新型生物制氢反应器的运行及产氢特性

以厌氧活性污泥为产氢菌种,糖蜜废水为底物,研究了新型外循环颗粒污泥膨胀床(ECGSB)生物制氢反应器的运行及产氢特性.结果表明,ECGSB反应器可在较高的容积负荷(VLR)下实现高效稳定的产氢,稳定运行时,反应器内可观察到自絮凝产氢颗粒污泥的形成,污泥平均浓度高达24.1gVSS/d,系统最大产氢能力为7.43m3/m3·d,发酵气中氢气体积含量为50%～56%.系统形成自絮凝产氢颗粒污泥是ECGSB反应器高效运行和产氢的关键,自絮凝产氢颗粒污泥既增加了活性产氢细菌的生物持有量,又提高了系统抗冲击负荷的能力.连续流运行各项参数表明,ECGSB反应器具有良好的运行稳定性和产氢优势;提出乙醇型发酵快速启动的调控对策,在发酵法生物制氢领域具有广泛的应用前景.     

有机废水发酵法生物制氢中试研究

利用厌氧细菌的产酸发酵作用进行生物制氢的生物制氢技术 ,在世界范围内受到普遍重视。然而 ,多数研究都集中在纯菌种的产氢机理上 ,而对混合菌种的研究较少。该文在小试研究成果的基础上 ,利用驯化的厌氧活性污泥进行了中试规模的生物制氢试验研究 ,获得了 30mol/kgVSS .d的持续产氢能力。试验结果表明 ,将运行参数控制在温度 35℃、pH4 0～ 4 5、HRT4～ 6h、ORP - 10 0～ - 12 5mV、进水碱度 30 0～ 5 0 0mg/L (以CaCO3 计 )、容积负荷 35～ 5 5kgCOD/m3 ·d等范围时 ,发酵法生物制氢反应器的最大持续产氢能力可达 5 7m3 /m3 ·d。中试制氢反应器具有良好的抗负荷冲击能力和运行稳定性 ,对制糖废水中的COD去除率可达到 2 0 %以上 ,去除单位COD可获得 2 6mol/kgCOD的产氢率。     

丁酸型发酵产氢的运行稳定性

着重对发酵法生物制氢反应系统的丁酸型发酵的运行稳定性进行了研究分析。结果表明,在有机负荷大于21kgCOD/m3·d的条件下,丁酸型发酵具有不稳定性,在负荷冲击下容易转变为丙酸含量较高的发酵类型,从而导致系统产氢能力的下降。分析认为,NADH/NAD+的平衡调节能力是影响系统运行稳定性的一个关键因素。在高负荷条件下,由于丁酸型发酵的产丁酸过程不能氧化过剩的NADH+H+,导致产乙酸过程生成的剩余NADH+H+在系统内大量积累,使反应系统难以达到氧化还原的平衡状态,最终影响了系统的稳定运行。     

连续流生物制氢反应器中有机负荷对产氢的影响

采用连续流搅拌槽式反应系统(CSTR)作为反应装置,以红糖水为发酵底物,污水处理厂剩余污泥为反应的启动污泥,在进水p H值为7.0±0.1、氧化还原电位(ORP)为-420 m V、温度(35±1)℃、水力停留时间(HRT)为6 h等影响因子调控下,达到稳定产氢(主要为乙醇型发酵)。在其他参数不变的条件下,通过改变有机负荷,着重研究其对产氢能力的影响,同时调节p H值使微生物保持较高活性。结果表明,当有机负荷从12 kg/(m3·d)上升为32 kg/(m3·d)时,产气和产氢速率均有持续增大的趋势。当有机负荷为32 kg/(m3·d)时,达最大产气速率(18.6 L/d),产氢速率为6.4 L/d,较初始有机负荷12 kg/(m3·d)时分别提高89%和87%。在系统运行过程中,进水p H值降低至5.85时,厌氧发酵微生物活性受到抑制,产氢速率有所下降,ORP上升至-328 m V。此时,向反应器内投加一定量的Na OH调节p H值,使反应器保持较高产氢速率的乙醇型发酵类型。     

基于UASB反应器的厨余厌氧发酵产氢研究

针对目前厨余连续流发酵产氢处理负荷不高、产氢率较低的难题,采用UASB反应器进行厨余发酵产氢研究。在温度为30℃,进水COD浓度为2 000~10 000 mg/L,水力停留时间为2~6 h条件下,产氢速率最大达到17.04 L/(L.d)。反应器内有颗粒污泥的形成,平均生物量达到6.17 g/L,为氢气的产生提供了有利保障。当出水pH为4.2~4.4,碱度为260~340 mg/L的条件下,乙醇和乙酸占挥发酸总量的89.2%,形成稳定的乙醇型发酵类型,反应器最高处理负荷COD达到60 kg/(m3.d)。试验结果表明,UASB反应器具有更高的产氢效能和更加稳定的产氢效果,能够为厨余发酵产氢提供有利的保障。     

