强化废水厌氧消化过程的导电材料及其特性影响

doi:10.16085/j.issn.1000-6613.2023-2163

摘要/Abstract

摘要：

厌氧消化是微生物在厌氧环境下降解有机底物并产生沼气的生物处理工艺，在降低能源依赖方面具有巨大潜力。然而传统厌氧技术由于甲烷产率低、微生物富集慢、反应器运行不稳定等问题，造成能源消耗和处理成本不断增加。导电材料可刺激互营细菌和产甲烷古菌之间的种间电子传递，进而提高产甲烷效率，广泛应用于废水厌氧处理领域。本文在梳理了碳基、金属基及其他导电材料介导厌氧消化强化效能的基础上，着重介绍了复合材料协同作用在高效生物降解和运行高稳定性方面的优势。从粒径、导电性能、表面特征等方面论述了材料不同物理化学特性对强化厌氧消化性能的影响，并对导电材料强化废水厌氧生物降解的研究前景进行了展望。

关键词: 厌氧消化, 直接种间电子传递, 碳基导电材料, 金属基导电材料, 复合导电材料

Abstract:

Anaerobic digestion of wastewater is a biological treatment process in which microorganisms degrade organic substrates in an anaerobic environment and produce biogas, which has great potential to reduce energy dependence. However, due to the low methane yield, easy acidification, slow microbial enrichment, and unstable reactor operation, the traditional anaerobic technology has caused increasing energy consumption and treatment costs. Conductive materials can stimulate the interspecific electron transfer between syntrophic bacteria and methanogenic archaea, thereby improving the efficiency of methanogenesis, and are widely used in the field of wastewater anaerobic treatment. On the basis of sorting out the enhanced efficiency of carbon-based, metal-based and other conductive materials mediated anaerobic digestion, the advantages of composite synergistic effect in efficient biodegradation and high stability of operation were emphatically introduced. The effects of different physical and chemical properties of materials on enhanced anaerobic digestion performance were discussed from the aspects of particle size, conductivity and surface characteristics, and the research prospect of enhanced anaerobic biodegradation of wastewater by conductive materials was prospected.

Key words: anaerobic digestion, direct interspecies electron transfer, carbon-based conductive materials, metal-based conductive materials, composite conductive materials

中图分类号:

X592

吕龙义, 韩沐达, 马培禹, 及文博, 王新元, 高文芳, 任芝军. 强化废水厌氧消化过程的导电材料及其特性影响[J]. 化工进展, 2024, 43(12): 6957-6967.

LYU Longyi, HAN Muda, MA Peiyu, JI Wenbo, WANG Xinyuan, GAO Wenfang, REN Zhijun. Conductive materials for enhanced anaerobic digestion of wastewater and influence of their properties[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 6957-6967.

图/表 6

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次数	12	67
比例	15%	85%

导电材料	废水种类	投加量/g·L^-1	反应体系	强化效果	参考文献
活性炭	食物垃圾废水	15	血清瓶	同等OLR下，平均CH₄产率为4.7g/(L·d)，是无AC反应器的2.5倍	[10]
颗粒活性炭	乳品废水	2	SBR	在每个循环运行结束时，CH₄产量增加了68%~125%	[11]
颗粒活性炭	垃圾焚烧渗滤液	75	UASB	对照组立即变质并在17天内坍塌；GAC组OLR提高到25.0kg/m³时，COD去除率保持在90%左右	[12]
颗粒活性炭	合成废水	25	UASB	COD去除率从56%提高到82%，CH₄产量从132mL/g提高到264mL/g	[13]
粉末活性炭	葡萄糖、生物油	10	血清瓶	CH₄产量提高24%，COD去除率提高15%	[14]
粉末活性炭	垃圾渗滤液	10	SBR	与对照组相比，PAC和PAC双反应沉淀组COD去除效率分别提高140%和78%	[15]
生物炭	葡萄糖	10	血清瓶	CH₄产率相比于对照组提高17.80%	[10]
生物炭	合成废水	5	UASB	CH₄产率相比于对照组提高1.47倍	[16]
碳布	新鲜渗滤液	10块	UASB	高有机负荷下，COD去除率从30%提高到80%	[17]
碳毡	葡萄糖和甘氨酸	—	CSTR	相比对照组，实验组的CH₄产率提高10.1%~23.0%	[18]
碳纤维	丙酸-丁酸盐	—	CSTR	CH₄比产量（mL/g）和产CH₄速率（d^-1）分别增加约2.4倍和6.7倍	[19]
单壁碳纳米管	葡萄糖	1	CSTR	CH₄产量和产率分别提高1.63倍和1.92倍	[20]
多壁碳纳米管	甜菜糖废水	1.5	EGSB	CH₄产量相比于对照组提高1.12倍	[21]
石墨	垃圾渗滤液	—	AnMBR	当进水COD浓度为3000mg/L时，COD去除率为78%；石墨可有效缓解膜污染	[22]
石墨毡	丙酸盐	—	ASBR	与对照组相比，CH₄产率提高19.1%	[23]
石墨烯	氨基乙酸	0.25~2	血清瓶	材料投加量为0.5~1g/L时，CH₄产量提高4%~6%	[24]
纳米石墨烯	合成废水	0.12	血清瓶	CH₄产量和产率分别提高1.5倍和1.51倍	[25]

