褐铁矿与固体含量对牛粪秸秆混合厌氧干式发酵的影响

干式厌氧发酵是处理农业废弃物的有效途径之一,其中总固体(TS)含量和外源添加剂是影响有机质产甲烷过程的重要影响因素。以牛粪与水稻秸秆为例,研究了不同的褐铁矿添加量以及TS含量对牛粪秸秆混合厌氧干式发酵产甲烷过程的影响,并对沼渣特性进行表征。结果表明:固定TS含量25%时,添加1%褐铁矿(基于底物TS含量)显著促进产甲烷过程,产气量比对照组增加了21 mL·g~(-1)(以VS计);对照组(无褐铁矿)和添加1%褐铁矿时,纤维素降解均随TS含量升高而降低;TS含量40%时,添加1%褐铁矿对产甲烷过程具有抑制作用,甲烷产率相比于对照组(TS含量25%)降低了71%。可见只有当TS含量25%时,添加适量褐铁矿才能有效促进牛粪秸秆混合厌氧发酵产甲烷过程。研究可为优化农业废弃物甲烷化提供参考。     

基质组分对厨余与污泥共发酵动力学特性的影响

通过厌氧发酵4阶段动力学实验、产甲烷抑制实验及单一VFA的产甲烷动力学实验,探明了厨余和污泥共发酵过程中,典型组分对其潜在的酸积累类型以及甲烷化过程的影响。结果表明,不同基质组分在厌氧发酵过程中的VFA组成比例以及单一VFA的产甲烷化动力学特性,对其产甲烷潜能及速率有着决定性影响。乙酸的甲烷化速率高达44.80 mL·d~(-1),丁酸略慢于乙酸,而丙酸和戊酸的甲烷化速率不足乙酸的1/2,其中丙酸的延滞期长达1.76 d。因此,产酸类型以乙酸为主的污泥、菜类在产甲烷阶段不存在延滞期;而蛋肉类及油的产甲烷速率受到丙酸、戊酸动力学特性的影响相对较慢。通过调整共发酵基质配比不仅能够提高发酵潜能,还能够优化VFA组成比例,实现较高的甲烷产率及甲烷化速率。     

氧化铁对不同有机负荷下餐厨垃圾厌氧消化产气的影响

进行了餐厨垃圾(FW)和接种污泥(Ⅰ)基于不同VS比(分别为FW/I=1,FW/I=3,FW/I=5)下的中温厌氧消化实验,对比了不同有机负荷下未添加氧化铁和添加氧化铁对餐厨垃圾厌氧消化产气的影响。结果表明,在FW/I=1时,餐厨垃圾厌氧消化体系的产气情况主要由接种污泥决定,添加氧化铁仅能在较小的程度上促进体系产甲烷能力提升;而在FW/I=3时,添加氧化铁可以帮助餐厨垃圾厌氧消化体系从低速产甲烷过程快速进入高速产甲烷,快速降解有机质实现稳定化;而对于FW/I=5时添加氧化铁可以解除由于有机负荷过高造成的酸抑制并恢复体系的产甲烷能力。因此,在实际应用厌氧消化技术处理餐厨垃圾中可以通过添加氧化铁来提高其有机负荷(OLR),提高处理效率,保证餐厨垃圾厌氧消化的正常运行和促进甲烷的产生。     

青岛市餐厨垃圾与菜市场垃圾混合高温厌氧消化研究

在中试规模下,研究青岛市餐厨垃圾与菜市场垃圾混合(质量比1∶1)高温厌氧消化实验,通过监测厌氧消化过程中产气量、气体组成等产气情况和消化液中pH值、SCOD、NH3-H、VFAs含量和组分等化学指标变化,确定混合厌氧消化的最大有机负荷,并分析混合高温厌氧消化技术的可行性,结果表明,(1)青岛市餐厨垃圾与菜市场垃圾混合高温厌氧消化产甲烷具有技术可行性;(2)混合厌氧消化的最大有机负荷可达4.069 kg VS/(m3.d);(3)当系统最大有机负荷时,每天每千克VS最高可产生甲烷量0.346 m3;(4)混合厌氧消化可削减氨氮对餐厨垃圾单独厌氧消化产沼气的影响。     