生物制氢反应器产氢产乙酸菌群对挥发酸的转化

采用间歇培养的方式,利用取自生物制氢反应器的厌氧活性污泥考察了活性污泥中产氢产乙酸菌群对乙醇、乙酸、丙酸、丁酸、戊酸和乳酸的转化和产氢。结果表明,培养时间为44h时,厌氧活性污泥发酵葡萄糖的累计产气量为356mL,累计产氢量为209mL,氢气含量为58.7%。发酵产物的组成成分乙醇为427.1mg/L、乙酸为716.5mg/L、丙酸为172.5mg/L、丁酸为689.4mg/L、戊酸为123.6mg/L。发酵生物制氢反应器厌氧活性污泥中产氢产乙酸菌群能够对乙醇和乳酸进行产氢产乙酸转化,厌氧污泥转化乙醇形成的乙酸含量约为270mg/L,累计产氢量为15mL;转化乳酸形成的乙酸含量约为190mg/L,累计产氢量为7mL。厌氧污泥不能对乙酸、丙酸、丁酸和戊酸进行产氢产乙酸转化,培养过程中也没有气体生成,分析认为产氢产乙酸菌群对挥发酸的转化不是发酵生物制氢反应器产氢的主要途径。     

生物制氢混合培养系统启动与运行的人工操作

采用连续流搅拌槽式反应系统(CSTR)作为反应装置,以糖蜜废水为发酵底物,污水处理厂剩余污泥为反应的启动污泥,着重对pH和氧化还原电位(ORP)调控下生物制氢反应器乙醇型发酵的启动进行了研究.结果表明:在温度为(35±1)℃,水力停留时间(HRT)为6h,进水COD为4000mg/L时,通过调节ORP和系统pH值可在约33d实现生物制氢反应器中微生物的主要代谢类型为乙醇型发酵,并实现稳定产氢.     

餐厨垃圾SBMR-ASBR两相厌氧消化产气性能研究

以学校食堂餐厨垃圾为原料,考察餐厨垃圾在SBMR-ASBR反应器中产酸和产甲烷性能。结果表明:高负荷下启动酸化相有利于系统快速形成稳定的乙醇型发酵,且可以避开丙酸型发酵,在10 g/(L.d)负荷(以VS计)下,稳定状态产酸率平均达到55 000 mg/L,VFA中乙醇和乙酸分别平均稳定在27 000 mg/L和23 000mg/L,两者共占总VFA的91%;甲烷相可以稳定运行的最高负荷为5 g/(L.d)(以VS计),此时,系统整体处理能力为3.3 g/(L.d),单位容积产气率达到2.3 L/(L.d),甲烷含量在65%～70%,TS,VS去除率分别达到77%,83%。在实际工程中可以高负荷启动酸化相,有利于系统形成稳定的乙醇型发酵和高负荷运行的甲烷相。     

厌氧活性污泥发酵制氢系统中的同型产乙酸作用及其控制

为提高厌氧活性污泥发酵生物制氢反应系统的产氢效能,以CSTR的运行为基础,通过系统活性污泥的间歇培养试验,探讨了同型产乙酸菌群对发酵制氢系统产氢效能的影响,并以CHCl3和二溴乙烷磺酸钠(BES)为抑制剂,研究了抑制同型产乙酸菌群活性的方法。结果表明:CSTR发酵产氢系统中,存在较强的同型产乙酸作用,是导致发酵气氢含量较低的主要原因;向反应体系中投加0.1%~1.0%(V/V)的CHCl3,可有效抑制同型产乙酸作用;在初始葡萄糖浓度5000mg/L、pH=7.0、污泥接种量1.6g MLVSS/L等条件下,CHCl3加入量为0.5%时,活性污泥的比产氢速率可达8.9mmolH2/gMLVSS,是不加抑制剂反应体系的2倍。10mmol/L剂量的BES,不仅对同型产乙酸菌无抑制作用,且可削弱CHCl3的抑制效果。     

产氢菌的投加方式对强化发酵菌群产氢的影响

通过间歇培养研究了产氢菌Ethanoligenens sp B49的投加方式对生物制氢反应器的混合发酵菌群生物强化作用的影响.结果表明,产氢菌的投加方式对发酵菌群的产氢能力有显著影响.产氢菌发酵液的直接投加使发酵菌群的产氢能力下降,并引起培养液中发酵产物乙醇和乙酸浓度的显著增加.分析认为,产氢菌发酵液对发酵菌群的末端产物抑制和低pH值抑制作用是导致产氢作用受到抑制的主要原因.离心后单独投加产氢菌菌体可提高发酵菌群的产氢能力,起到强化产氢的作用.投加10.8%的产氢菌强化发酵菌群时,培养45h的累计产氢量为155.0 mL.比强化前发酵菌群培养的产氢量提高了21.5%.因此在利用产氢菌生物强化发酵菌群的研究中,应采用离心分离后单独投加产氢菌菌体的方式进行生物强化.     

