组合处理进一步降低了Zn和As的浸出浓度，但随着组合处理中(NH₄)₂HPO₄投加量的增加，η(As)明显降低，甚至为负值，0.4% CaO+1.28% (NH₄)₂HPO₄处理组的η(As)降为−46.15%。磷钙组合主要弱化了单一(NH₄)₂HPO₄对As的活化作用，CaO与低量(NH₄)₂HPO₄组合更有助于4种金属元素的综合稳定。

考虑到Na₂S·9H₂O和磷酸盐分别对As和Zn稳定能力强的特点，硫磷复配后的稳定化效果如图5(c)所示。在投加1.2%~4.8%复配剂后，Zn、Cd和Cu的稳定率均高于96%，但As均被活化，η(As)为−171.66%~−23.08%，其中，控制药剂投加量为1.2%，4种金属元素均达标，η仅为68.07%，2.4%和4.8%处理后As浸出超标。硫磷组合剂对As活化性较强，须控制投加量≤1.2%。

3. 结论

1)单一硫化物和磷酸盐对重金属的稳定化结果表明，3种药剂中Na₃PO₄·12H₂O对重金属的稳定效果最好，Na₂S·9H₂O对As的稳定效果最好，(NH₄)₂HPO₄易对As产生活化作用，从药剂投加量角度考虑，与GB 8978-1996最高允许排放浓度相比，达标稳定4种金属元素综合稳定化效应次序依次为0.46% Na₃PO₄·12H₂O(η 82.26%)>0.64% (NH₄)₂HPO₄(η 87.42%)>2.42% Na₂S·9H₂O(η 96.36%)，Na₃PO₄·12H₂O最优。

2)单一钙基、镁基和无机配伍对重金属的稳定化结果表明，单一MgO(投加比0.4%时，η(Zn) 99.97%，η(Cd) 99.76%)或CaO处理即可使之达标，硫钙组合提高了单一Na₂S·9H₂O对Zn、Cd的稳定化水平，η(Zn)从45.53%~88.97%升至99.80%以上，0.4% CaO与2.42% Na₂S·9H₂O的组合对As稳定效果优于单一CaO，对4种金属元素η高达99.08%，优于单一处理；磷钙和磷硫配伍中磷酸盐过量易活化As。各处理满足4种金属元素均达标的综合稳定效应大小顺序依次为0.4% MgO>0.4% CaO>(0.4% CaO+0.61% Na₂S·9H₂O)>(0.4% CaO+0.32% (NH₄)₂HPO₄)>1.2% (Na₂S·9H₂O∶(NH₄)₂HPO₄∶Na₃PO₄·12H₂O=2∶1∶3)。

3) MgO、Na₃PO₄·12H₂O、硫钙组合为优选稳定剂，CaO过量和组合剂中磷酸盐过量均不利于As的同时稳定。

图 1 水样中有机组分变化

Figure 1. Variations of organic components of wastewater samples

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图 2 水样的DOM三维荧光光谱图分析

Figure 2. Three-dimensional fluorescence spectrum analysis of DOM in dyeing wastewater samples

