超声联合低温热水解促进剩余污泥破解和厌氧消化的研究

为了探索超声和低温热水解预处理技术对剩余污泥厌氧消化性能的影响,进行了单独超声、单独热水解和二者联合的实验研究.以温度和超声能量为控制参数,研究了不同预处理技术对污泥破解度DD（Disintegration degree of SCOD）和有机质溶出的影响.结果表明：联合预处理技术对DD和有机质浓度的增加效果比超声和热水解单独作用之和分别高4.04%、36.62mg/L. DD和实际输入能量之间存在较高的线性相关性（R²=0.977）,即在本研究条件下,输入能量越高,污泥破解效果越好.超声和热水解联合预处理后污泥厌氧消化产甲烷量较原泥增加了30.2%～55.4%.DD和厌氧消化性能之间存在二次非线性关系（R²=0.821）,且厌氧消化性能最高达到877.76LCH₄/kg VSS去除,该峰值出现在超声能量12000kJ/kg TS和热水解温度80℃联合作用条件下.     

超声联合热碱技术促进剩余污泥破解的参数优化

为了进一步提高超声联合技术破解污泥的效果,在前期双因素的研究基础上,采用3因素3水平的响应曲面法分析了热水解温度(60,70,80°C)、加碱量(0.04,0.07,0.10g/g TS)和超声能量(4000,8000,12000k J/kg TS)对污泥破解度的影响.回归分析结果表明污泥破解度与三因素之间符合三元二次方程:Y=-196.87+6.11X_1+487.53X_2+0.0039X_3-1.742X_1X_2-0.000024X_1X_3+0.0044X_2X_3-0.0398X_1~2-2488.33X_2~2-1.33×10-7X_3~2,其中X_1、X_2、X_3分别为温度、加碱量和超声能量.模型拟合度高达97.548%,表明该模型能较好地模拟超声联合热碱预处理参数和预测污泥破解度.根据模型得出最佳预处理工艺组合为:温度73.06℃,加碱量0.085g/g TS,超声能量9551k J/kg TS.最佳工艺参数下污泥破解度实测值为60.411%.经济性分析表明,超声联合热碱预处理条件下每t污泥处理费较未处理污泥降低了20.42元,在本研究条件下具有较高的经济可行性.     

酸-碱预处理促进剩余污泥厌氧消化的研究

为提高剩余污泥的厌氧消化效率,投加酸和碱对污泥进行预处理,对比分析了不同预处理方式（单独碱处理、酸-碱处理和碱-酸处理）对污泥水解酸化的影响,并研究了各种预处理方式对后续厌氧消化产甲烷效率的影响.结果表明,单独碱处理的溶解性化学需氧量（SCOD）溶出量比酸碱联合处理要大16%左右,预处理第8 d,达到5 406.1 mg.L-1.采用先酸（pH 4.0,4d）后碱（pH 10.0,4 d）预处理,在污泥水解酸化过程中,乙酸产量及其占总短链脂肪酸（SCFAs）的质量分数均高于其他预处理方式,其乙酸产量（以COD/VSS计）可达到74.4 mg.g-1,占总SCFAs的60.5%.酸-碱预处理后污泥混合液的C∶N比值为25左右,C∶P比值在35～40之间,这比单独碱处理和碱-酸处理后的C∶N和C∶P比值更有利于后续厌氧消化.通过对比研究发现,酸-碱预处理后,厌氧消化到第15 d,酸-碱预处理污泥的累积甲烷产量（CH4/VSS加入）达到136.1 mL.g-1,分别是空白对照、碱-酸预处理和单独碱预处理方式的2.5、1.7和1.6倍,厌氧消化效率最高.经过8 d酸-碱预处理和15 d的厌氧消化,挥发性悬浮固体（VSS）总去除率达到60.9%,污泥减量效果比其他预处理要好.很显然,酸-碱预处理方式更有利于污泥厌氧消化及污泥减量化.     

碱热联合破解污泥效果及动力学研究

研究了碱热联合处理对污泥的破解效果并进行了动力学分析.结果表明,碱的加入显著提高了热处理的破解效果,NaOH的破解效果比Ca(OH)2好.碱热联合处理脱水泥饼的适宜处理参数为140℃、90min、Ca(OH)2和NaOH投加量为0.25g/g总固体(TS).在该条件下,溶解性化学需氧量(SCOD)比未加碱时分别增加了41.26%和198%,质量减少率分别为50%、57%.采用NaOH碱热破解污泥后的SCOD值与热处理温度(T)、处理时间(t)及投碱量(A)的关系可以用幂指数模型表示:SCODNa=10178.17[T ]0.43 [A ]0.59t 0.24.     

