高铁酸钾破解剩余污泥的水解效能分析

为了有效提高污泥水解效率、缩短厌氧消化时间,以K₂FeO₄为氧化剂破解剩余污泥,考察K₂FeO₄投加量（50~500 g/kg,以干质量计）对污泥破解率的影响,分析水解液各项特征指标并对其可生化性能进行预测,探究该方法作为污泥厌氧预处理的可行性.结果表明:污泥水解效率随着K₂FeO₄投加量的增加而升高,当搅拌速率为500 r/min、反应时间为2 h、K₂FeO₄投加量为500 g/kg的条件下,可实现最高的污泥破解率（34.6%）.污泥水解液中有机物以多糖、蛋白质为主,并有少量挥发性有机酸;污泥破解过程也伴随着P和NH₄+-N的释放,上清液中ρ（TP）最高可达496 mg/L,且以正磷酸盐为主（约310 mg/L）,可对其进行回收.采用三维荧光体积积分的方法对污泥水解液的可生化性能进行预测,发现污泥经K₂FeO₄预处理后,水解液中RB（易降解有机质）和PB（难降解有机质）荧光强度均明显增加,当K₂FeO₄投加量为50 g/kg时,F_digestion（生物可降解性指数）达到最大值（4.75）,预测此时污泥的可生化性能最佳.以K₂FeO₄为氧化剂预处理污泥可有效提升污泥水解效率,但若作为厌氧消化预处理,应综合考虑污泥破解率和可生化性能.研究显示,搅拌速率为500 r/min、反应时间为2 h、K₂FeO₄投加量为50 g/kg预处理条件下污泥的可生化性能最佳.      

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.     

A new process to improve short-chain fatty acids and bio-methane generation from waste activated sludge

As an important intermediate product, short-chain fatty acids(SCFAs) can be generated after hydrolysis and acidification from waste activated sludge, and then can be transformed to methane during anaerobic digestion process. In order to obtain more SCFA and methane,most studies in literatures were centered on enhancing the hydrolysis of sludge anaerobic digestion which was proved as un-efficient. Though the alkaline pretreatment in our previous study increased both the hydrolysis and acidification processes, it had a vast chemical cost which was considered uneconomical. In this paper, a low energy consumption pretreatment method, i.e. enhanced the whole three stages of the anaerobic fermentation processes at the same time, was reported, by which hydrolysis and acidification were both enhanced, and the SCFA and methane generation can be significantly improved with a small quantity of chemical input. Firstly, the effect of different pretreated temperatures and pretreatment time on sludge hydrolyzation was compared. It was found that sludge pretreated at 100°C for 60 min can achieve the maximal hydrolyzation. Further, effects of different initial p Hs on acidification of the thermal pretreated sludge were investigated and the highest SCFA was observed at initial p H 9.0with fermentation time of 6 d, the production of which was 348.63 mg COD/g VSS(6.8 times higher than the blank test) and the acetic acid was dominant acid. Then, the mechanisms for this new pretreatment significantly improving SCFA production were discussed. Finally,the effect of this low energy consumption pretreatment on methane generation was investigated.     

热碱预处理后得克隆对污泥厌氧发酵产酸及污泥特性的影响

为了探究新兴污染物得克隆（DPs）对剩余活性污泥（WAS）发酵产酸及污泥特征的影响,以WAS及DPs为研究对象,建立序批式反应器,在中温条件下探究了不同含量的DPs对WAS发酵的影响.结果表明,DPs对污泥厌氧发酵产短链脂肪酸（SCFA）具有明显的抑制作用,当DPs含量为300.0mg/kg TSS时,SCFA的最大产量仅为151.2mg COD/g VSS,是空白样品的0.7倍.DPs的存在会影响WAS的理化性质,且DPs促进了污泥的分解,但抑制了水解和酸化过程,且随着DPs浓度的增加抑制作用越明显.同时,DPs抑制有机质的释放,当DPs含量为300.0mg/kg TSS,溶解性化学需氧量（SCOD）的最大浓度仅为空白组的0.74倍,溶解性蛋白质与多糖的浓度也低于空白组.此外,DPs还影响NH₄⁺-N和PO₄^3--P的释放,高剂量的DPs促进了发酵液内NH₄⁺-N和PO₄³-P的释放.     

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.     