剩余活性污泥和厨余垃圾续批式混合中温消化试验研究

将加碱水解和未水解剩余活性污泥与厨余垃圾混合后进行序批式中温厌氧消化,对生化产甲烷势(BMP)进行了测定.剩余活性污泥的水解通过添加NaOH进行,合理的NaOH投量为40 mmol/L,在25 ℃和35 ℃下经过6 h的水解后SCOD水解率分别提高27.4%和31.1%.厨余垃圾、25℃和35℃下水解污泥的最终甲烷产量分别为607、284、312 mL/g(VS),两种水解污泥比未水解污泥分别高出43%、57.6%,水解污泥和厨余垃圾混合消化的可降解能力要优于未水解污泥和厨余垃圾的混合进料.     

干式厌氧消化过程挥发酸对硫酸盐还原菌的影响

在牛粪干式厌氧消化过程中,通过添加不同挥发酸(乙酸、丙酸、丁酸),考察消化稳定阶段,挥发性脂肪酸的分布特征,挥发性脂肪酸酸组成变化对硫酸盐还原菌(SRB)的影响,微生物种群组成和种群间关系。实验结果表明,挥发性脂肪酸对SRB还原速率的贡献依次为:丙酸丁酸乙酸。相比乙酸和丁酸,添加一定量的丙酸,更有利于激活SRB的活性,从而加强SRB与产甲烷菌(MB)的种间协同,保证厌氧系统的稳定运行。     

长链脂肪酸对餐厨垃圾厌氧消化产甲烷的影响

为研究中温条件下长链脂肪酸(LCFA)的含量及代谢对餐厨垃圾厌氧消化过程的影响,考察了LCFA添加量分别为0、0.6、1.2、1.8、2.4、3和3.6 g·L~(-1)条件下产沼气量、累积甲烷产量以及代谢中间产物挥发性脂肪酸/乙醇的浓度和组成。结果表明:在中温餐厨垃圾厌氧产甲烷的过程中,虽然LCFA也能够被微生物代谢转化生成甲烷,但LCFA的存在会对产甲烷过程造成一定程度的抑制作用;当其含量较低时抑制作用较为微弱,当其含量较高(2.4 g·L~(-1))时,甲烷产量及产甲烷速率都会受到较大影响;特别是当LCFA含量高于3.6 g·L~(-1)时,体系出现较强的抑制现象。通过实验累积值与理论甲烷产率的对比可以发现,LCFA含量越高的反应器中实验累积值/理论值的比值越低,表明有机物的转化效率越低。通过对厌氧过程中间产物的检测可知,LCFA含量越多的反应器中初期累积的挥发性脂肪酸浓度越高,当反应体系的LCFA浓度超过2.4 g·L~(-1)时,累积的乙酸和丙酸浓度较高,丙酸降解过程和乙酸代谢产甲烷的过程受到一定程度的延滞和抑制作用,降解速率低于正常水平,厌氧发酵的能力和效率受到影响。     

低强度超声波预处理对厨余垃圾厌氧消化的影响

以厨余垃圾为研究对象,实验研究产气效率、pH、SCOD、甲烷浓度及生物降解率5个参数的变化趋势,比较低强度超声波处理对厨余垃圾厌氧消化产气特性的影响,结果表明:(1)低强度超声波处理对厨余垃圾厌氧消化产生明显效果,在不同的超声波强度(100、175和250 W)或处理时间(20和40 min)下,产气效率、累计产气量、pH下降幅度、SCOD增加幅度随处理时间和超声功率增加而增加;在超声波强度250 W和处理时间60 min下出现抑制作用;(2)在超声波强度250 W和处理时间40 min条件下,超声波对厨余垃圾厌氧消化增强效果最明显,累计产气量由未处理的3 513 mL提高至5 007 mL,提高42.6%,甲烷气体浓度由51.25%提高至58.8%,生物降解率由58.11%提高至73.5%.     