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图 3 各水样荧光参数

Figure 3. Fluorescence parameters of dyeing wastewater samples

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表 1 常规无机水质指标变化特征

Table 1. Regular characteristics of dyeing wastewater samples

采样点Sampling spots	pH	色度Colourity	浊度/NTUTurbidity	电导率/（μs·cm⁻¹） Conductivity	TDS/(mg·L⁻¹)	TP/(mg·L⁻¹)	${\mathrm{P}\mathrm{O}}_{4}^{3-}{\text{-}}\mathrm{P}$ /(mg·L⁻¹)	${\mathrm{N}\mathrm{H}}_{4}^{+}{\text{-}}\mathrm{N}$ /(mg·L⁻¹)	${\mathrm{N}\mathrm{O}}_{2}^{-}{\text{-}}\mathrm{N}$ /(mg·L⁻¹)	${\mathrm{N}\mathrm{O}}_{3}^{-}{\text{-}}\mathrm{N}$ /(mg·L⁻¹)	TN/(mg·L⁻¹)
S1	7.32±0.35	150±38	1.78±1.63	6563±926	4177±877	0.19±0.08	0.09±0.01	0.92±0.76	0.15±0.09	5.27±2.29	13.07±5.44
S2	6.95±0.28	45±10	0.54±0.16	6698±904	4564±1078	0.02±0.01	0.01±0.00	1.60±2.01	0.13±0.01	4.49±1.34	12.62±1.78
S3	6.91±0.48	5±0	0.12±0.01	350±68	193±84	0	0	0.16±0.10	0.01	0.71±0.17	1.59±0.46
S4	7.48±0.14	55±6	0.57±0.50	11340±2855	8343±3134	0.17±0.01	0.05±0.03	3.10±4.13	0.18±0.02	6.70±1.50	19.28±4.45
S5	7.52±0.33	78±22	0.77±0.44	8573±883	5312±1092	0.05±0.01	0.02±0.003	2.35±2.99	0.13±0.05	5.23±1.27	14.44±2.86
注：所有数据为4次采样的均值±标准差.　　Note: All data are calculated from results of four sampling events (mean ± standard deviation).

采样点Sampling spots	pH	色度Colourity	浊度/NTUTurbidity	电导率/（μs·cm⁻¹） Conductivity	TDS/(mg·L⁻¹)	TP/(mg·L⁻¹)	${\mathrm{P}\mathrm{O}}_{4}^{3-}{\text{-}}\mathrm{P}$ /(mg·L⁻¹)	${\mathrm{N}\mathrm{H}}_{4}^{+}{\text{-}}\mathrm{N}$ /(mg·L⁻¹)	${\mathrm{N}\mathrm{O}}_{2}^{-}{\text{-}}\mathrm{N}$ /(mg·L⁻¹)	${\mathrm{N}\mathrm{O}}_{3}^{-}{\text{-}}\mathrm{N}$ /(mg·L⁻¹)	TN/(mg·L⁻¹)
S1	7.32±0.35	150±38	1.78±1.63	6563±926	4177±877	0.19±0.08	0.09±0.01	0.92±0.76	0.15±0.09	5.27±2.29	13.07±5.44
S2	6.95±0.28	45±10	0.54±0.16	6698±904	4564±1078	0.02±0.01	0.01±0.00	1.60±2.01	0.13±0.01	4.49±1.34	12.62±1.78
S3	6.91±0.48	5±0	0.12±0.01	350±68	193±84	0	0	0.16±0.10	0.01	0.71±0.17	1.59±0.46
S4	7.48±0.14	55±6	0.57±0.50	11340±2855	8343±3134	0.17±0.01	0.05±0.03	3.10±4.13	0.18±0.02	6.70±1.50	19.28±4.45
S5	7.52±0.33	78±22	0.77±0.44	8573±883	5312±1092	0.05±0.01	0.02±0.003	2.35±2.99	0.13±0.05	5.23±1.27	14.44±2.86
注：所有数据为4次采样的均值±标准差.　　Note: All data are calculated from results of four sampling events (mean ± standard deviation).

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表 2 主要阴阳离子组成

Table 2. Anions and cations composition in dyeing wastewater samples

采样点	Na/(mg·L⁻¹)	Al/(mg·L⁻¹)	Ca/(mg·L⁻¹)	K/(mg·L⁻¹)	Fe/(mg·L⁻¹)	Mg/(mg·L⁻¹)	Si/(mg·L⁻¹)	Cl⁻/(mg·L⁻¹)	SO₄^2-/(mg·L⁻¹)	HCO₃⁻/(mg·L⁻¹)
S1	1264.43±182.47	4.41±7.07	38.86±7.86	24.81±0.24	2.62±2.35	0.72±1.09	13.01±1.83	827.69±508.72	788.09±473.08	516.59±225.20
S2	1259.94±191.28	13.62±11.10	52.17±1.79	24.92±0.77	2.45±0.55	0.80±1.05	12.00±1.33	980.28±381.53	849.49±334.98	381.25±196.88
S3	46.36±3.51	2.23±2.50	0.30±0.40	49.88±17.44	1.09±1.23	0.00±0.00	2.43±1.67	45.77±29.09	12.24±8.32	31.24±7.30
S4	2255.83±615.78	23.69±7.41	100.16±33.36	0.75±0.41	5.12±3.56	5.51±4.15	20.53±4.09	1612.68±852.62	1441.73±750.81	619.53±199.94
S5	1639.95±154.72	5.83±2.34	65.62±7.14	33.99±6.14	1.44±1.44	2.09±1.79	15.85±0.86	1348.12±192.41	1319.25±90.82	520.41±206.15
注：所有数据为4次采样的均值±标准差.　　Note: All data are calculated from results of four sampling events (mean ± standard deviation).