High hydrogen production rate on RuS2@MoS2 hybrid nanocatalyst by PEM electrolysis

A new nanocatalyst, which combines the electrocatalytic activity of MoS₂ nanosheets and RuS₂ nanoparticles (NPs), was prepared through a safe and scalable, one-step “bottom-up” approach. It delivers high current density, with a Tafel slope of 36 mV/dec and a very small overpotential. The high exposure of MoS₂ edges on the RuS₂ NPs, the stronger d character of RuS₂ and the electrical coupling of these two nanomaterials, grown together, were responsible for the high hydrogen production rates of 10.2 l/h (PEM cell 5cm × 5 cm, current density about 1.1 A/cm², power consumption 41.8 W, corresponding to 3.8 KWh/Nm³ of energy consumption, efficiency 93%).     

发酵原料水解率对CSTR反应器产气率影响的研究

文中以泰康镇奶牛广场的新鲜奶牛粪便为原料,对发酵原料水解率对CSTR反应器产气率的影响因素进行探索研究。采用单因素、正交试验方法,得到最优工艺条件组合：加酶量1000U／g;投料浓度8％;加酶时间6h;搅拌时间8h。     

Simultaneous coproduction of hydrogen and methane from sugary wastewater by an “ACSTRH–UASBMet” system

A two-phase “ACSTR_H–UASB_Met” system has been investigated at the stepwise decreased HRT for the simultaneous production of hydrogen and methane in this study. Hydrogen could be continuously produced from the two-phase hydrogen fermentation of sugary wastewater in ACSTR and effluents from hydrogen fermentation were converted into methane in UASB reactor. At optimum conditions (HRT_H: 5 h, HRT_Met: 15 h), the highest hydrogen production rate of 5.69 (±0.06) mmol L⁻¹ h⁻¹ was obtained from sugary wastewater and methane was continuously produced from effluents of hydrogen fermentation with a production rate of 3.74 (±0.13) mmol L⁻¹ h⁻¹. The total bioenergy recovery by coproduction of hydrogen and methane from sugary wastewater reached 19.37 W and a total of 92.41% of substrate was converted to the biogas (hydrogen and methane) with two-phase anaerobic fermentation.     

Biohydrogen from molasses with ethanol-type fermentation: Effect of hydraulic retention time

Though ethanol-type fermentation has many advantages for improving hydrogen production rate (HPR) in continuously mode hydrogen producing system, information on this fermentation is very deficient. The effect of hydraulic retention time (HRT) on biohydrogen production and operational stability of ethanol-type fermentation was investigated in a continuous stirred tank reactor (CSTR) using molasses as substrate. Five HRTs were examined, ranging from 4 to 10 h. At HRT 5 h, the highest HPR of 12.27 mmol L⁻¹ h⁻¹ was obtained from ethanol-type fermentation in the pH range of 4.3–4.4. During the whole operation process, ethanol, butyrate and acetate were the predominant metabolites. A total COD concentration of ethanol and acetate accounted for above 73.3% of total soluble microbial products. Linear regression showed that HPR and ethanol production rate were proportionately correlated at all HRTs which could be expressed as y = 0.9821x − 3.5151 (r² = 0.9498). It is meaningful that the proposed recovery of both hydrogen and ethanol from fermentation process can improve energy production rate and economic profit. Results demonstrated that the best energy production rate was 15.50 kJ L⁻¹ h⁻¹, occurred at HRT = 5 h.     

Comparison of thermophilic and hyperthermophilic dark fermentation with subsequent mesophilic methanogenesis in expanded granular sludge bed reactors

Herein, dark fermentation (DF, V = 5.5 L) and subsequent mesophilic methanogenesis (V = 43.5 L) are run as expanded granular sludge bed reactors (EGSB) at thermophilic (υDF = 60 °C) and hyperthermophilic (υDF = 80 °C) temperatures. A synthetic glucose wastewater is run with a 22.5 g/L chemical oxygen demand (COD) and 48–9 h hydraulic retention times (HRTs), giving organic loading rates (OLRs) of 11–60 g COD/L/d for DF. The maximum hydrogen production rate (HPR) is HPR = 3.0 m³/m³/d for HRT = 9 h with a 50 L/kg COD hydrogen yield (HY) and 40 vol% H₂. Methane production rate (MPR) reaches MPR = 2.6 m³/m³/d with 70 vol% CH₄ at HRT = 2.8 d. The highest H₂ yields are HY = 180 L/kg COD with 53 vol% H₂ (thermophilic, HRT = 48 h). Hyperthermophilic temperatures led to lower HPRs (0.7 m³/m³/d) and MPRs (1.6 m³/m³/d). 53% of Thermoanaerobacterium thermosaccharolyticum as an H₂ producer are found. Discoloration of granular sludge from black to white and granule stability was observed in DF.     