含固率对超声联合热碱预处理及厌氧消化的影响

含固率是影响污泥预处理效果的重要因素。对含固率为1.5%、5%、10%的污泥进行超声联合热碱预处理及厌氧消化,以探究含固率对污泥破解效果及产气量的影响,发现VSS的减少率和氨氮的增长率随污泥含固率的提高而减小。厌氧消化27d后,经预处理作用后污泥的含固率为1.5%、5%、10%,VSS浓度较原泥依次减少了64.5%、54.6%、20.1%,氨氮浓度较原泥依次增加了97.3%、47.5%、25.6%,厌氧消化产气量较原泥分别增加了32.0%、40.1%、18.9%,且产气量均在第20天之前便达到了原泥30 d的总产气量。综合考虑污泥体积、总减量效果以及产气量,采用含固率5%的污泥进行预处理以及后续的厌氧消化过程更合适。     

预处理对造纸污泥厌氧消化产甲烷性能的影响研究

采用碱(NaOH)和生物(蘑菇渣、绿色木霉)2种方法分别预处理造纸污泥,并将预处理后的造纸污泥与味精废液进行联合厌氧消化,研究不同预处理方式对造纸污泥的影响以及对后续联合厌氧消化甲烷产率的影响.结果表明,造纸污泥经过碱(NaOH)预处理和生物预处理(蘑菇渣、绿色木霉)后,污泥颗粒的结构变得紧实、平滑,颗粒间的孔隙度减少,污泥絮体中的纤维长度明显变短、污泥中的SCOD增加了35.5%~1130%、VSS降低了6%~19%、SVsludge增加了32%~192%,NH3-N浓度提高了36%~62.4%,表明预处理后污泥中的大分子物质被降解成小分子物质,且碱预处理对污泥产生的变化较生物处理大;经预处理后的造纸污泥与味精废液联合厌氧消化,甲烷得率分别为:NaOH预处理0.32m3 CH4/kg VS、蘑菇渣预处理0.23 m3 CH4/kg VS,较CK分别提高了54%~88%和12%~34%,可见碱预处理提高甲烷产率效果更明显,由于蘑菇渣预处理具有成本低、解决二次污染、实现废物再利用等优点,因此两者在预处理提高造纸污泥厌氧消化甲烷产率方面都具有重要意义.     

三种预处理方法对污泥的破解效果

运用热水解、超声波和微波等3 种方法预处理污水剩余污泥,通过测定污泥pH 值、可溶性蛋白质、总糖和可溶解性化学需氧量(SCOD)等指标考察其对污泥破解效果的影响.结果表明,在各种预处理中,污泥pH 值变化不显著.污泥破解效果随处理强度的增加而增强.超声波ED=2W/L,t =10min 条件时,污泥的破解效果最好,可溶解性蛋白质、总糖和SCOD 浓度分别为1013.6,512.6,4184 mg/L;SCOD/TCOD 值较原始污泥升高了41.73%.从实际应用和运行成本考虑,长时间而低强度的处理都能够达到较为理想的破解效果,即热处理(t=75min,T=45℃),超声波处理(t =10min,ED=0.5W/L),微波处理(t =300s, p =70W). 在能耗相同的条件下,破解效果为超声波>微波>热水解.     

城市污水污泥超声波预处理的研究

文章通过分析污泥耗氧率(SOUR)和破解率(DDCOD)的变化,研究了浓度为9.5g/L的生活污泥在频率为28kHz的超声波下,不同超声波声能密度和超声时间作用对污泥预处理效果的影响。试验结果表明,在适当的声能密度和超声时间下,超声波预处理可以明显提高污泥破解率,同时提高污泥的生物活性,试验结果为超声波预处理与污泥处理工艺联用以提高污泥减量化效率提供了依据。     

