基于pH调控的城市污泥厌氧发酵产酸小试研究

本研究设计了热碱预处理-半连续流厌氧发酵污泥处理工艺,探究了p H对热碱预处理污泥产酸性能的影响,同时对发酵液作为碳源回用于污水厂强化脱氮除磷进行了质量衡算.在30 L厌氧发酵罐中考察了偏中性(p H=6.5)和碱性(p H=10.0)条件下热碱预处理污泥发酵的挥发性脂肪酸(VFA)产生及分布、蛋白质及碳水化合物的消耗和氮磷释放情况.结果表明,污泥热碱预处理-半连续流厌氧发酵工艺的VFA产量稳定,在p H为6.5和10.0的条件下,发酵罐中平均VFA产率分别为333.29 mg·g-1(以每g VS产生的COD(mg)计,下同)和250.64 mg·g-1,p H为6.5时产酸更稳定,且产量较高,但碱性条件更适合产乙酸.两种p H条件下的SCOD、溶解性蛋白质、溶解性多糖、氮和磷的释放都无较大差异.质量衡算结果表明,以处理量为50000 m3·d-1的城市污水处理厂为例,其产生的污泥经过热碱预处理-半连续流厌氧发酵产酸工艺,产生的VFA能够满足该污水处理厂脱氮除磷提标改造的碳源需求.     

剩余污泥微波-淘洗及零价铁强化发酵性能

为解决微波预处理高含固率污泥存在碳源溶出率低和释放的碳源有效性低的问题,本文选用淘洗的方法,同时将零价铁（ZVI）添加到淘洗污泥的混合液和上清液中进行厌氧发酵以强化碳源的有效性.结果表明,淘洗显著提升了微波预处理高含固率（TS=11%~17%）污泥的碳溶出率,水淘和碱淘较未淘洗时碳源溶出率分别提高了13%~68%、146%~308%.ZVI的加入不仅显著提高了挥发性脂肪酸（VFAs）溶出率,还能将大分子碳源定向转化为乙酸、丙酸等低分子碳源.混合液+ZVI、上清液+ZVI发酵的VFAs溶出量分别为317和354mg/g VSS,超过微波污泥VFAs溶出量的30倍.添加ZVI发酵后,丙酸、乙酸、丁酸等小分子碳源的比例有所上升,混合液中的占比分别为34%、26%、18%,上清液中的占比分别为39%、27%、20%,提升了污泥碳源的利用价值.研究表明,微波-淘洗预处理联合ZVI发酵技术能够有效提高剩余污泥中高效碳源的溶出率,这为剩余污泥的碳源化提供了一条新思路.     

Potassium ferrate pretreatment promotes short chain fatty acids yield and antibiotics reduction in acidogenic fermentation of sewage sludge

During the acidogenic fermentation converting waste activated sludge (WAS) into short-chain fatty acids (SCFA), hydrolysis of complex organic polymers is a limiting step and the transformation of harmful substances (such as antibiotics) during acidogenic fermentation is unknown. In this study, potassium ferrate (K₂FeO₄) oxidation was used as a pretreatment strategy for WAS acidogenic fermentation to increase the hydrolysis of sludge and destruct the harmful antibiotics. Pretreatment with K₂FeO₄ can effectively increase the SCFA production during acidogenic fermentation and change the distribution of SCFA components. With the dosage of 0.2 g/g TS, the maximum SCFA yield was 4823 mg COD/L, which is 28.3 times that of the control group; acetic acid accounts for more than 90% of the total SCFA. The higher dosage (0.5 g/g TS) can further increase the proportion of acetic acid, but inhibit the overall performance of SCFA production. Apart from the promotion of hydrolysis and acidogenesis, K₂FeO₄ pretreatment can also simultaneously oxidizes and degrades part of the antibiotics in the sludge. When the dosage is 0.5 g/g TS, the degradation efficacy of antibiotics is the most significant, and the contents of ofloxacin, azithromycin, and tetracycline in the sludge are reduced by 69%, 42%, and 50%, respectively. In addition, K₂FeO₄ pretreatment can also promote the release of antibiotics from sludge flocs, which is conducive to the simultaneous degradation of antibiotics in the subsequent biological treatment process.     