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表 3 各水样荧光峰位置与荧光峰强度

Table 3. The locations and intensities of fluorescence peaks of dyeing wastewater samples

采样点Sampling spots	A峰(色氨酸类)Peak A (Tryptophan-like)		B峰（酪氨酸类）Peak A (Tyrosine -like)		C峰（富里酸类）Peak A (Fulvic-like)		D峰（SMP类）Peak A (SMP -like)
采样点Sampling spots	Ex/Em	荧光峰强度Fluorescence intensity	Ex/Em	荧光峰强度Fluorescence intensity	Ex/Em	荧光峰强度Fluorescence intensity	Ex/Em	荧光峰强度Fluorescence intensity
S1	235/340	1243	225/285	598	255/455	1047	280/320	850
S2	235/345	690	225/285	544	—	—	275/320	536
S3	235/335	263	225/285	230	—	—	—	—
S4	235/340	1960	225/285	1402	—	—	280/320	1487
S5	235/345	809	225/285	661	—	—	275/320	548

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我国是纺织品生产和出口大国，根据世界贸易组织的统计数据，我国在世界纺织品出口中所占份额在2019年升至39.2%。每生产1 kg的纺织产品大约需要100—200 L的高质量水，因而会产生大量印染废水^[1]。印染废水通常具有高色度（50—2500 度）、高化学需氧量（COD）（150—30000 mg·L⁻¹）、较高总溶解固体（TDS）（1500—12000 mg·L⁻¹）和硫酸盐（500—1000 mg·L⁻¹）以及可生化性较低的水质特征^[2—3]。染色过程中添加的硫酸钠等染色辅助药剂，导致印染废水中无机离子较高。此外，在染色工艺过程使用的染料中主要发色基团为偶氮基（—N=N—）、羰基（—C=O）、硝基（—N=O）、醌基、以及诸如胺基、羧基、磺酸基、羟基等助色基团，染料中有 60%—70% 为难降解的偶氮染料，所有染料中有15%—20%会被排放到环境中进而造成严重环境危害^[4—5]。根据《纺织染整工业废水治理工程技术规范（HJ 471—2020）》，印染废水处理工艺普遍为混凝-沉淀/气浮-水解酸化-好氧-深度处理或间接排放，常规处理后的深度处理工艺或回用处理工艺一般为混凝沉淀法、化学氧化法、膜分离法、曝气生物滤池法、生物活性炭法、过滤法、吸附法等工艺中的一种或几种工艺组合。化学氧化法对难降解残余有机物有较好的去除效果，但无法去除无机离子，而膜处理工艺因其优异的有机、无机污染物去除效果及易于规范化操作管理，在实际工程中得到了推广应用^[6—10]。膜污染是膜工艺正常运行的重要控制要素，人们对膜污染特征与污染机制做了众多研究^{[3, 11—12]}，反渗透RO膜污染一般分为颗粒和胶体污染、无机和结垢污染、有机污染和生物污染四大类^[13]，具体的膜污染特征与处理水质密切相关。

目前人们对实际染整废水深度处理过程中，有机组分和无机组分特征及其变化规律的研究不足，尤其对溶解性有机物（DOM）组分的变化特征及其来源研究较少，对染整废水深度处理过程中水质特征与RO膜污染的内在联系还缺乏统一认识。因此本研究针对采用典型常规处理工艺（即混凝—沉淀—好氧）+深度处理工艺的浙江某染整废水处理厂，重点考察该厂超滤（UF）+反渗透（RO）深度处理工艺过程中，各单元出水的无机离子组成与DOM组分的变化特征，并进行了DOM的来源解析，研究结果可为深入了解实际染整废水深度处理过程中的水质变化特征，以及下一步探讨实际染整废水处理过程中的水质特征与膜污染机制内在联系提供科学参考依据。

某实际染整废水深度处理过程中无机组分与溶解性有机物的变化

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