Enhanced nitrogen removal upon the addition of volatile fatty acids from activated sludge by combining calcium peroxide and low-thermal pretreatments

This study investigated a combined low-thermal and CaO₂ pretreatment to enhance the volatile fatty acid (VFA) production from waste activated sludge (WAS). The fermentative product was added to a sequencing batch reactor (SBR) as an external carbon source to enhance nitrogen removal. The results showed that the combined pretreatment improved WAS solubilization, releasing more biodegradable substrates, such as proteins and polysaccharides, from TB-EPS to LB-EPS and S-EPS. The maximum VFA production of 3529 ± 188 mg COD/L was obtained in the combined pretreatment (0.2 g CaO₂/g VS + 70 °C for 60 min), which was 2.1 and 1.4-fold of that obtained from the sole low-thermal pretreatment and the control test, respectively. Consequently, when the fermentative liquid was added as an external denitrification carbon source, the effluent total nitrogen decreased to Class A of the discharge standard for pollutants in rural wastewater treatment plants in most areas of China.     

矿化垃圾对剩余污泥厌氧水解、酸化的影响

通过向剩余污泥发酵系统中加入不同剂量的矿化垃圾的方法,探究了矿化垃圾对剩余污泥厌氧水解、酸化过程的影响.结果表明,添加1/3g/g TSS(总悬浮固体)剂量以内的矿化垃圾能显著提高WAS的水解、酸化过程,且矿化垃圾的最佳投加量为1/3g/g TSS,在此条件下,试验组SCOD/TCOD以及最大产酸量(183.45mg COD/g VSS,发酵时间为6d)均高于空白组(79.45mg COD/g VSS,发酵时间为10d).机理研究表明,矿化垃圾能够促进污泥的溶解、蛋白质和多糖的水解以及氨基酸和葡萄糖的酸化.在投加矿化垃圾的反应体系中与水解、酸化有关酶的活性也均高于空白试验组,进一步证实了矿化垃圾能够强化污泥厌氧发酵的水解酸化反应.     

Co-fermentation of waste activated sludge with food waste for short-chain fatty acids production: effect of pH at ambient temperature

Effect of pH ranging from 4.0 to 11.0 on cofermentation of waste activated sludge (WAS) with food waste for short-chain fatty acids (SCFAs) production at ambient temperature was investigated in this study. Experimental results showed that the addition of food waste significantly improved the performance of WAS fermentation system, which resulted in the increases of SCFAs production and substrate reduction. The SCFAs production at pH 6.0, 7.0, 8.0, and 9.0 and fermentation time of 4 d was respectively 5022.7, 6540.5, 8236.6, and 7911.7 mg COD·L⁻¹, whereas in the blank tests (no pH adjustment, pH 8.0 (blank test 1), no food waste addition, pH 8.0 (blank test 2), and no WAS addition (blank test 3)) it was only 1006.9, 971.1, and 1468.5 mg COD·L⁻¹, respectively. The composition of SCFAs at pH from 6.0 to 9.0 was also different from other conditions and propionic acid was the most prevalent SCFA, which was followed by acetic and n-butyric acids, while acetic acid was the top product under other conditions. At pH 8.0 a higher volatile suspended solids (VSS) reduction of 16.6% for the mixture of WAS and food waste than the sole WAS indicated a synergistic effect existing in fermentation system with WAS and food waste. The influence of pH on the variations of nutrient content was also studied during anaerobic fermentation of the mixture of WAS and food waste at different pH conditions. The release of NH₄⁺-N increased with fermentation time at all pH values investigated except 4.0, 5.0 and in blank test one. The concentrations of soluble phosphorus at acidic pHs and in the blank test one were higher than those obtained at alkaline pHs. Ammonia and phosphorus need to be removed before the SCFAs-enriched fermentation liquid from WAS and food waste was used as the carbon source.     