猪粪与玉米秸秆混合中温发酵产气效果

以猪粪及碱液预处理后的玉米秸秆为原料,在恒温35℃和料液总固体质量分数为5%的条件下,以实验室内培养的不产气厌氧活性污泥为接种物,研究猪粪与玉米秸秆不同配比(干物质比分别为1∶3、1∶2、1∶1、2∶1、3∶1和0∶1(单一猪粪))混合发酵对产气效果的影响。研究结果表明,在35℃条件下,猪粪与玉米秸秆以2∶1配比的累积产气量最大,为15 157 mL;其次是1∶1样品,累积产气量为15 088 mL。但甲烷产量最高为1∶1样品,56 d共产甲烷9 137 mL,甲烷气占总产气量的60.6%。通过对发酵过程中pH及COD的测定,证明经碱液预处理后的玉米秸秆能与猪粪混合稳定发酵,发酵前后厌氧消化液中COD的降解率可达50%以上。进一步研究分析得出,将玉米秸秆和猪粪按一定比例混合发酵不仅可以缩短发酵周期、提高产气速率,而且可以大幅提升原料的产气潜力。     

浮萍与剩余污泥厌氧消化产沼气实验

为了提高浮萍厌氧消化产沼气能力,对比浮萍和剩余污泥的单独以及混合厌氧消化过程的产气情况,得到当两种底物混合厌氧消化时,具有互补优势,缩短了产甲烷过程的酸化期,累积产气量实际值比计算值提高11%。此外,研究底物的预处理以及底物与接种物比例对厌氧过程的影响,结果表明,浮萍经热碱预处理后比未处理组甲烷产量增加了8%,且厌氧消化产沼气时间缩短;当底物与接种物比例为1∶1时,整个反应过程的pH维持在6.00以上,利于产甲烷过程,体系中积累的挥发性脂肪酸(VFAS)最多,且获得的总沼气产量和总甲烷产量最大,分别为3 309 m L和1 883 m L,比最低的1∶2.5组分别高出151 m L和304 m L。     

Analysis of the syntrophic anaerobic digestion of volatile fatty acids using enriched cultures in a fixed-bed reactor

Volatile fatty acids (VFAs) are key intermediates in anaerobic digestion. Enriched acetogenic and methanogenic cultures were used for the syntrophic anaerobic digestion of VFAs in a continuous fixed-bed reactor at mesophilic conditions. The interactive effects of propionic (HPr), butyric (HBu), and acetic (HAc) acids were analyzed. Furthermore, hydraulic retention time (HRT) and methanogen-to-acetogen ratios (M/As) were investigated as the key microbiological and operating variables of VFA anaerobic degradations. Experiments were carried out based on central composite design (CCD) and results were analyzed using response surface methodology (RSM). Effluent concentrations of HPr, HBu, HAc, and biogas production rate (BPR) were directly measured as responses. The optimum conditions were found to be HPr = 1122.9 mg/L, HBu = 1792.4 mg/L, HAc = 1735.4 mg/L, HRT = 21 hours, and M/A = 2.4 (corresponding to the maximum VFA removal and BPR). The results of verification experiments and predicted values from fitted correlations were in close agreement at a 95% confidence interval.     

利用气相色谱法测定剩余污泥厌氧消化产生的混合VFA

厌氧消化是剩余污泥处理的重要方法,消化过程中会产生大量的挥发性脂肪酸(VFA)。讨论了气相色谱在恒温条件下对剩余污泥厌氧消化过程中产生乙酸、丙酸、异丁酸、正丁酸、异戊酸、正戊酸测定的可行性。结果表明:各种酸出峰时间间隔清晰,易于识别;从数据平行测试的变异系数看,异戊酸的变异系数最大,也仅为3.23%,表明测试方法具有良好的可重复性;回收率实验表明,剩余污泥消化液中各种VFA组分的回收率在96%～105%之间,符合文献规定的测试要求。     

含固率对牛粪常温厌氧消化的影响

在常温、pH值为7.0下,采用10 L玻璃瓶作为反应器对含固率(TS)分别为2%、6%、10%和14%的4组牛粪溶液进行厌氧消化实验,系统运行48 d,分析了厌氧消化过程中的COD(化学需氧量)、pH、VFA(挥发性脂肪酸)和产气量的变化。结果表明,进料TS是影响牛粪厌氧消化产气效果的重要因素,调节牛粪进料TS至10%,可以使其厌氧消化获得最佳的产气效果,COD去除率为24.6%,产气中甲烷含量为56.1%。     

食品废弃物厌氧消化产乙酸的研究

通过实验,研究了pH、总固体浓度(TS)、碳氮比(C/N)对食品废弃物厌氧消化产乙酸的影响,详细考察了挥发性脂肪酸(VFA)的组成和浓度及乙酸浓度随时间的变化规律.结果表明,pH为6.5、TS为7%(质量分数)、C/N为16:1时,总VFA的最大质量浓度为31.56 g/L,乙酸的最大质量浓度为19.46 g/L.     

