利用污水污泥制备有机物聚集介质的可行性探析

doi:10.19965/j.cnki.iwt.2021-0817

摘要/Abstract

摘要：

将城市污水中富含的有机物质或化学能回收利用，转化为有价值的产品或能源，是当前城市污水处理领域的研究热点。低浓度有机物的富集浓缩是实现城市污水有机物回收利用的首要前提。利用絮凝捕集方法将污水有机物转移聚集至污泥中，具有富集过程能耗低、碳转化损失少的优点。阐述分析了高分子有机絮凝剂的制备原理，尤其是天然高分子絮凝剂改性制备过程中各组分的作用、特性与效果，并将污泥水热处理液相产物中大分子有机物的组成和特性与之进行对比分析，介绍了接枝共聚、醚化、氧化等几种常见改性手法。结合相关实验研究，论证探析了以污水污泥为原料，通过水热处理和改性制备获取可用于城市污水有机物富集回收的絮凝聚集介质的可行性及意义，并提出了进一步深入研究需要解决的问题。

关键词: 城市污水资源化, 污泥水热处理, 有机絮凝剂, 聚集介质

Abstract:

At present，it is a hot research topic in the field of urban sewage treatment to convert organic matter or chemical energy in urban sewage into valuable products or energy. Enrichment and concentration of low-concentration organic matter in municipal wastewater is the first prerequisite for achieving organic matter recycling. Using flocculation capture method to transfer organic matter from sewage to sludge has the advantages of low energy consumption and less loss of carbon conversion during the enrichment process. This paper analyzed the preparation principle of organic polymer flocculant，especially the function，characteristic and effect of each component of the natural macromolecule flocculant during the modification. The composition and properties of macromolecule organic matter in liquid phase product of sludge hydrothermal treatment were compared with that of organic polymer flocculant. Several common modification methods such as graft copolymerization，etherification and oxidation were introduced. Combining with related experimental researches，the feasibility and significance of using sewage sludge as raw material to obtain aggregation medium which could be used for the enrichment and recovery of organic matter in municipal sewage by hydrothermal treatment and modification were discussed，and the problems needed to be further studied and solved were put forward.

Key words: recycling urban sewage, sludge hydrothermal treatment, organic flocculant, aggregation medium

中图分类号:

X703.1

王灵芝, 黄勇, 查晓, 张悦, 陈硕君, 王璐, 李大鹏. 利用污水污泥制备有机物聚集介质的可行性探析[J]. 工业水处理, 2022, 42(10): 22-30.

Lingzhi WANG, Yong HUANG, Xiao ZHA, Yue ZHANG, Shuojun CHEN, Lu WANG, Dapeng LI. The feasibility of using sewage sludge to prepare organic and aggregation medium[J]. Industrial Water Treatment, 2022, 42(10): 22-30.

https://www.iwt.cn/CN/Y2022/V42/I10/22

图/表 9

图1 聚丙烯酰胺的4种典型结构

Fig. 1 Four typical structures of PAM

图2 丙烯酰胺合成聚丙烯酰胺反应示意

Fig. 2 Schematic diagram of synthesis of polyacrylamide by acrylamide

表1 几种常见天然高分子材料对比

Table 1 Comparison of several common natural polymers

种类	相对分子质量	官能团	参考文献
木质素	1.0×10³~2.0×10⁴	甲氧基、酚羟基、醇羟基、羰基、羧基	〔22〕
壳聚糖	2.0×10⁵	氨基和羟基	〔23〕
淀粉	1.5×10⁵	羟基	〔24〕

图3 木质素接枝丙烯酰胺反应示意

Fig. 3 Schematic diagram of lignin grafted polyacrylamide reaction

表2 美拉德反应的典型产物

Table 2 Typical products of Maillard reaction

种类	分子结构	活性官能团
N-葡萄糖基胺		羟基
1-氨基-1-脱氧-2-酮糖		羟基
羰基化合物		羟基
糠醛衍生物		羟基
氨基酮		氨基
丁间醇醛聚合物		羟基