超声波-氢氧化钙联合破解剩余污泥的效果

在对超声波、Ca(OH)2单独破解污泥效果研究的基础上,运用响应面法对超声波-Ca(OH)2联合破解剩余污泥的效果进行研究。结果表明:超声波单独破解剩余污泥过程中,污泥破解效果与超声波能量密度和作用时间均成正相关;Ca(OH)2单独破解剩余污泥过程中,当Ca(OH)2投加量为0.04 mol/L时,污泥破解效果最佳,1 h内污泥的破解率(DD)由控制样的0.61%增长到7.48%;联合破解剩余污泥效果优于2种单独破解效果,污泥破解率与超声波能量密度(A)、Ca(OH)2投加量(B)、联合作用时间(C)满足三元二次方程方程DD=-2.660-0.057A+484.738B-0.048C+0.441AB-2.233×10-3AC-0.088×BC-2.909×10-4A2-6 055.000 B2+2.117×10-4C2,且超声波与Ca(OH)2联合破解污泥过程中存在协同效应,当超声波能量密度为0.10 kW/L、Ca(OH)2投加量为0.04 mol/L、联合作用时间为60min时,污泥的破解率达到19.60%,此时协同效应最强。     

超声波促进好氧/缺氧污泥消化过程中水解酶活性变化研究

为评价超声波促进污泥好氧/缺氧消化的作用,采用频率28 kHz,声能密度为0.15 kW.L-1和超声时间10 min的超声参数与好氧/缺氧消化衔接,研究了污泥的SS、VSS及水解酶活性(淀粉酶、α-葡萄糖苷酶、蛋白酶、磷酸酶)在消化过程中的变化趋势,同时以未经超声处理的消化污泥作为对照.结果表明,经过超声波-好氧/缺氧消化13 d,VSS去除率为44.3%,高出对照污泥14.9%.污泥中水解酶活性随消化天数增加呈先增加后减少的变化趋势,其中超声污泥的淀粉酶和葡萄糖苷酶活性在第5 d达到峰值,此时VSS淀粉酶活性为0.104μmol.g-1,葡萄糖苷酶活性为0.637μmol.g-1.超声污泥中胞内蛋白酶和胞外蛋白酶在第7 d达到峰值,胞内蛋白酶活性为23.68μmol.g-1,远远大于胞外蛋白酶,在污泥消化过程中起主导作用.超声污泥中酸性磷酸酶活性高于对照污泥,而碱性磷酸酶对环境改变较为敏感,超声波预处理改变污泥内部性质,导致碱性磷酸酶活性减少.     

Combined alkaline and ultrasonic pretreatment of sludge before aerobic digestion

Alkaline and ultrasonic sludge disintegration can both be used as pretreatments of waste activated sludge (WAS) for improving the subsequent anaerobic or aerobic digestion. The pretreatment has been carried out using different combination of these two methods in this study. The effect was evaluated based on the quantity of soluble chemical oxygen demand (SCOD) in the pretreated sludge as well as the degradation of organic matter in the following aerobic digestion. For WAS samples with combined pretreatment, the released COD was in high level than those with ultrasonic or alkaline treatment. When combined with the same ultrasonic treatment, NaOH treatment resulted in more solubilization of WAS than Ca(OH)2. For combined NaOH and ultrasonic treatments with different sequences, the released COD were in the order: simultaneous treatment > ultrasonic treatment following NaOH treatment > NaOH treatment following ultrasonic treatment. For simultaneous treatment, low NaOH dosage (100 g/kg dry solid), short duration (30 min) of NaOH treatment, and low ultrasonic specific energy (7 500 kJ/kg dry solid) were beneficial for sludge disintegration. Using combined NaOH and ultrasonic pretreatment with the optimium parameters, the degradation efficiency of organic matter was increased from 38.0% to 50.7%, which is much higher than with ultrasonic (42.5%) or with NaOH pretreatment (43.5%) in the subsequent aerobic digestion at the same retention time.     

碱辅助条件下的污泥微波热水解特性研究

向污泥中加入NaOH进行微波热水解实验.结果表明,每1 g污泥悬浮固体(SS)添加NaOH 0.1 g时,污泥中的挥发性悬浮固体(VSS)快速水解,170℃的VSS溶解率达到60%以上,热水解后污泥的有机物含量(VSS/SS)降低至25%.80、120、150和170℃热水解5 min的污泥液相COD浓度分别为9.8、12.8、15.1和14.5 g/L,相应SCOD/TCOD为24.0%、31.3%、36.9%和35.6%.随温度的升高和时间的延长热水解污泥pH越低,最低值10.5.在每1 g SS添加0~0.2g NaOH的范围内,当添加量0.05 g时,VSS和SS的溶解率增加幅度降低.分别对NaOH添加量0.05 g热水解5 min和添加量0.1 g热水解1 min的污泥进行BMP厌氧消化实验.结果表明,添加量为0.05 g时热水解污泥的厌氧消化性能提高,经150℃处理污泥的产气量最大,比未处理污泥高28.5%,而在添加量为0.1 g时,污泥的厌氧消化性能受到抑制,产气量低于未处理污泥.     

