Organics recovery from municipal wastewater: research advances in capture technologies

doi:10.16085/j.issn.1000-6613.2020-0878

Abstract

Abstract:

Nowadays, the problem of high energy consumption and carbon emission during the organic matter removal in municipal wastewater treatment plant becomes increasingly obvious. Subsequently, the concept of organics recovery, which has both environmental and economic profits, attracted more and more attention. Efficient capture of organic matter from low-intensity municipal wastewater to generate high concentration organics, determines the economic and technical feasibility of organics recovery. Many well-known water treatment processes, such as membrane filtration, high-loaded activated sludge process, flocculation, have been re-recognized and applied to organics capture due to their high organic matter retention characteristics. In this paper, according to the concentration process of organic matter in these technologies, they were divided into two categories: “directional aggregation” and “passive accumulation”. Based on understanding their capture mechanism, this paper further discussed the approaches to improve their capture efficiency and short slabs that need to overcome for large-scale application. Then, this paper summarized the recovery methods of the concentrated organics, and pointed out that the key of maximum recovery is to select the appropriate pretreatment according to the characteristics of concentrated organics. Finally, based on the technology maturity, energy consumption and operation cost of organics capture process, the feasibility of wastewater treatment system aiming at resource recovery was prospected.

Key words: organics recovery, organics capture, capture efficiency, high-loaded activated sludge process, flocculation, membrane filtration

摘要：

当今的城市污水处理系统中，有机物去除过程的高额能耗和碳排放问题逐渐被重视。随之，兼具环境意义和经济效益的有机物回收理念日益受到关注。而将污水中的有机物富集或浓缩到易利用的浓度，也即污水碳捕获，是影响其回收技术经济性的关键。大众熟知的水处理工艺，如膜分离、高负荷活性污泥法、絮凝等，凭借着高的有机物保留特性而被重新认识。本文根据这些工艺在捕获过程中有机物的转移方向，将它们归类为“转移聚集”（主要是高负荷活性污泥法、絮凝）和“被动富集”（主要是膜分离）两大类进行讨论。在介绍它们各自捕获机制、捕获率、研究进展的基础上，讨论进一步提升捕获率的途径及其在规模化应用中需要克服的问题。随后本文综述了捕获产物的能源化与产品化途径，并认为根据其性质选择合适的预处理是提升资源化程度的关键。最后围绕碳捕获工艺的成熟度、能耗及运行费用，讨论了生活污水资源化工艺流程的构建。

关键词: 有机物回收, 碳捕获, 捕获率, 高负荷活性污泥法, 絮凝, 膜分离

CLC Number:

X703

GUO Chaoran, HUANG Yong, ZHU Wenjuan, CHEN Liyuan, WANG Lingzhi, ZHANG Yue, XU Chutian, LI Dapeng. Organics recovery from municipal wastewater: research advances in capture technologies[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1619-1633.

郭超然, 黄勇, 朱文娟, 陈丽媛, 王灵芝, 张悦, 徐楚天, 李大鹏. 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.

Figures/Tables 11

工艺类型	污泥龄（SRT）/d	污泥负荷率（F/M，SLR） /g BOD·(gVSS)^-1·d^-1	溶解氧（DO） /mg·L^-1	水力停留时间（HRT）/h	再生时间	文献来源
工艺类型	污泥龄（SRT）/d	污泥负荷率（F/M，SLR） /g BOD·(gVSS)^-1·d^-1	溶解氧（DO） /mg·L^-1	水力停留时间（HRT）/h	/h	文献来源
传统活性污泥法（CAS）	3～15	0.2～0.6	2	4～12	—	[22,28]
高负荷活性污泥法（HRAS）	0.2～2	2～10	0.5～1	0.5～1	—	[22,28]
高负荷“吸附-再生”法（HRCS）	0.2～1	2～10	0.5～1	0.17～1	0.25～0.66	[13-14,28-29]