表3 自由基接枝共聚的常见单体

Table 3 Common monomers of free radical graft copolymerization

单体类型	单体	参考文献
非离子型	丙烯酰胺	〔44〕
非离子型	N-乙烯基甲酰胺	〔45〕
阳离子型	3-氯-2-羟丙基三甲基氯化铵	〔46〕
阳离子型	〔2-（甲基丙烯酰氧）乙基〕三甲基氯化铵	〔47〕
阴离子型	甲基丙烯酸	〔48〕
阴离子型	2-丙烯酰胺基乙醇酸	〔49〕

图4 木质素和2，3-环氧丙基三甲基氯化铵醚化反应

Fig. 4 Etherification of lignin and 2，3-epoxy propyl trimethylammonium chloride

图5 纤维素氧化反应式

Fig. 5 Cellulose oxidation reaction formula

图6 以污水污泥为原料原位制备聚集介质的城市污水资源化处理工艺

Fig. 6 Urban sewage recycling treatment process with sewage sludge by in situ preparation of aggregation medium from sewage sludge

参考文献 59

1	孙茜萍. 絮凝-超滤去除城市污水中有机物的实验研究［J］. 工业水处理，2019，39（6）：73-76. doi:10.11894/iwt.2018-0881
	SUN Xiping. Experimental research on the removal of organic matter from urban sewage by the combined process flocculation-ultrafiltration［J］. Industrial Water Treatment，2019，39（6）：73-76. doi:10.11894/iwt.2018-0881
2	ALLOUL A， GANIGUÉ R， SPILLER M，et al. Capture-ferment-upgrade：A three-step approach for the valorization of sewage organics as commodities［J］. Environmental Science & Technology，2018，52（12）：6729-6742. doi:10.1021/acs.est.7b05712
3	NOGAJ T M， RAHMAN A， MILLER M W，et al. Soluble substrate removal determination through intracellular storage in high-rate activated sludge systems using stoichiometric mass balance approach［J］. New Biotechnology，2019，52：84-93. doi:10.1016/j.nbt.2019.05.005
4	KIMURA K， YAMAKAWA M， HAFUKA A. Direct membrane filtration（DMF） for recovery of organic matter in municipal wastewater using small amounts of chemicals and energy［J］. Chemosphere，2021，277：130244. doi:10.1016/j.chemosphere.2021.130244
5	CAGNETTA C， SAERENS B， MEERBURG F A，et al. High-rate activated sludge systems combined with dissolved air flotation enable effective organics removal and recovery［J］. Bioresource Technology，2019，291：121833. doi:10.1016/j.biortech.2019.121833
6	郭超然，黄勇，朱文娟，等. 城市污水有机物回收：捕获技术研究进展［J］. 化工进展，2021，40（3）：1619-1633.
	GUO Chaoran， HUANG Yong， ZHU Wenjuan，et al. Organics recovery from municipal wastewater：Research advances in capture technologies［J］. Chemical Industry and Engineering Progress，2021，40（3）：1619-1633.
7	CHEN Yun， LIN Hui， SHEN Nan，et al. Phosphorus release and recovery from Fe-enhanced primary sedimentation sludge via alkaline fermentation［J］. Bioresource Technology，2019，278：266-271. doi:10.1016/j.biortech.2019.01.094
8	SALEHIZADEH H， YAN Ning， FARNOOD R. Recent advances in polysaccharide bio-based flocculants［J］. Biotechnology Advances，2018，36（1）：92-119. doi:10.1016/j.biotechadv.2017.10.002
9	LIU Ruiting， CHI Lina， WANG Xinze，et al. Review of metal （hydr）oxide and other adsorptive materials for phosphate removal from water［J］. Journal of Environmental Chemical Engineering，2018，6（4）：5269-5286. doi:10.1016/j.jece.2018.08.008
10	FENG Qiyun， GAO Baoyu， YUE Qinyan，et al. Flocculation performance of papermaking sludge-based flocculants in different dye wastewater treatment：Comparison with commercial lignin and coagulants［J］. Chemosphere，2021，262：128416. doi:10.1016/j.chemosphere.2020.128416