导电材料	废水种类	投加量/g·L^-1	反应体系	强化效果	参考文献
活性炭	食物垃圾废水	15	血清瓶	同等OLR下，平均CH₄产率为4.7g/(L·d)，是无AC反应器的2.5倍	[10]
颗粒活性炭	乳品废水	2	SBR	在每个循环运行结束时，CH₄产量增加了68%~125%	[11]
颗粒活性炭	垃圾焚烧渗滤液	75	UASB	对照组立即变质并在17天内坍塌；GAC组OLR提高到25.0kg/m³时，COD去除率保持在90%左右	[12]
颗粒活性炭	合成废水	25	UASB	COD去除率从56%提高到82%，CH₄产量从132mL/g提高到264mL/g	[13]
粉末活性炭	葡萄糖、生物油	10	血清瓶	CH₄产量提高24%，COD去除率提高15%	[14]
粉末活性炭	垃圾渗滤液	10	SBR	与对照组相比，PAC和PAC双反应沉淀组COD去除效率分别提高140%和78%	[15]
生物炭	葡萄糖	10	血清瓶	CH₄产率相比于对照组提高17.80%	[10]
生物炭	合成废水	5	UASB	CH₄产率相比于对照组提高1.47倍	[16]
碳布	新鲜渗滤液	10块	UASB	高有机负荷下，COD去除率从30%提高到80%	[17]
碳毡	葡萄糖和甘氨酸	—	CSTR	相比对照组，实验组的CH₄产率提高10.1%~23.0%	[18]
碳纤维	丙酸-丁酸盐	—	CSTR	CH₄比产量（mL/g）和产CH₄速率（d^-1）分别增加约2.4倍和6.7倍	[19]
单壁碳纳米管	葡萄糖	1	CSTR	CH₄产量和产率分别提高1.63倍和1.92倍	[20]
多壁碳纳米管	甜菜糖废水	1.5	EGSB	CH₄产量相比于对照组提高1.12倍	[21]
石墨	垃圾渗滤液	—	AnMBR	当进水COD浓度为3000mg/L时，COD去除率为78%；石墨可有效缓解膜污染	[22]
石墨毡	丙酸盐	—	ASBR	与对照组相比，CH₄产率提高19.1%	[23]
石墨烯	氨基乙酸	0.25~2	血清瓶	材料投加量为0.5~1g/L时，CH₄产量提高4%~6%	[24]
纳米石墨烯	合成废水	0.12	血清瓶	CH₄产量和产率分别提高1.5倍和1.51倍	[25]

导电材料	反应底物	投加量/g·L^-1	反应器	强化效果	参考文献
针铁矿	醋酸、丙酸和丁酸	5	血清瓶	CH₄产量增加40%~165%，改善酸胁迫下的性能	[36]
磁铁矿	醋酸盐	2	ASTR	COD去除率和CH₄产量相比对照组分别提高31.1%和101.5%	[37]
赤铁矿	合成废水	0.75	血清瓶	CH₄产量相比对照组增加35%	[38]
ZVI	合成废水	0.2~5	血清瓶	投加量为2g/L时，CH₄产量提高84.12%	[39]
Fe₃O₄	合成废水	10	ASBR	最大CH₄产率提高15.4%，滞后期缩短13.9%	[40]
Fe₂O₃	合成废水	30mmol/L	血清瓶	CH₄产量相比于对照组提高22.4%	[41]
Fe(OH)₃	合成废水	30mmol/L	血清瓶	CH₄产量比对照组高38.2%	[41]
nZVI	合成蔗糖废水	50mmol/L	塑料厌氧反应器	COD去除率降低30.4%，CH₄产量降低22.5%	[42]
nFe₃O₄	合成蔗糖废水	50mmol/L	塑料厌氧反应器	COD去除率提高26.1%，CH₄产量提高76.2%	[42]