接种比对餐厨垃圾干式厌氧发酵启动的影响

针对不同接种比对餐厨垃圾干式厌氧发酵启动的影响,对比分析了VS接种比分别为0.36和0.90两种情况下,餐厨垃圾干式厌氧发酵启动过程中pH、NH4-N、COD、VFA、甲烷含量等指标的变化。实验结果表明,启动初期2组样品pH分别快速降至4.74和5.68,均呈酸化状态,经碱液调整后,接种比为0.36的处理仍无法正常产气,接种比为0.90的处理,pH逐步提高,系统正常运行,经72 d的发酵实验,COD去除率达90.29%,甲烷含量高于60%的沼气产量达255.4 L,分析可见,VS接种比是干式厌氧发酵处理的重要参数;此外,与传统湿式厌氧发酵处理相比,餐厨垃圾干式厌氧发酵在较高的VFA和氨氮浓度下,仍能正常运行,采用干式厌氧发酵技术处理餐厨垃圾是可行的。     

Biohydrogen production from dairy manures with acidification pretreatment by anaerobic fermentation

Background, aim, and scope  

Hydrogen is a clean and efficient energy source and has been deemed as one of the most promising carriers of new energy for the future. From an engineering point of view, producing hydrogen by mixed cultures is generally preferred because of lower cost, ease of control, and the possible use of organic waste as feedstock. The biological hydrogen production has been intensively studied in recent decades. So far, most investigates of biohydrogen production are still confined to using pure carbohydrates and carbohydrate-rich wastewater. Nowadays, the large amounts of livestock manure, which come from cattle feedlots, poultry, and swine buildings, are causing a major environmental issue because it has become a primary source of odors, gases, dust, and groundwater contamination. The increasingly stringent requirements for pollution control on livestock manures are challenging the scientific community to develop new waste treatment strategies. Thus, there is a pressing need to develop nonpolluting and renewable energy source utilizing the organic waste (e.g., livestock manure). It is well known that anaerobic digestion had successfully been used for the disposal of manures to produce methane in the last two decades. Recently, an alternative strategy has been developed to convert livestock manures (e.g., dairy manures) to biohydrogen as a high value-added clean energy source instead of methane. However, little information is available on hydrogen production from dairy manure via the mixed anaerobic microbe. As far as we know, the hydrogen production is habitually accompanied with production of volatile fatty acids (VFAs), such as acetate, butyrate, and propionate, which are also an optimal feedstock for production of methane by anaerobic digestion. Provided that the biohydrogen production from dairy manure is further combined with the anaerobic digestion of the effluent from the producing hydrogen reactor that would be a one-stone two-bird paradigm, it not only produces a clean and readily usable biologic energy but also cleans up simultaneously the environment in a sustainable fashion.     

混合水解对打捆麦秸水解产酸的影响

为研究混合水解对麦秸水解产酸的影响，以猪粪、厨余和蔬菜废物为原料，研究其分别与麦秸混合水解产酸的特性，分析了水解过程中pH值、COD、SCOD和VFAs的变化。结果表明，除麦秸＋蔬菜废物最佳出料时间为3～9d外，麦秸、麦秸＋厨余垃圾、麦秸＋猪粪水解液最佳出料时间均为3～7d，7d后水解液COD浓度下降；将蔬菜废物与麦秸混合水解，水解液pH值降低幅度最大，水解液中总有机酸浓度最高，pH值最低为5．31，有机酸浓度最高达6．46g／L，且水解液中SCOD浓度、SCOD／COD比值最大；添加猪粪明显促进了麦秸有机物的水解溶出，麦秸单位干物质水解率和产酸率较对照分别提高了43％～134％和50．53％，但对提高水解液SCOD浓度、SCOD／COD比、TVFA浓度、降低水解液pH值的效果不如蔬菜废物；添加厨余垃圾的效果介于猪粪和蔬菜废物之间。从促进麦秸水解产酸的角度，以添加猪粪的效果最好。     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.