11	郭超然. 基于水热技术的城市污水有机碳捕获与利用方法［D］. 苏州：苏州科技大学，2020. doi:10.1016/j.ccst.2021.100011
	GUO Chaoran. Organic carbon capture and utilization of municipal wastewater based on hydrothermal technology［D］. Suzhou：Suzhou University of Science and Technology，2020. doi:10.1016/j.ccst.2021.100011
12	CHU Yongbao， LI Min， LIU Jinwei，et al. Molecular insights into the mechanism and the efficiency-structure relationship of phosphorus removal by coagulation［J］. Water Research，2018，147：195-203. doi:10.1016/j.watres.2018.10.006
13	GALARNEAU E， GEHR R. Phosphorus removal from wastewaters：Experimental and theoretical support for alternative mechanisms［J］. Water Research，1997，31（2）：328-338. doi:10.1016/s0043-1354(96)00256-4
14	LIU Huan， BASAR I A， NZIHOU A，et al. Hydrochar derived from municipal sludge through hydrothermal processing：A critical review on its formation，characterization，and valorization［J］. Water Research，2021，199：117186. doi:10.1016/j.watres.2021.117186
15	OWEN A T， FAWELL P D， SWIFT J D. The preparation and ageing of acrylamide/acrylate copolymer flocculant solutions［J］. International Journal of Mineral Processing，2007，84（1/2/3/4）：3-14. doi:10.1016/j.minpro.2007.05.003
16	葛亚玲. 壳聚糖接枝共聚絮凝剂的制备及其絮凝性能［D］. 重庆：重庆大学，2017.
	GE Yaling. Study on the preparation and flocculation performance of chitosan grafted copolymer flocculant［D］. Chongqing：Chongqing University，2017.
17	舒型武，郑怀礼. 阳离子型有机絮凝剂研究进展［J］. 现代化工，2001，21（10）：13-16. doi:10.3321/j.issn:0253-4320.2001.10.004
	SHU Xingwu， ZHENG Huaili. Advances in cationic organic flocculant［J］. Modern Chemical Industry，2001，21（10）：13-16. doi:10.3321/j.issn:0253-4320.2001.10.004
18	高华星，饶炬，陆兴章，等. 人工合成有机高分子絮凝剂［J］. 化工时刊，2000（9）： 5-10.
	GAO Huaxing， RAO Ju， LU Xingzhang， et al. Synthetic organic polymer flocculant［J］. Chemical Industry Times，2000（9）：5-10.
19	LEE C S， ROBINSON J， CHONG M F. A review on application of flocculants in wastewater treatment［J］. Process Safety and Environmental Protection，2014，92（6）：489-508. doi:10.1016/j.psep.2014.04.010
20	YIN Zhihong， CHU Ruoyu， ZHU Liandong，et al. Application of chitosan-based flocculants to harvest microalgal biomass for biofuel production：A review［J］. Renewable and Sustainable Energy Reviews，2021，145：111159. doi:10.1016/j.rser.2021.111159
21	郑怀礼. 聚丙烯酰胺类絮凝剂与絮凝科学［M］. 成都：科学出版社，2020：0-333.
	ZHENG Huaili. Polyacrylamide flocculants and flocculation science［M］. Chengdu：Science Press，2020：0-333.
22	WANG Bin， WANG Shuangfei， LAM S S，et al. A review on production of lignin-based flocculants：Sustainable feedstock and low carbon footprint applications［J］. Renewable and Sustainable Energy Reviews，2020，134：110384. doi:10.1016/j.rser.2020.110384
23	HASAN A， FATEHI P. Synthesis and characterization of lignin-poly（acrylamide）-poly（2-methacryloyloxyethyl） trimethyl ammonium chloride copolymer［J］. Journal of Applied Polymer Science，2018，135（23）： 46338. doi:10.1002/app.46338