Minimizing the entropy production in a chemical process for dehydrogenation of propane

We minimize the total entropy production of a process designed for dehydrogenation of propane. The process consists of 21 units, including a plug-flow reactor, a partial condenser, two tray distillation columns and a handful of heat exchangers and compressors. The units were modeled in a manner that made them relatively insensitive to changes in the molar flow rates, to make the optimization more flexible. The operating conditions, as well as to some degree the design of selected units, which minimized the total entropy production of the process, were found. The most important variables were the amount of recycled propane and propylene, conversion and selectivity in the reactor, as well as the number of tubes in the reactor. The optimal conversion, selectivity and recycle flows were results of a very clear trade-off among the entropy produced in the reactor, the partial condenser and the two distillation columns. Although several simplifying assumptions were made for computational reasons, this shows for the first time that it is also meaningful to use the entropy production as an objective function in chemical engineering process optimization studies.     

龙岩市垃圾卫生填埋场填埋气体产量预测研究

对填埋气的回收利用,既能减排温室气体,又能回收能源。根据龙岩市的垃圾组成、填埋场处理量等条件,系统地分析了各种产气模型的计算方法、优缺点及适用条件,合理地选择了产气模型和参数。根据该模型计算出龙岩市垃圾填埋场气体产量和气发电机装机容量。     

Comprehensive modeling of photo-fermentation process for prediction of hydrogen production

Hydrogen production via modern technologies and without using fossil fuels has been found considerably important recently. Photo-fermentation is introduced as one of the most effective methods without high risk for bio-hydrogen production. In this study, comprehensive modeling and simulation of bio-hydrogen production is carried out through photo-fermentation process. In this way, different applicable models are considered to predict the kinetics of microbial growth. Also, new modified mathematical models are particularly proposed for photo-fermentation to forecast the specific growth rate of microorganisms, substrate consumption and hydrogen production rates. Various combinations of the models are applied and predictions of the models are validated by experimental data related to the growth of Rhodobacter Sphaeroides on malate as the substrate. The combination, entitled as MVA1, is introduced as the best one to predict kinetic factors in photo-fermentation. The presented models can be used as an excellent starting point to accomplish experimental and industrial works.     

新村油田古26区块线性注水效果评价

到2008年底,新村油田古26区块共有油水井272口,其中注水井99口,抽油井173口。累积产油85．3235×10^4t,采出程度9．44％。区块开发初期,采用反九点法采油井网开发,区块油井见水快,产量递减快,地层压力分布不均衡,表现出明显的裂缝性油田注水开发特征。通过实施线性注水,有效减缓了区块含水上升速度快、产量递减快的矛盾,线性注水前后,因含水上升造成产量递减占区块递减构成比例有所减少,由2003年的14．10％减少到2007年的5．17％,减少8．93个百分点;2004～2006年注采系统调整使区块产量递减率分别下降了1．35％、0．36％和0．70％;线性注水前后对比,非主力层产出由31．1％上升到32．2％,非主力层吸水由29．5％上升到36．3％。利用采油速度、递减率、地层压力、存水率等开发指标对古26区块线性注水效果进行了评价。     

Biological fermentative hydrogen and ethanol production using continuous stirred tank reactor

Hydrogen and ethanol are promising biofuels and have great potential to become alternatives to fossil fuels. The influence of organic loading rates (OLRs) on the production of fermentative hydrogen and ethanol were investigated in a continuous stirred tank reactor (CSTR) from fermentation using molasses as substrate. Four OLRs were examined, ranging from 8 to 32 kg/m³·d. The H₂ and ethanol production rate in CSTR initially increased with increasing OLR (from 8 to 24 kg/m³ d). The highest H₂ production rate (12.4 mmol/h l) and ethanol production rate (20.27 mmol/h l) were obtained in CSTR both operated at OLR = 24 kg/m³ d. However, the H₂ and ethanol production rate tended to decrease with an increase of OLR to 32 kg/m³ d. The liquid fermentation products were dominated by ethanol, accounting for 31-59% of total soluble metabolities. Linear regression results show that ethanol production rate (y) and H₂ production rate (x) were proportionately correlated which can be expressed as y = 0.5431x + 1.6816 (r² = 0.7617). The total energy conversion rate based on the heat values of H₂ and ethanol was calculated to assess the overall efficiency of energy conversion rate. The best energy conversion rate was 31.23 kJ/h l, occurred at OLR = 24 kg/m³ d.