碳捕获工艺	所需介质	优点	缺点
混凝/絮凝	无机絮凝剂：铁、铝盐，如Al₂(SO₄)₃、FeCl₃	①价格低廉，如FeCl₃约为1200CNY·t^-1[31] ②碳捕获效果好，同时对磷去除率高	①投加量较高，一般为每升几十毫克Fe或Al ②污泥产量大 ③残余水中的铝元素过高会产生环境风险，导致在动物体内蓄积
	有机高分子絮凝剂：如聚丙烯酰胺（PAM）、聚二甲基二烯丙基氯化铵（PDADMAC）、聚乙烯亚胺（PEI）等	①投加量低，一般为每升几毫克 ②架桥能力强，其形成的絮体大而结实、沉降速度快	①单独使用时，有机碳捕获效果一般逊于无机絮凝剂 ②其中残余聚合物单体会产生环境风险。如丙烯酰胺具有中枢神经毒性^[32]
	天然高分子絮凝剂：淀粉、壳聚糖、纤维素、瓜尔胶、单宁等天然有机高分子改性后产物	①毒性小，且易在自然环境中降解 ②原料来源广泛，可从多种动植物中提取，属于可再生资源	天然原料价格仍较高，如淀粉约 5000CNY·t^-1、壳聚糖约250000CNY·t^{-1 [33]}
	微生物絮凝剂：一类微生物代谢产物，由糖蛋白、多糖、蛋白质等组成	①与污染物亲和性强，絮凝效果好 ②安全无毒，且易在自然环境中降解	①提取方法复杂繁琐、产品储存稳定性差^[34] ②离规模化生产、应用还有较大差距
	载体絮凝：在传统絮凝过程中，引入高密度的不溶解颗粒以促进絮体的增长和沉淀过程的网捕作用，常见载体有细砂、磁种（磁铁矿、钛铁矿等）^[35]	①效率高，节约絮凝剂用量 ②利用旋流器、磁鼓可将细砂、磁种这样的重介质回收再使用	对池体构型和设备技术要求高，现多为完整的专利技术，如Actiflo工艺和DensaDeg 工艺^[36]
气浮	大量、高度分散的微气泡	①无需外来补充介质 ②处理效率高、占地面积小、技术及工艺成熟	①对溶解性有机碳无捕获效果 ②对胶体和亲水性颗粒需要外加药剂强化捕获效率 ③含氧气泡释放中则会有有机碳损失
吸附	沸石、各种生物质制备的活性炭及其改性产物	对溶解性有机碳捕获能力强	吸附效率、沉降性能、能否回收及成本都面临实际考验

碳捕获工艺	所需介质	优点	缺点
混凝/絮凝	无机絮凝剂：铁、铝盐，如Al₂(SO₄)₃、FeCl₃	①价格低廉，如FeCl₃约为1200CNY·t^-1[31] ②碳捕获效果好，同时对磷去除率高	①投加量较高，一般为每升几十毫克Fe或Al ②污泥产量大 ③残余水中的铝元素过高会产生环境风险，导致在动物体内蓄积
	有机高分子絮凝剂：如聚丙烯酰胺（PAM）、聚二甲基二烯丙基氯化铵（PDADMAC）、聚乙烯亚胺（PEI）等	①投加量低，一般为每升几毫克 ②架桥能力强，其形成的絮体大而结实、沉降速度快	①单独使用时，有机碳捕获效果一般逊于无机絮凝剂 ②其中残余聚合物单体会产生环境风险。如丙烯酰胺具有中枢神经毒性^[32]
	天然高分子絮凝剂：淀粉、壳聚糖、纤维素、瓜尔胶、单宁等天然有机高分子改性后产物	①毒性小，且易在自然环境中降解 ②原料来源广泛，可从多种动植物中提取，属于可再生资源	天然原料价格仍较高，如淀粉约 5000CNY·t^-1、壳聚糖约250000CNY·t^{-1 [33]}
	微生物絮凝剂：一类微生物代谢产物，由糖蛋白、多糖、蛋白质等组成	①与污染物亲和性强，絮凝效果好 ②安全无毒，且易在自然环境中降解	①提取方法复杂繁琐、产品储存稳定性差^[34] ②离规模化生产、应用还有较大差距
	载体絮凝：在传统絮凝过程中，引入高密度的不溶解颗粒以促进絮体的增长和沉淀过程的网捕作用，常见载体有细砂、磁种（磁铁矿、钛铁矿等）^[35]	①效率高，节约絮凝剂用量 ②利用旋流器、磁鼓可将细砂、磁种这样的重介质回收再使用	对池体构型和设备技术要求高，现多为完整的专利技术，如Actiflo工艺和DensaDeg 工艺^[36]
气浮	大量、高度分散的微气泡	①无需外来补充介质 ②处理效率高、占地面积小、技术及工艺成熟	①对溶解性有机碳无捕获效果 ②对胶体和亲水性颗粒需要外加药剂强化捕获效率 ③含氧气泡释放中则会有有机碳损失
吸附	沸石、各种生物质制备的活性炭及其改性产物	对溶解性有机碳捕获能力强	吸附效率、沉降性能、能否回收及成本都面临实际考验

生活污水COD/mg·L^-1	药剂	投加量/mg·L^-1	COD去除率/%
751	硫酸铁（FS）	80	85.9	王东海等^[39]
303	氯化铁（FC）	25	77	Chen等^[27]
76.3～240.4	硫酸铝（AS）	70	79.5	黄天寅等^[40]
480±37	硫酸铝	约10	65	Chakraborty等^[17]
130～200	碱式氯化铝（BAC）	100	85	张敬东等^[41]
235～426	聚合氯化铝（PAC）+阳离子助凝剂	100+2	78	亓化亮等^[42]
522	氯化铁+阴离子助凝剂	50+10	73	Aiyuk等^[43]
300	聚丙烯酰胺（PAM）	0.1875	58.8	吴小宁^[44]
481.2	阳离子聚丙烯酰胺（CPAM）	0.5	44.8	刘海龙等^[45]
540	羧甲基瓜尔胶接枝PAM产物	9	61	Pal等^[46]
210	植物单宁阳离子改性絮凝剂	100	50	Beltrán等^[47]