24	MOHD ASHARUDDIN S， OTHMAN N， ALTOWAYTI W A H，et al. Recent advancement in starch modification and its application as water treatment agent［J］. Environmental Technology & Innovation，2021，23：101637. doi:10.1016/j.eti.2021.101637
25	SANCHEZ-SALVADOR J L， BALEA A， MONTE M C，et al. Chitosan grafted/cross-linked with biodegradable polymers：A review［J］. International Journal of Biological Macromolecules，2021，178：325-343. doi:10.1016/j.ijbiomac.2021.02.200
26	RAJ V， SHIM J J， LEE J. Grafting modification of okra mucilage：Recent findings，applications，and future directions［J］. Carbohydrate Polymers，2020，246：116653. doi:10.1016/j.carbpol.2020.116653
27	KUMAR M， GEHLOT P S， PARIHAR D，et al. Promising grafting strategies on cellulosic backbone through radical polymerization processes：A review［J］. European Polymer Journal，2021，152：110448. doi:10.1016/j.eurpolymj.2021.110448
28	YIN Jun， LIU Jiaze， CHEN Ting，et al. Influence of melanoidins on acidogenic fermentation of food waste to produce volatility fatty acids［J］. Bioresource Technology，2019，284：121-127. doi:10.1016/j.biortech.2019.03.078
29	WANG Liping， LI Aimin. Hydrothermal treatment coupled with mechanical expression at increased temperature for excess sludge dewatering： The dewatering performance and the characteristics of products［J］. Water Research，2015，68： 291-303. doi:10.1016/j.watres.2014.10.016
30	PENAUD V， DELGENÈS J， MOLETTA R. Characterization of soluble molecules from thermochemically pretreated sludge［J］. Journal of Environmental Engineering，2000，126（5）： 397-402. doi:10.1061/(asce)0733-9372(2000)126:5(397)
31	WANG Qiandi， XU Qiongying， DU Zhengliang，et al. Mechanistic insights into the effects of biopolymer conversion on macroscopic physical properties of waste activated sludge during hydrothermal treatment：Importance of the Maillard reaction［J］. Science of the Total Environment，2021，769：144798. doi:10.1016/j.scitotenv.2020.144798
32	HAO Shilai， REN Shuang， ZHOU Nan，et al. Molecular composition of hydrothermal liquefaction wastewater from sewage sludge and its transformation during anaerobic digestion［J］. Journal of Hazardous Materials，2020，383：121163. doi:10.1016/j.jhazmat.2019.121163
33	ZHANG Dian， FENG Yiming， HUANG Haibo， et al. Recalcitrant dissolved organic nitrogen formation in thermal hydrolysis pretreatment of municipal sludge［J］. Environment International，2020，138：105629. doi:10.1016/j.envint.2020.105629
34	DWYER J， STARRENBURG D， TAIT S，et al. Decreasing activated sludge thermal hydrolysis temperature reduces product colour，without decreasing degradability［J］. Water Research，2008，42（18）：4699-4709. doi:10.1016/j.watres.2008.08.019
35	FENG Li， LI Xuhao， LU Wencong，et al. Preparation of a graft modified flocculant based on chitosan by ultrasonic initiation and its synergistic effect with kaolin for the improvement of acid blue 83（AB 83） removal［J］. International Journal of Biological Macromolecules，2020，150：617-630. doi:10.1016/j.ijbiomac.2020.02.076