利用养殖场废水厌氧发酵生物制氢技术研究

在批式厌氧反应器中,以厌氧消化污泥作为天然产氢菌源,通过养殖场废水的厌氧发酵生产氢气,考察了厌氧污泥和碳氮营养物质对养殖场废水产氢的影响,并对液相产物的分布、产氢动力学进行了分析.试验分为4个处理.结果表明,加入营养物质接种污泥的养殖场废水氢气含量、累积产氢量和单位COD氢气产量最高可达到50.65%、334.80mL和287.10mL/g.而未接种污泥的原始养殖场废水累积产氢量和单位COD氢气产量仅为59.24mL和67.05mL/g.污泥和碳氮营养物质对产氢能力均有显著地促进作用,加入碳氮源后微生物群促进了原养殖废水有机物的氢的形成.液相末端产物中,乙酸、丁酸占总挥发酸的61%～86%,产氢过程属于典型的乙酸-丁酸型发酵.总挥发性酸含量的提高,其产氢能力也增大. Gompertz模型能够很好地拟合其产氢过程.     

Mechanisms of allicin exposure for the sludge fermentation enhancement: Focusing on the fermentation processes and microbial metabolic traits

As a frequently used product with antimicrobial activity, consumed allicin might be discharged and concentrated in waste-activated sludge (WAS). However, the influence of allicin (as an exogenous pollutant) on WAS fermentation has not been clearly revealed. This study aimed to disclose the impacts of allicin on volatile fatty acid (VFA) generation during WAS fermentation. The results showed that the appropriate presence of allicin (10 mg/g TSS) significantly enhanced the VFA yield (1894 versus 575 mg COD/L in the control) with increased acetate proportion (24.3%). Further exploration found that allicin promoted WAS solubilization, hydrolysis and acidification simultaneously. Metagenomic analysis revealed that the key genes involved in extracellular hydrolysis metabolism (i.e., CAZymes), membrane transport (i.e., gtsA and ytfT), substrate metabolism (i.e., yhdR and pfkC) and fatty acid synthesis (i.e., accA and accD) were all highly expressed. Allicin also induced the bacteria to produce more signalling molecules and regulate cellular functions, thereby enhancing the microbial adaptive and regulatory capacity to the unfavourable environment. Moreover, the variations in fermentative microbes and their contributions to the upregulation of functional genes (i.e., ytfR, gltL, INV, iolD and pflD) for VFA generation were disclosed. Overall, the simultaneous stimulation of functional microbial abundances and metabolic activities contributed to VFA production in allicin-conditioned reactors.     

Influence of carbon sources on nutrient removal in A/O-MBRs: Availability assessment of internal carbon source

Both internal carbon source and some external carbon sources were used to improve the nutrient removal in Anaerobic-Anoxic-Oxic-Membrane Bioreactor (A²/O-MBRs), and their technical and cost analysis was investigated. The experimental results showed that the nutrient removals were improved by all the carbon source additions. The total nitrogen and phosphorus removal efficiency were higher in the experiments with external carbon source additions than that with internal carbon source addition. It was found that pathways of nitrogen and phosphorus transform were different dependent on different carbon source additions by the mass balance analysis. With external carbon source addition, the simultaneous nitrification and denitrification occurred in aerobic zone, and the P-uptake in aerobic phase was evident. Therefore, with addition of C-MHP (internal carbon source produced from sludge pretreatment by microwave-H₂O₂ process), the denitrification and phosphorus-uptake in anoxic zone was notable. Cost analysis showed that the unit nitrogen removal costs were 57.13 CNY/kg N of C-acetate addition and 54.48 CNY/kgN of C-MHP addition, respectively. The results indicated that the C-MHP has a good technical and economic feasibility to substitute external carbon sources partially for nutrient removal.     