导电材料	反应底物	投加量/g·L^-1	反应器	强化效果	参考文献
针铁矿	醋酸、丙酸和丁酸	5	血清瓶	CH₄产量增加40%~165%，改善酸胁迫下的性能	[36]
磁铁矿	醋酸盐	2	ASTR	COD去除率和CH₄产量相比对照组分别提高31.1%和101.5%	[37]
赤铁矿	合成废水	0.75	血清瓶	CH₄产量相比对照组增加35%	[38]
ZVI	合成废水	0.2~5	血清瓶	投加量为2g/L时，CH₄产量提高84.12%	[39]
Fe₃O₄	合成废水	10	ASBR	最大CH₄产率提高15.4%，滞后期缩短13.9%	[40]
Fe₂O₃	合成废水	30mmol/L	血清瓶	CH₄产量相比于对照组提高22.4%	[41]
Fe(OH)₃	合成废水	30mmol/L	血清瓶	CH₄产量比对照组高38.2%	[41]
nZVI	合成蔗糖废水	50mmol/L	塑料厌氧反应器	COD去除率降低30.4%，CH₄产量降低22.5%	[42]
nFe₃O₄	合成蔗糖废水	50mmol/L	塑料厌氧反应器	COD去除率提高26.1%，CH₄产量提高76.2%	[42]

导电材料	反应底物	投加量/g·L^-1	反应器	强化效果	参考文献
PANI	偶氮染料废水	0.1~0.8	血清瓶	添加0.4g/L PANI可以使厌氧污泥的脱色效率提高约20%	[49]
PANI纳米棒	蔗糖	0.6	血清瓶	0.6g/L PANI纳米棒的剂量使CH₄的产生加速了约2倍	[50]
Fe₃O₄@PANI	葡萄糖	0.6~5.4	血清瓶	CH₄产率提高26.98%；最佳用量为0.6g/L	[51]
Fe₂O₃@PANI	葡萄糖	1.2	血清瓶	Fe₂O₃@PANI复合改良厌氧系统的CH₄产量是添加氧化铁和PANI的系统总和的约1.5倍	[52]
ZVI@C@PANI	合成废水	1.8~2.5	血清瓶	在最佳剂量（2g/L）下，与未添加纳米复合材料的厌氧系统相比，CH₄产量增加了71.36%	[53]
PPy@PANI	葡萄糖	0.2~1.4	血清瓶	在初始4h内，CH₄产率提高70.2%，产量增加28.3%；最佳用量为0.6g/L	[54]
PU/(PPy+PANI)	城市废水	1.8	nMBR	投加PU/(PPy+PANI)的中试组在间歇模式下COD去除率为80%	[55]
PANI水凝胶	蔗糖	0.1~0.4	血清瓶	材料添加0.3g/L，CH₄生成率提高了28.77%	[56]
PANI + PET	醋酸钠	—	血清瓶	与空白组相比，CH₄产率提高9%	[57]
PANI + PVDF	醋酸钠	—	血清瓶	与空白组相比，CH₄产率提高25%	[57]
PPy	废弃污泥	0.3	血清瓶	PPy使累积CH₄产量提高了27.83%	[58]
聚乙烯+石墨粉	合成废水	0.0181~0.0354	连续流反应器	与无石墨的HDPE组相比，CH₄的产率提高7.8%~26.6%；与空白组相比，提高了15.5%~31.3%	[59]
改性黑磷	合成废水	0.03%~0.15%	玻璃反应釜	质量分数0.03%组沼气产量和TCOD去除率（387.6mL/g和71.5%）高于空白组（326.3mL/g和55.5%）	[60]
高炉粉尘	合成废水	0.02~0.05	UASB	CH₄产量增加了73%~346%	[61]
胆碱	废弃活性污泥	0~1	蒸煮器	以0.75g/L作为最佳胆碱给药浓度，EGs中的累积沼气产量增加了35.55%~36.73%	[62]
次氯酸钙	废弃活性污泥	0~1.25	血清瓶	CH₄含量从0提高到1.0g/L，CH₄的产量从(164.8±4.2)mL/g增加到(220.5±6.2)mL/g	[63]
钨酸钠	废弃污水污泥	0~0.25	分批厌氧消化器	在钨酸钠存在下，甲烷菌的占比从3.02%显著增加到31.20%	[64]
不锈钢	合成废水	0~6.4	UASB	CH₄产量从39.4mL/d增加到159.9mL/d	[65]
TiO₂	合成废水	0~2	厌氧间歇反应器	CH₄产量相比于对照组提高14%	[66]
泡沫镍	乙醇	2.45	槽式反应器	CH₄的最大产率达到94.5mL/(g·d)，与对照相比增加了27.4%	[47]