36	TIAN Zhenle， ZHANG Liping， SANG Xinxin，et al. Preparation and flocculation performance study of a novel amphoteric alginate flocculant［J］. Journal of Physics and Chemistry of Solids，2020，141：109408. doi:10.1016/j.jpcs.2020.109408
37	TAVAKOLIAN M， WIEBE H， SADEGHI M A，et al. Dye removal using hairy nanocellulose：Experimental and theoretical investigations［J］. ACS Applied Materials & Interfaces，2020，12（4）：5040-5049. doi:10.1021/acsami.9b18679
38	TANG Xiaomin， HUANG Ting， ZHANG Shixin，et al. The role of sulfonated chitosan-based flocculant in the treatment of hematite wastewater containing heavy metals［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2020，585：124070. doi:10.1016/j.colsurfa.2019.124070
39	HU Pan， XI Zhonghua， LI Yan，et al. Evaluation of the structural factors for the flocculation performance of a co-graft cationic starch-based flocculant［J］. Chemosphere，2020，240：124866. doi:10.1016/j.chemosphere.2019.124866
40	ZHOU LÜ， ZHOU Hongjie， YANG Xiaoyu. Preparation and performance of a novel starch-based inorganic/organic composite coagulant for textile wastewater treatment［J］. Separation and Purification Technology，2019，210：93-99. doi:10.1016/j.seppur.2018.07.089
41	NGEMA S S， BASSON A K， MALIEHE T S. Synthesis，characterization and application of polyacrylamide grafted bioflocculant［J］. Physics and Chemistry of the Earth，Parts A/B/C，2020，115：102821. doi:10.1016/j.pce.2019.102821
42	IBRAHIM A G， SALEH A S， ELSHARMA E M，et al. Chitosan-g-maleic acid for effective removal of copper and nickel ions from their solutions［J］. International Journal of Biological Macromolecules，2019，121：1287-1294. doi:10.1016/j.ijbiomac.2018.10.107
43	SONG Yuefei， HU Qihua， LI Tiemei，et al. Advanced reclamation of hairwork dyeing effluent using tree-shaped cellulose flocculants and subsequent optimization of dual-membrane performance and fouling behavior［J］. Journal of Cleaner Production，2020，268：122348. doi:10.1016/j.jclepro.2020.122348
44	YANG Zhen， HOU Tianyang， MA Jiangya，et al. Role of moderately hydrophobic chitosan flocculants in the removal of trace antibiotics from water and membrane fouling control［J］. Water Research，2020，177：115775. doi:10.1016/j.watres.2020.115775
45	HASAN A， FATEHI P. Cationic kraft lignin-acrylamide as a flocculant for clay suspensions：1. Molecular weight effect［J］. Separation and Purification Technology，2018，207：213-221. doi:10.1016/j.seppur.2018.06.047
46	MISHRA D K， TRIPATHY J， SRIVASTAVA A，et al. Graft copolymer（chitosan-g-N-vinyl formamide）：Synthesis and study of its properties like swelling，metal ion uptake and flocculation［J］. Carbohydrate Polymers，2008，74（3）：632-639. doi:10.1016/j.carbpol.2008.04.015
47	GUO Kangying， GAO Baoyu， YUE Qinyan，et al. Characterization and performance of a novel lignin-based flocculant for the treatment of dye wastewater［J］. International Biodeterioration & Biodegradation，2018，133：99-107. doi:10.1016/j.ibiod.2018.06.015