零价铁和微波预处理组合强化污泥厌氧消化

以中温(100℃)常压的微波预处理结合零价铁投加为对象,考察了低投加量5. 19～41. 51 g·kg~(-1)(以TS计)、高投加量83. 35～853. 46 g·kg~(-1)(以TS计)下的零价铁对微波预处理污泥厌氧消化的进一步强化作用.结果表明,微波预处理与零价铁组合可使污泥厌氧消化产甲烷潜势提升17%～23%.零价铁对微波预处理后污泥厌氧消化具有一定的促进作用,且提升了厌氧消化初期(1～4 d)产甲烷速率,零价铁投加量为31. 13 g·kg~(-1)(以TS计)时,产甲烷潜势提升了7. 42%,反应第2 d的产甲烷速率提高了11. 02%.高投加量的零价铁并未表现出更好的强化效果.零价铁促进了厌氧消化初期溶解性有机物的释放,投加量为31. 13 g·kg~(-1)(以TS计)时,溶解性蛋白质较单独预处理组提高21. 16%,并且零价铁投加加快了乙酸、异丁酸、异戊酸的消耗.零价铁的投加,导致上清液中的磷酸根和硫酸根浓度降低,相应地,上清液中铁元素的浓度反而下降,说明零价铁的形态转化后,易与磷酸盐、硫反应形成沉淀,这可能是铁投加作用效果不明显的重要原因.     

盐度强化剩余污泥碱性发酵产酸

短链脂肪酸(SCFAs)是生物脱氮除磷的优质碳源,为提高剩余污泥碱性发酵SCFAs的产量,分别在20℃和35℃条件下,考察了不同盐度(0~25g/L)对剩余污泥碱性(pH=10)发酵的影响.结果表明:在20℃和35℃条件下,投加适量的氯化钠均可提高SCFAs产量,且氯化钠投加量为15g/L时SCFAs产量最大,较不投加时分别提高了42.3%和15.0%.进一步的研究表明,适量的投加氯化钠促进了生成SCFAs所需底物(蛋白质和多糖)的释放,同时提高了发酵系统的C/N(SCFAs/NH4+-N).因此,盐度联合碱性pH值可强化剩余污泥发酵产生SCFAs,同时达到剩余污泥减量的效果.     

Optimizing food waste hydrothermal parameters to reduce Maillard reaction and increase volatile fatty acid production

The occurrence of the Maillard reaction and melanoidins formation during the hydrothermal treatment of food waste can reduce the yield of volatile fatty acids (VFA); however, few studies have investigated the adverse effects of the Maillard reaction. This study identified the impact of hydrothermal treatment parameters on hydrolysis and melanoidins formation and optimized the hydrothermal treatment conditions to enhance VFA production by minimizing the impact of the Maillard reaction. A response surface methodology was employed to optimize the hydrothermal treatment parameters and VFA production was evaluated. Results showed that temperature, reaction time, and pH were significant interacting factors with respect to hydrolysis and melanoidins formation while the C/N ratio and moisture content of food waste had little impact. The optimal conditions for hydrothermal treatment (temperature of 132 °C, reaction time of 27 min, and a pH of 5.6) enhanced VFA production by 22.1%. Under optimal hydrothermal treatment conditions, a higher initial C/N ratio further increased VFA production.     

流量分配对短程生物脱氮过程中N2O产生的影响

利用SBR反应器,通过在线pH曲线控制好氧-缺氧反应时间,成功实现了短程生物脱氮,并考察了分段进水条件下流量分配对SBR反应器运行性能及N2O产量的影响.结果表明,与原水分2次在不同阶段等量加入反应器的二段进水方式相比,原水分3次等量进入反应器的三段进水方式能够有效降低脱氮过程中外碳源投加量和氧化亚氮产量;氧化亚氮主要产生于硝化过程,反硝化过程能够将硝化阶段积累的N2O还原至N2.2次、3次等量进水条件下,生物短程脱氮过程中乙醇投加量分别为0.8和0.6 mL,N2O释放量分别为8.86和5.05 mg·L-1(以N计).硝化过程中NO-2-N的积累是导致系统N2O产生的主要原因.     