紫外耦合游离亚硝酸强化剩余污泥厌氧发酵产酸研究

为打破传统厌氧发酵过程中污泥破壁溶胞困难和产酸效能低的瓶颈,探究了紫外光（UV）耦合游离亚硝酸（FNA）预处理对污泥发酵产酸的影响,并与热（H）和超声法（US）耦合FNA预处理进行了对比分析.结果表明,UV辅助FNA联合预处理（FNA-UV）对细胞破碎和胞外聚合物的剥离具有协同效应,·OH和·O₂^-作为反应中间体,其强度远高于其他预处理组（FNA-US和FNA-H）,与·NO,·NO₂及ONOO^-等中间产物共同促进了溶解性有机物的释放,溶解性碳水化合物和蛋白质含量相比FNA组分别提升60%和90%,进而为后续水解产酸过程提供了充足的底物.FNA-UV组短链脂肪酸（SCFAs）浓度于第4d达到峰值,为（201.8±4.8） mg COD/g VSS,相比FNA组提升67%,乙酸占比高达56.8%.通过发酵末期对各体系进行碳平衡分析表明,紫外耦合FNA预处理在污泥减量、溶解性有机物的释放与转化、SCFAs的产生方面具有重要作用.微生物群落分析表明,FNA-UV对功能菌群的富集发挥重要作用,表现为厌氧发酵菌和反硝化菌的有效增强,相比其他各组提升了23.7%~270.6%.     

玉米秸秆干式厌氧发酵乙酸产生规律及其对发酵的影响

为解决玉米秸秆干式厌氧发酵系统因乙酸积累而致发酵失败、工程运行不稳定等问题,利用气相色谱仪对玉米秸秆干式厌氧发酵过程中w(乙酸)和w(CH₄)进行检测,结合相关性分析和回归分析等方法,研究了乙酸动态产生趋势、w(TS)(TS为总固体)与w(乙酸)的相关性,以及w(乙酸)对CH₄产生的作用机制. 结果表明:发酵过程中w(乙酸)先增后降,w(TS)由20%增至30%,w(乙酸)增加的持续时间由5 d延至15 d. Pearson相关性分析结果表明,w(TS)与w(乙酸) 呈极显著负相关(R<-0.979,P<0.01). 一元线性回归分析得到拟合方程y=-1 214.8w(TS)+668.2,由斜率(-1 214.8)可知,w(TS)对产乙酸过程具有较明显的抑制作用. 玉米秸秆干式厌氧发酵系统内w(乙酸)为160~451 mg/g,随着w(乙酸)的增加,底物CH₄产率经历上升、稳定、下降后再稳定和下降4个阶段,其中w(乙酸)为212~312 mg/g时,底物CH₄产率(大于120 m3/t,以秸秆干质量计)最大,其次为w(乙酸)在>312~410 mg/g时的80~120 m3/t.      

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.     

Modified ADM1 for modeling free ammonia inhibition in anaerobic acidogenic fermentation with high-solid sludge

Anaerobic acidogenic fermentation with high-solid sludge is a promising method for volatile fatty acid (VFA) production to realize resource recovery. In this study, to model inhibition by free ammonia in high-solid sludge fermentation, the anaerobic digestion model No. 1 (ADM1) was modified to simulate the VFA generation in batch, semi-continuous and full scale sludge. The ADM1 was operated on the platform AQUASIM 2.0. Three kinds of inhibition forms, e.g., simple inhibition, Monod and non-inhibition forms, were integrated into the ADM1 and tested with the real experimental data for batch and semi-continuous fermentation, respectively. The improved particle swarm optimization technique was used for kinetic parameter estimation using the software MATLAB 7.0. In the modified ADM1, the K_s of acetate is 0.025, the k_m,ac is 12.51, and the K_{I_NH3} is 0.02, respectively. The results showed that the simple inhibition model could simulate the VFA generation accurately while the Monod model was the better inhibition kinetics form in semi-continuous fermentation at pH 10.0. Finally, the modified ADM1 could successfully describe the VFA generation and ammonia accumulation in a 30 m³ full-scale sludge fermentation reactor, indicating that the developed model can be applicable in high-solid sludge anaerobic fermentation.     

Enhanced dewaterability of waste activated sludge by UV assisted ZVI-PDS oxidation

Ultraviolet（UV） assisted zero-valent iron（ZVI）-activated sodium persulfate（PDS） oxidation（UV-ZVI-PDS） was used to treat waste activated sludge（WAS） in this study.The dewaterability performance and mechanism of WAS dewatering were analyzed.The results showed that UV-ZVI-PDS can obtain better sludge dewatering performance in a wide pH range（2.0-8.0）.When the molar ratio of ZVI/PDS was 0.6,UV was 254 nm,PDS dosage was 200 mg/g TS（total solid）,pH was 6.54,reaction time was 20 min,the CST（capillary s...     