Enhancement of thermophilic anaerobic digestion of thickened waste activated sludge by combined microwave and alkaline pretreatment

Pretreatment of thickened waste activated sludge (TWAS) by combined microwave and alkaline pretreatment (MAP) was studied to improve thermophilic anaerobic digestion efficiency. Uniform design was applied to determine the combination of target temperature (110–210°C), microwave holding time (1–51 min), and NaOH dose (0–2.5 g NaOH/g suspended solids (SS)) in terms of their effect on volatile suspended solids (VSS) solubilization. Maximum solubilization ratio (85.1%) of VSS was observed at 210°C with 0.2 g-NaOH/g-SS and 35 min holding time. The effects of 12 different pretreatment methods were investigated in 28 thermophilic batch reactors by monitoring cumulative methane production (CMP). Improvements in methane production in the TWAS were directly related to the microwave and alkaline pretreatment of the sludge. The highest CMP was a 27% improvement over the control. In spite of the increase in soluble chemical oxygen demand concentration and the decrease in dewaterability of digested sludge, a semi-continuous thermophilic reactor fed with pretreated TWAS without neutralization (at 170°C with 1 min holding time and 0.05 g NaOH/g SS) was stable and functioned well, with volatile solid (VS) and total chemical oxygen demand (TCOD) reductions of 28% and 18%, respectively, which were higher than those of the control system. Additionally, methane yields (L@STP/g-CODadded, at standard temperature and pressure (STP) conditions of 0°C and 101.325 kPa) and (L@STP/g VSadded) increased by 17% and 13%, respectively, compared to the control reactor.     

碱处理促进剩余污泥解的试验研究

研究了热碱水解法对剩余污泥特性参数(溶解性化学需氧量、挥发性脂肪酸、氨氮、pH值与污泥浓度等)的影响.碱的加入减弱了污泥细胞壁对高温的抵抗力,加剧了剩余污泥细胞内有机质的释放与水解,改变了污泥的性质.在反应温度为170℃、pH 13、反应时间为75 min的条件下,溶解性化学需氧量(SCOD)达到了最大融出量17956 mg/L,此时SCOD与总化学需氧量(TCOD)之比为0.65.在pH 13,反应时间为60 min时悬浮固体(SS)、挥发性悬浮固体(VSS)均达到了最大溶解率,其值分别为67%和72%.经热碱水解处理后的剩余污泥SCOD随着原污泥浓度的增大而增大,呈现了良好的线性关系,相关系数R2达到了0.97以上,而且随着pH值的增大,融出率也不断增大,在pH 13时达到最高值672 mg/g.另外,通过正交试验可以得出170℃时各因素对SCOD影响的重要性,依次为污泥浓度、DH值、反应时间.     

Enhancing the total organic carbon measurement efficiency for water samples containing suspended solids using alkaline and ultrasonic pretreatment methods

In this study,we investigated the effect of sample pretreatments(ultrasonication and alkaline extraction) on total organic carbon(TOC) measurements for water samples containing suspended solids(SS) of four different origins(algae,soil,sewage sludge,and leaf litter) to more clearly assess the impact of particulate organic carbon(POC) in water.The effects each of ultrasonication(power,pulse,etc.) and alkaline extraction condition(concentration,time,etc.) on the TOC recovery and precision were investigated,and the results were compared with those of a new sample pre treatment method combining both methods.Alkaline treatment(0.01 mol/L NaOH) showed higher precision than ultrasonication(100/5 on/off pulse),and notably,the differences among the measured TOC values in samples of different origins were also further reduced in the alkaline treatment.This suggests that the ultrasonic pretreatment results can be mainly attributed to the increase in POC recovery through particle size reduction,whereas the alkaline treatment results are achieved through the enhancement of POC solubilization.It is also particularly noteworthy that a higher TOC recovery of 87.6%±7.4% with a higher precision of 8.4%could be obtained using the combined method,compared to each treatment(ultrasonic:TOC recovery 34.7%,relative standard deviation 63.1%;alkaline:49.6% and 23.0%,respectively).Thus,simultaneous pretreatment with ultrasonication and alkaline extraction is expected to increase the oxidation rate of organic matter and the homogeneity of the samples,minimizing the loss of POC measurement values,and thereby improving the reliability of the TOC measurements of water samples containing SS.     