膜技术	膜组件、材料、孔径	进水性质	富集程度	膜通量 /L·m^-2·h^-1	跨膜压差（TMP）/10⁴Pa	清洗方式	文献
微滤	中空纤维式，PVDF（聚偏氟乙烯），0.1μm	城市污水（格栅出水），COD 345.3mg·L^-1±157.25mg·L^-1，含30mg·L^-1 PAC（聚氯化铝）	COD捕获率70%，浓缩液COD 16g·L^-1	总均值13.3（共295h，含3个周期）	<7	当TMP达到7×10⁴Pa时进行物理清洗	[10]
微滤	中空纤维膜，PVDF，0.1μm，二级MF串联	城市污水（初沉池进水），COD 240mg·L^-1	COD捕获率75%，二级浓缩液COD 3600～6843mg·L^-1	恒定膜通量运行，MF1 20.8，MF2 16.7	UF1<3 UF2 <2 200h	每隔12h进行30s的化学清洗，药剂为次氯酸钠或柠檬酸	[23]
动态膜过滤	平板式，3层不锈钢筛网，25μm	城市污水（格栅出水），COD 305mg·L^-1	COD去除率63%，浓缩液COD 2～2.5g·L^-1	30～60（共192h，含4个周期）	<4	每隔一个周期（48h）进行一次表面气扫反冲洗	[9]
陶瓷膜过滤	平板式，α-Al₂O₃，0.1μm	城市污水，COD 233.0mg·L^-1±30.0mg·L^-1，含FeCl₃ 20mg Fe·L^-1	COD去除率：90%浓缩液COD约2.1g·L^-1	恒定膜通量运行，41.7	<3.5	每隔3～5d进行一次化学清洗，药剂为酸碱、次氯酸钠或双氧水	[63]
正渗透	平板式，CTA（三醋酸纤维），0.3～1nm，（HTI生产）	城市污水（初沉出水），COD 522mg·L^-1，驱动液NaCl 0.5～4mol·L^-1	COD去除率96.5%，浓缩液COD 2714～3289mg·L^-1	受驱动液影响，初始在25到8不等，体积浓缩10倍后维持在5左右	—	气水冲洗+化学清洗（1%次氯酸钠浸泡）	[74]
正渗透	平板式，CTA（三醋酸纤维），0.3～1nm，（HTI生产）	人工配水，TOC 163.4 mg·L^-1，驱动液NaCl 0.5~4mol·L^-1	TOC去除率97%，污水体积缩小10倍，TOC富集4.4～5.9倍	5.3～6.4（共168h，含7个周期）	—	化学清洗（1%次氯酸钠浸泡）	[75]

碳捕获工艺	污泥龄	加药	TN去除率/%	NH $4 +$ -N去除率/%	TP去除率/%	PO $4 3 -$ -P去除率/%	文献
HRAS	SRT=0.5d	无	22.3±4.6	8.2±2.1	15.2±2.1	5.1±2.3	[80]
	SRT=2.4d	无	42.6±4.1	29.6±3.0	28.3±4.7	14.7±2.0
	SRT=0.22d	无	—	17±4	35±11	43±8	[21]
	SRT=0.22d	无	—	12±4	23±5	29±9
	SRT=0.9d	无	—	19±4	—	13±4	[16]
		30mg·L^-1 FeCl₃	—	—	—	99
CEPT	—	25mg·L^-1 FeCl₃	—	9.1	95	—	[27]
动态膜过滤	—	无	22.9	8.7	14.5	5.8	[9]
陶瓷膜过滤	—	15mg-Al·L^-1	—	43.1	99.5	—	[63]
正渗透	—	无	94.9	94.1	95.3	—	[67]

碳捕获工艺	污泥龄	加药	TN去除率/%	NH $4 +$ -N去除率/%	TP去除率/%	PO $4 3 -$ -P去除率/%	文献
HRAS	SRT=0.5d	无	22.3±4.6	8.2±2.1	15.2±2.1	5.1±2.3	[80]
	SRT=2.4d	无	42.6±4.1	29.6±3.0	28.3±4.7	14.7±2.0
	SRT=0.22d	无	—	17±4	35±11	43±8	[21]
	SRT=0.22d	无	—	12±4	23±5	29±9
	SRT=0.9d	无	—	19±4	—	13±4	[16]
		30mg·L^-1 FeCl₃	—	—	—	99
CEPT	—	25mg·L^-1 FeCl₃	—	9.1	95	—	[27]
动态膜过滤	—	无	22.9	8.7	14.5	5.8	[9]
陶瓷膜过滤	—	15mg-Al·L^-1	—	43.1	99.5	—	[63]
正渗透	—	无	94.9	94.1	95.3	—	[67]

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