利用剩余污泥水解酸化液合成聚羟基脂肪酸酯的研究

以城市污水处理厂剩余污泥水解酸化产物为原料,研究了罗氏真养菌(Ralstonia eutropha)H16在水解酸化液中的生长规律和聚羟基脂肪酸酯(PHAs)积累特性,同时分析了H16对水解酸化液中各种有机酸组分的利用规律. 结果表明,以剩余污泥52℃中温水解酸化48h的水解酸化液为培养基,在HAc水解酸化液(C/N/P=100/10/1, TOC＝2881mg/L,乙酸占总有机酸含量36.1%)中,H16最先利用乙酸和正丁酸来进行自身的生长和PHAs的合成,合成的主要产物是聚羟基丁酸酯(PHB);随后开始利用丙酸和正戊酸,在此过程中聚羟基戊酸酯(PHV)的含量也逐步上升,菌体量同步增长, H16在40h左右处于平稳期,并且达到最大积累率为12.51%(占菌体干重);最后利用的是异丁酸和异戊酸,但是此时H16已经进入衰亡期,菌体量和PHAs合成率都在下降.当以HVa水解酸化液(C/N/P=100/10/1, TOC＝2358mg/L,异戊酸占总有机酸含量29.0%)为培养基时, H16在18h达到生长的峰值,24h达到PHAs合成率的最大值为32.14%(占菌体干重),PHV为PHAs的主要形式.     

剩余污泥微生物发酵合成微生物油脂制备生物柴油技术研究

提高剩余污泥微生物发酵合成微生物油脂的含量是促进剩余污泥制备生物柴油技术的重要研究方向.本研究首先比较了BD法、二甲亚砜-甲醇法和酸热法对剩余污泥微生物油脂提取率的影响.结果发现,酸热法提取得到的微生物油脂含量最高,进一步甲酯化合成的生物柴油产率最高达到2.1%.通过控制发酵过程pH和调节初始C/N,可以提高剩余污泥微生物发酵合成可酯化油脂的含量,在pH=4、C/N=100条件下发酵合成的微生物油脂甲酯化得到的生物柴油产量和产率可提高至1.81 g·L~(-1)和13.06%.在此基础上重点比较了4种模拟含糖废水对剩余污泥微生物发酵合成油脂的影响.结果表明,木糖为碳源时合成的微生物油脂进一步甲酯化为生物柴油的产量和产率显著高于乳糖、蔗糖和葡萄糖,分别达到3.90 g·L~(-1)和24.55%.研究表明,以剩余污泥微生物为菌源,采用木糖等含糖废水为培养基,通过控制发酵条件可以强化剩余污泥微生物合成可酯化的微生物油脂含量,进而提高生物柴油产量.     

An innovative wood-chip-framework substrate used as slow-release carbon source to treat high-strength nitrogen wastewater

Removal of nitrogen in wastewater before discharge into receiving water courses is an important consideration in treatment systems. However, nitrogen removal efficiency is usually limited due to the low carbon/nitrogen (C/N) ratio. A common solution is to add external carbon sources, but amount of liquid is difficult to determine. Therefore, a combined wood-chip-framework substrate (with wood, slag and gravel) as a slow-release carbon source was constructed in baffled subsurface-flow constructed wetlands to overcome the problem. Results show that the removal rate of ammonia nitrogen (NH₄⁺-N), total nitrogen (TN) and chemical oxygen demand (COD) could reach 37.5%–85%, 57.4%–86%, 32.4%–78%, respectively, indicating the combined substrate could diffuse sufficient oxygen for the nitrification process (slag and gravel zone) and provide carbon source for denitrification process (wood-chip zone). The nitrification and denitrification were determined according to the location of slag/gravel and wood-chip, respectively. Nitrogen removal was efficient at the steady phase before a shock loading using slag-wood-gravel combined substrate because of nitrification–denitrification process, while nitrogen removal was efficient under a shock loading with wood-slag-gravel combined substrate because of ANAMMOX process. This study provides a new idea for wetland treatment of high-strength nitrogen wastewater.     