高固体污泥微波热水解特性变化

考察浓度7%、9%和13%的高固体污泥微波热水解特性,通过生化产甲烷潜能(BMP)实验,分析热处理污泥厌氧消化性能的变化.结果表明,微波加热升温速度快,污泥中悬浮性挥发固体(VSS)和悬浮固体(SS)溶解,液相COD、TOC、氨氮、TN和TP浓度增大, pH值降低.水解效率受污泥浓度影响显著,浓度13%的污泥VSS和SS溶解率低于7%和9%的污泥.170℃热水解5min,9%污泥的VSS和SS溶解率分别为23%和18%, SCOD浓度为41g/L, TOC和氨氮浓度达到30g/L和1g/L.热水解污泥厌氧消化性能提高,9%污泥的产气量在170℃、5min和10min比未处理污泥增加27%和30.8%.热水解时间对提高消化性能影响不大,热水解由5 min到10min,120℃、150℃和170℃的产气量分别增加4%、3.6%和5.7%.     

低强度超声波与酸、碱协同对污泥溶胞的影响

在能量密度为0.05W·mL-1和pH范围3.0～12.0条件下,研究了超声波辐射与酸、碱协同对污泥溶胞效果的影响.结果表明,溶解性化学需氧量(SCOD)、溶解性磷(SP)和溶解性糖(SA)含量随pH增大均呈先降后升趋势.当pH为3.0时,污泥溶胞效果不高,随污泥溶液碱性增强,SCOD、SP和SA含量随pH呈指数增长,说明强碱性环境有利于污泥溶胞.超声波辐射可显著提高污泥溶胞率,而且pH越大超声波辐射改善的溶胞效率越高.pH=11.0时超声波辐射60min以内,SCOD、SP和SA含量与时间均呈线性关系,超声波/碱协同污泥溶胞为一级反应.pH大于9.0的碱性条件下,超声波辐射和提高pH均可降低VSS/TSS.依据实验数据,应用非线性优化技术得到SCOD与pH和超声波辐射时间的数学模型,其平均相对误差小于2.6%.     

污泥超声处理及其在好氧消化中的应用

污泥好氧消化工艺可以有效实现污泥的稳定和减量,为了进一步提高好氧消化的效率,促进有机质的降解,在对污泥超声处理性能研究的基础上,考察了不同超声辅助处理手段对污泥好氧消化的影响.结果表明,经1.0 W/mL超声处理10 min后,污泥上清液中溶解性COD增加了5.4倍,污泥总悬浮固体减少了16%;而经0.05 W/mL超声处理10 min后,污泥比耗氧速率可提高29%.用这2种超声预处理好氧消化的进泥时,污泥有机质降解率没有明显改变,但用1.0 W/mL超声处理好氧消化的回流污泥时,污泥有机质降解率提高了15%,而且消化污泥的沉降性能良好,上清液中有机质含量增加很少,因此,后者可以用于改善污泥好氧消化工艺.     

Insights on the solubilization products after combined alkaline and ultrasonic pre-treatment of sewage sludge

This work provides insights on the solubilization products after a simultaneous combination of alkaline and ultrasonic (ALK + ULS) pre-treatment of sewage sludge. Soluble chemical oxygen demand (SCOD) increased from 1200 to 11,000 mg/L after such treatment. Organics with molecular weight around 5.6 kDa were solubilized because of the synergistic effect of ultrasound and alkali. Organics with molecular weight larger than 300 kDa increased from 7.8% to 60%, 16% and 42.3% after ULS, ALK and ALK + ULS treatment, respectively. Excitation emission matrix fluorescence spectroscopy analysis identified soluble microbial product-like and humic acid-like matters as the main solubilization products. Sludge anaerobic biodegradability was significantly enhanced with the simultaneous application of ALK + ULS pre-treatment. ALK + ULS pre-treatment resulted in 37.8% biodegradability increase compared to the untreated sludge. This value was higher compared to the biodegradability increase induced by individual ALK pre-treatment (5.7%) or individual ULS pre-treatment (20.7%) under the same conditions applied.