Effects of different sludge disintegration methods on sludge moisture distribution and dewatering performance

A key step in sludge treatment is sludge dewatering. However, activated sludge is generally very difficult to be dewatered. Sludge dewatering performance is largely affected by the sludge moisture distribution. Sludge disintegration can destroy the sludge structure and cell wall, so as change the sludge floc structure and moisture distribution, thus affecting the dewatering performance of sludge. In this article, the disintegration methods were ultrasound treatment, K₂FeO₄ oxidation and KMnO₄ oxidation. The degree of disintegration (DD_COD), sludge moisture distribution and the final water content of sludge cake after centrifuging were measured. Results showed that three disintegration methods were all effective, and K₂FeO₄ oxidation was more efficient than KMnO₄ oxidation. The content of free water increased obviously with K₂FeO₄ and KMnO₄ oxidations, while it decreased with ultrasound treatment. The changes of free water and interstitial water were in the opposite trend. The content of bounding water decreased with K₂FeO₄ oxidation, and increased slightly with KMnO₄ oxidation, while it increased obviously with ultrasound treatment. The water content of sludge cake after centrifuging decreased with K₂FeO₄ oxidation, and did not changed with KMnO₄ oxidation, but increased obviously with ultrasound treatment. In summary, ultrasound treatment deteriorated the sludge dewaterability, while K₂FeO₄ and KMnO₄ oxidation improved the sludge dewaterability.     

Effects of different sludge disintegration methods on sludge moisture distribution and dewatering performance

A key step in sludge treatment is sludge dewatering. However, activated sludge is generally very difficult to be dewatered. Sludge dewatering performance is largely affected by the sludge moisture distribution. Sludge disintegration can destroy the sludge structure and cell wall, so as change the sludge floc structure and moisture distribution, thus affecting the dewatering performance of sludge. In this article, the disintegration methods were ultrasound treatment, K₂FeO₄ oxidation and KMnO₄ oxidation. The degree of disintegration (DDCOD), sludge moisture distribution and the final water content of sludge cake after centrifuging were measured. Results showed that three disintegration methods were all effective, and K₂FeO₄ oxidation was more efficient than KMnO₄ oxidation. The content of free water increased obviously with K₂FeO₄ and KMnO₄ oxidations, while it decreased with ultrasound treatment. The changes of free water and interstitial water were in the opposite trend. The content of bounding water decreased with K₂FeO₄ oxidation, and increased slightly with KMnO₄ oxidation, while it increased obviously with ultrasound treatment. The water content of sludge cake after centrifuging decreased with K₂FeO₄ oxidation, and did not changed with KMnO₄ oxidation, but increased obviously with ultrasound treatment. In summary, ultrasound treatment deteriorated the sludge dewaterability, while K₂FeO₄ and KMnO₄ oxidation improved the sludge dewaterability.     

Effects of acid,acid-ZVI/PMS,Fe(Ⅱ)/PMS and ZVI/PMS conditioning on the wastewater activated sludge(WAS)dewaterability and extracellular polymeric substances(EPS)

The effects of four conditioning approaches:Acid,Acid-zero-valent iron(ZVI)/peroxydisulfate(PMS),Fe(Ⅱ)/PMS and ZVI/PMS,on wastewater activated sludge(WAS) dewatering and organics distribution in supernatant and extracellular polymeric substances(EPS) layers were investigated.The highest reduction in bound water and the most WAS destruction was achieved by Acid-ZVI/PMS,and the optimum conditions were pH 3,ZVI dosage 0.15 g/g dry solid(DS),oxone dosage 0.07 g/g DS and reaction time 10.6 min with the reductions in capillary suction time(CST) and water content(Wc) as 19.67% and 8.49%,respectively.Four conditioning approaches could result in TOC increase in EPS layers and supernatant,and protein(PN) content in tightly bound EPS(TB-EPS).After conditioning,organics in EPS layers could migrate to supernatant.Polysaccharide(PS) was easier to migrate to supernatant than PN.In addition,Acid,Acid-ZVI/PMS or Fe(Ⅱ)/PMS conditioning promoted the release of some polysaccharides containing ring vibrations v P=O,v C-O-C,v C-O-P functional groups from TB-EPS.ESR spectra proved that both radicals of SO_4~-· and·OH contributed to dewatering and organics transformation and migration.CST value of WAS positively correlated with the ratios of PN/PS in LB-EPS and total EPS,while it negatively correlated with TOC,PN content and PS content in TB-EPS,as well as PS content in supernatant and LB-EPS.BWC negatively correlated to zeta potential and TOC value,PN content,and HA content in supernatant.     