Life cycle comparison of hydrothermal liquefaction and lipid extraction pathways to renewable diesel from algae

Algae biomass is an attractive biofuel feedstock when grown with high productivity on marginal land. Hydrothermal liquefaction (HTL) produces more oil from algae than lipid extraction (LE) does because protein and carbohydrates are converted, in part, to oil. Since nitrogen in the algae biomass is incorporated into the HTL oil, and since lipid extracted algae for generating heat and electricity are not co-produced by HTL, there are questions regarding implications for emissions and energy use. We studied the HTL and LE pathways for renewable diesel (RD) production by modeling all essential operations from nutrient manufacturing through fuel use. Our objective was to identify the key relationships affecting HTL energy consumption and emissions. LE, with identical upstream growth model and consistent hydroprocessing model, served as reference. HTL used 1.8 fold less algae than did LE but required 5.2 times more ammonia when nitrogen incorporated in the HTL oil was treated as lost. HTL RD had life cycle emissions of 31,000 gCO₂ equivalent (gCO₂e) compared to 21,500 gCO₂e for LE based RD per million BTU of RD produced. Greenhouse gas (GHG) emissions increased when yields exceeded 0.4 g HTL oil/g algae because insufficient carbon was left for biogas generation. Key variables in the analysis were the HTL oil yield, the hydrogen demand during upgrading, and the nitrogen content of the HTL oil. Future work requires better data for upgrading renewable oils to RD and requires consideration of nitrogen recycling during upgrading.     

过氧化钙(CaO2)联合生物炭对河道底泥的修复

底泥内源污染是导致河道黑臭反复的主要因素.为防止河道黑臭现象反复,以无锡市滨湖区某一河道为实验地点,采用CaO_2联合生物炭原位覆盖技术修复黑臭河道底泥,研究了该技术对泥水水质、底泥酸挥发性硫化物(AVS)和磷形态以及微生物的影响,探究该技术对黑臭底泥修复效果.结果表明, CaO_2联合生物炭覆盖可显著提高泥水体系溶解氧(DO)浓度和氧化还原电位(ORP),其中上覆水DO浓度和ORP分别保持在2 mg·L~(-1)和50 mV以上.间隙水氨氮(NH~+_4-N)、化学需氧量(COD)和总磷(TP)去除率分别达到了43.40%、 41.18%和50.97%.底泥AVS去除率达到了37.03%,高通量测序表明,底泥厌氧微生物相对丰度明显降低,出现热单胞菌属(Thermomonas)、Dechloromonas、变形菌属(Proteus hauser)、脱硫微菌属(Desulfomicrobium)和硫杆菌属(Thiobacillus)等脱氮除硫菌群.底泥中磷转化为稳定的铁铝结合态磷和钙结合态磷.因此,CaO_2联合生物炭原位覆盖对黑臭底泥具有良好的修复作用.     

污泥厌氧产酸发酵液作碳源强化污水脱氮除磷中试研究

为研究城市污泥厌氧产酸发酵液作为补充碳源强化生活污水脱氮除磷系统的效果和可行性,建造了一个总有效体积为4 660 L的A2/O中试反应系统,以实际城市污水为研究对象,考察了添加污泥产酸发酵液后的污水脱氮除磷效果并和单纯添加乙酸作碳源的效果进行了比较.结果表明,在进水COD为243.7 mg·L-1、NH+4-N为30.9 mg·L-1、TN为42.9 mg·L-1、TP为2.8 mg·L-1、硝化液回流比为200%和污泥回流比为100%的条件下,向缺氧池中投加乙酸能增强系统脱氮除磷效果,反应器的最佳进水流量和投加碳源SCOD增量分别为7 500 L·d-1和50 mg·L-1.污泥发酵液代替乙酸作为外加碳源时的平均出水COD、NH+4-N、TN和TP去除率分别为81.60%、88.91%、64.86%和87.61%,相对应的出水浓度分别为42.18、2.77、11.92和0.19 mg·L-1,满足我国《城镇污水处理厂污染物排放标准》GB 18918-2002所规定的一级A标准.结果表明,投加污泥产酸发酵液作为脱氮除磷碳源可达到和乙酸同样的效果,具有实际可行性,这为城市污泥处理处置实现资源化提供了一条新的可行途径.     