48	WANG Shoujuan， KONG Fangong， GAO Weijue，et al. Novel process for generating cationic lignin based flocculant［J］. Industrial & Engineering Chemistry Research，2018，57（19）：6595-6608. doi:10.1021/acs.iecr.7b05381
49	KONG Fangong， WANG Shoujuan， PRICE J T，et al. Water soluble kraft lignin-acrylic acid copolymer：Synthesis and characterization［J］. Green Chemistry，2015，17（8）：4355-4366. doi:10.1039/c5gc00228a
50	YADAV M， SAND A， BEHARI K. Synthesis and properties of a water soluble graft（chitosan-g-2-acrylamidoglycolic acid） copolymer［J］. International Journal of Biological Macromolecules，2012，50（5）：1306-1314. doi:10.1016/j.ijbiomac.2012.03.010
51	BERTELLA S， LUTERBACHER J S. Lignin functionalization for the production of novel materials［J］. Trends in Chemistry，2020，2（5）：440-453. doi:10.1016/j.trechm.2020.03.001
52	GUO Kangying， GAO Yao， GAO Baoyu，et al. Structure-activity relationships of the papermill sludge-based flocculants in different dye wastewater treatment［J］. Journal of Cleaner Production，2020，266：121944. doi:10.1016/j.jclepro.2020.121944
53	王丹凤. 阳离子改性壳聚糖、纤维素合成污泥脱水絮凝剂［D］. 长春：吉林大学，2016.
	WANG Danfeng. Synthesis of novel sludge dewatering flocculant of chitosan and cellulose modified by cation［D］. Changchun：Jilin University，2016.
54	SUOPAJÄRVI T， LIIMATAINEN H， HORMI O，et al. Coagulation-flocculation treatment of municipal wastewater based on anionized nanocelluloses［J］. Chemical Engineering Journal，2013，231：59-67. doi:10.1016/j.cej.2013.07.010
55	SUOPAJÄRVI T， LIIMATAINEN H， HORMI O， et al. Coagulation-flocculation treatment of municipal wastewater based on anionized nanocelluloses［J］. Chemical Engineering Journal，2013，231： 59-67. doi:10.1016/j.cej.2013.07.010
56	ERAGHI KAZZAZ A， FATEHI P. Technical lignin and its potential modification routes：A mini-review［J］. Industrial Crops and Products，2020，154：112732. doi:10.1016/j.indcrop.2020.112732
57	YANG Ran， LI Haijiang， HUANG Mu，et al. A review on chitosan-based flocculants and their applications in water treatment［J］. Water Research，2016，95：59-89. doi:10.1016/j.watres.2016.02.068
58	GUO Chaoran， WANG Lingzhi， HUANG Yong，et al. Capturing organics from municipal wastewater using a primary sludge-derived polymer［J］. Journal of Water Process Engineering，2022，46：102567. doi:10.1016/j.jwpe.2022.102567
59	王灵芝. 利用水热液相产物制备污水有机物聚集介质研究［D］. 苏州：苏州科技大学，2022. doi:10.1063/5.0079108
	WANG Lingzhi. Study on the preparation of wastewater organic matter aggregation media by hydrothermal liquid phase products［D］. Suzhou：Suzhou University of Science and Technology，2022. doi:10.1063/5.0079108

[1]	刘雪奇, 周洪, 梅拥军, 张圆, 崔艾军, 高秋月. PAC/PI/PAM去除飞机除冰废水中增稠剂的研究[J]. 工业水处理, 2018, 38(3): 77-80.
[2]	李国轲, 耿仁勇, 曹慧, 高肖汉, 吕雪川, 范志平. 季铵盐阳离子有机絮凝剂的研究进展[J]. 工业水处理, 2015, 35(11): 1-4.
[3]	苗庆显, 高立芹, 秦梦华. 水处理有机絮凝剂的研究进展[J]. 工业水处理, 2006, 26(10): 14-17.
[4]	戴萍, 高宝玉, 许鹏举, 岳钦艳. BT-02有机絮凝剂与PAC复配用于印染废水的脱色研究[J]. 工业水处理, 2004, 24(12): 41-42.
[5]	陈元彩, 肖锦. 天然有机高分子絮凝剂研究与应用[J]. 工业水处理, 1999, 19(4): 11-13,45.
[6]	赵景霞, 回军, 王有华, 谢大宁, 林大泉. ZB4109絮凝剂的研制及应用[J]. , 1999, 19(1): 3-6.

选择文件类型/文献管理软件名称

选择包含的内容