废铁屑对剩余污泥厌氧消化特性的影响

为探明废铁屑（RSI）对中温厌氧消化特性的影响,利用RSI为外源添加剂研究其投加对剩余污泥厌氧消化水解酸化、产气效率以及污泥表面形态的影响.结果表明:①剩余污泥酸化水解产物VFAs的主要成分是乙酸,其含量随RSI投加量的增加呈先升后降的趋势.②RSI投加量适中（不超过20 g/L）时可促进乙、丁酸型发酵,抑制丙酸型发酵,进而提高剩余污泥厌氧消化效率.③当RSI投加量分别为0、1、5、10、20和30 g/L时,累积甲烷产率分别为135.4、141.9、159.2、178.9、209.3和180.7 mL/g（以VS计）,甲烷含量分别为51.2%~56.4%、53.9%~58.6%、58.1%~62.5%、59.5%~68.3%、61.1%~71.2%和51.9%~61.4%.RSI最佳投加量为20 g/L,与空白组相比,累积甲烷产率和甲烷含量分别提升了54.6%和23.0%.④结合扫描电镜-X射线能谱（SEM-EDX）分析方法发现,在厌氧消化过程中微生物可促进RSI的溶解,且随RSI投加量的增加,消化污泥表面的铁元素含量也随之增加.⑤RSI的投加会提高蛋白酶和纤维素酶的活性,但若投加量过高则会产生负面效应.研究显示,外源添加剂RSI投加量适中（不超过20 g/L）时可促进剩余污泥厌氧消化效率.      

表面活性剂促进剩余污泥酶水解的研究

为了提高污泥酶水解的效率,研究向污泥中投加表面活性剂十二烷基硫酸钠（sodium dodecyl sulfate,SDS）强化污泥酶水解的效果.结果表明,SDS极大促进了剩余污泥酶水解,且复合酶的处理效果优于单酶.复合酶的投加量为0.06 g/g时,SCOD溶出率随SDS投加量成正比增加.SDS为0.20 g/g时,S...     

生物酶对初沉污泥厌氧发酵产短链脂肪酸的调控研究

旨在通过生物酶调节(碱性蛋白酶、中性蛋白酶和α-淀粉酶)提高初沉污泥的厌氧发酵效率,并通过微生物群落结构解析,SCFAs (short-chain fatty acids,SCFAs)组分分析等揭示其调控机理.结果表明,3种生物酶均可增强初沉污泥水解和产酸作用,碱性蛋白酶调控系统对初沉污泥厌氧发酵的促进效果最为明显,发酵第4d SCFAs的产量和产率分别达到1508mg COD/L和0.174g COD/g VSS.对比控制组,SCFAs的产量和产率分别增加了1129mg COD/L和0.13g COD/g VSS.微生物群落结构分析表明,在碱性蛋白酶调控发酵系统中,Lentimicrobium、Proteiniphilum和Bacteroides等发酵相关菌群的相对丰度得到了改善,Methanosaeta、Methanospirillum等产甲烷古菌的活性受到了抑制.同时,生物酶调控对促进发酵过程乙酸占比也有促进作用.     

垃圾渗滤液浓缩液高铁酸钾联合PAC处理技术研究

以碟管式反渗透(DTRO)处理垃圾渗滤液产生的浓缩液为研究对象,采用高铁酸钾联合聚合氯化铝(PAC)处理浓缩液.结果表明,在单独采用高铁酸钾的条件下,DTRO浓缩液COD、UV_(254)和色度去除率随着高铁酸钾投加量的增加而升高.高铁酸钾投加量为10 g·L~(-1),pH为5时,COD、UV_(254)和色度去除效果最佳,反应在40 min内基本完成,COD、UV_(254)、色度去除率分别为38.5%、35.7%和68.5%.通过响应曲面法分析高铁酸钾联合PAC处理DTRO浓缩液效果可得,高铁酸钾投加量在10.0～13.0 g·L~(-1)之间,pH调节至3.0～4.0,PAC投加量为13.0～15.0 g·L~(-1)时,DTRO浓缩液COD去除率可达74%.