pH对果蔬、园林垃圾混合厌氧水解产酸的影响

采用厌氧水解技术处理果蔬、园林混合垃圾,探究pH值对产酸效果的影响。在45℃、pH=6的条件下,第11天时反应器内消化液的挥发性脂肪酸(VFA)浓度达到最大值12.94 g/L,是未调控pH条件下VFA浓度的3.37倍,同时使达到最大值的时间减少了20%,大大提高了产酸效率。同时,调控pH可以促进溶解性有机物(SCOD)转化为挥发性脂肪酸,VFA/SCOD在pH=6条件下第11天时达到最大值,为48.73%。进一步对比分析不同条件下的消化液VFA组分和氨氮浓度,调控pH=6可使发酵类型从乙醇型发酵转为丁酸型发酵,也有利于蛋白质的分解。     

CaO2投加量及投加方式对剩余污泥厌氧发酵产生短链脂肪酸的影响

以污水处理厂剩余活性污泥作为研究对象,在中温条件下,按照不同投加量和投加方式投加过氧化钙（CaO₂）进行预处理,考察其对污泥发酵产酸和产甲烷的影响,以期确定CaO₂最佳投加量和投加方式.结果表明,在（35±1）℃条件下,投加CaO₂可提高剩余污泥发酵液pH值,从而促进有机物的快速溶出.在同样投加剂量条件下,一次性投加比多次投加更有利于污泥的溶解以及短链脂肪酸的积累.当一次性投加0.2g CaO₂/g VSS时,发酵液中乙酸浓度在第7d达到最高值（169mg COD/g VSS）,同时乙酸在6种主要酸中所占比例达到最大（71.0%）.与一次性投加方式相比较,多次投加CaO₂对产甲烷的抑制作用较小,不利于SCFAs的积累.     

不同电解质对电化学预处理剩余污泥厌氧发酵产挥发性脂肪酸的影响

电化学预处理剩余污泥(waste activated sludge, WAS)厌氧发酵(anaerobic fermentation, AF)产挥发性脂肪酸(volatile fatty acids, VFAs)具有良好的应用价值和环境效益,然而不同电解质对电化学预处理剩余污泥以及厌氧发酵的效果具有较大影响。因此,实验考查了不同电解质(空白对照,NaCl,Na₂SO₄和CaCl₂)在电流强度为1 A、预处理时间为60 min的电化学处理条件下,对剩余污泥厌氧发酵产VFAs的影响。结果表明:当0.05 mol/L NaCl作为电解质时,在电化学预处理阶段污泥有机质(溶解性COD、多糖、蛋白质等)溶出效果较其他电解质更好。在厌氧发酵阶段,该条件下VFAs最大累积量可达到2625.8 mg COD/L,相比空白对照组提升了51.6%,表明NaCl作为电解质的电化学预处理不仅能够有效促进剩余污泥中有机质溶出,而且有利于产酸微生物(如Firmicutes和Bacteroidetes)的富集,从而促进厌氧发酵产VFAs,达到提高污泥资源化利用率的目的。     

基于优质碳源提供的CAMBR复合工艺短程硝化-反硝化除磷研究

挥发性脂肪酸(VFA)是反硝化除磷过程可以利用的优质碳源,为此本研究结合厌氧折流板反应器(ABR)微生物相分离和膜生物反应器(MBR)出水水质优良的特性,构建了CAMBR复合工艺,并通过优化ABR水力停留时间(HRT)等运行条件以提供优质碳源,实现高效反硝化除磷.研究表明,当ABR的HRT为4.8 h时,可获得充足的VFA作为优质碳源,并实现消耗VFA的量为56.1 mg·L~(-1)的同时获得10.43 mg·L~(-1)的释磷,即释放1 mg磷需要的VFA量为5.38 mg,同时实现12.35 mg·L~(-1)的吸磷,而MBR池的吸磷为1.33 mg·L~(-1).短程硝化除磷过程中,缺氧消耗1 mg PO_4~(3-)-P需要0.62 mg的NO-x-N,吸收1 mg PO_4~(3-)-P所需NO_2~--N的量为1.67~2.04 mg.系统出水水质稳定,COD、TN和溶解性PO_4~(3-)-P的平均去除率分别为91%、84%和93%,出水平均浓度分别为30、7.15和0.55 mg·L~(-1),表明CAMBR复合工艺生在处理生活污水过程中可获得稳定高效的反硝化除磷效果.