APPLICATION OF GASndashLIQUID TWO-PHASE CROSS-FLOW FILTRATION TO PILOT-SCALE METHANE FERMENTATION

ABSTRACT

As part of a national project, “Aqua-Renaissance '90,” by the MITI, a pilot-scale evaluation of membrane-enhanced anaerobic fermentation, has progressed for the wastewater from a pulp and paper mill. A novel membrane filtration system was newly proposed with the aim of saving energy. That is, a gas-liquid two-phase cross-flow filtration which was generated with liquid circulation by an air-lift pump effect, was combined in the anaerobic bioreactor. It was confirmed that the membrane filtration not only offered very stable and large permeate flux, but enhanced the processing efficiency by retaining the microorganisms in the bioreactor. Furthermore, the power consumption per unit permeate volume in the membrane system of 1.78 kWh/m³ was achieved. which was a very highperformance result from the viewpoint of saving energy, as compared with 3ndash;5 kWh/m³ of conventional liquid single-phase cross-flow filtration.     

Dyeing and printing wastewater treatment using a membrane bioreactor with a gravity drain

A laboratory-scale membrane bioreactor (MBR) with a gravity drain was tested for dyeing and printing wastewater treatment from a wool mill. The MBR was operated with continuous permeate by gravity and without chemical cleaning for 135 days. Results showed that excellent effluent quality could meet the reuse water standard in China. The average concentrations of COD, BOD₅, turbidity and color in the effluent were 36.9 mg l⁻¹, 3.7 mg l⁻¹, 0.2 NTU and 21 dilution times (DT), respectively. The average removal rates of COD, BOD₅, turbidity and color were 80.3%, 95.0%, 99.3% and 58.7%, respectively. The membrane flux increased with increasing of aeration intensity, and its increasing rate was related to pressure-heads. The higher the pressure-head, the greater the impact of aeration intensity on membrane flux. Statistical analysis also showed that both the pressure-head and aeration intensity significantly affected membrane flux. Due to its compact design, simple operation and easy maintenance, MBR with a gravitational filtration system hs low energy consumption and is cost-effective to build and operate. If the life expectancy of the membrane is set for 3–4 years and the membrane flux is set at 15 l/m²·h, such a MBR would be very competitive.     

Sustainable fuel cell integrated membrane desalination systems

According to the United Nations, between two and seven billion people will face water shortages by the year 2050. Further, it is estimated that the amount of water available per person will shrink by a third during the next two decades. Inadequate supply of good-quality water coupled with higher water demand due to rapid population growth and industrialisation in developing countries are among the major reasons for the worsening water situation. Current shortages of potable water around the world and looming water scarcity especially in the developing countries is the driving force behind the implementation of membrane technologies for seawater and brackish water desalination. Typical energy consumption in seawater reverse osmosis (RO) plants operating at 40–45% product water recovery and with energy recovery from the high pressure reject stream currently is about 3–4 kWh/m³. The near-term goal of the industry is to reduce energy consumption to less than 2 kWh/m³ by using a combination of energy efficient RO pumps, more efficient energy recovery devices, high performance low energy RO membranes, hybrid membrane systems, advanced pretreatment technologies and alternate energy integrated membrane systems. The beneficial aspects of using alternate energy systems such as on-site distributed fuel cell systems integrated with membrane desalination units in remote locations are discussed.     

太阳能光热-光电中空纤维真空膜蒸馏系统理论与实验研究

自主设计并搭建了太阳能光热-光电中空纤维膜蒸馏系统,太阳能光热采用面积1.82 m²真空管集热系统,光伏发电采用面积1.63 m²多晶硅电池板。实验方面,研究了不同工况下,热料液在不同流动方式时膜通量的差异;研究了在不同跟踪方式下太阳辐照度对系统性能的影响。结果表明：料液在管程流动的膜通量大于壳程的膜通量,且进口料液温度取50~70℃之间为宜;自动跟踪下膜组件入口温度比非跟踪高2~3℃,可以延长膜蒸馏系统运行时间1~2 h,且在相同的自然环境下,自动跟踪方式最大膜通量8.89 kg/(m²·h)远高于非跟踪方式时4.26 kg/(m²·h)。理论方面,分析了以水为工质的中空纤维膜蒸馏的传热和传质过程,建立了传热传质理论计算数学模型;分析了辐照强度、膜表面温差、膜丝内表面传热系数、传热与传质通量的定量关系,计算了膜面温度与理论膜通量,对比了实验值与理论值。系统运行稳定,能量综合利用效率高,性能可靠,为工程应用奠定了理论和实验基础。     

Ultrasonic defouling of reverse osmosis membranes used to treat wastewater effluents

On-line ultrasonic cleaning was used to remove fouling from a commercially important polyamide based reverse osmosis membrane during cross-flow filtration of CaSO₄, Fe³⁺ and carboxyl cellulose solutions. In each case, the permeate flux of the membrane increased significantly, with virtually no decrease in rejection in the presence of ultrasonication. Membrane surface characterization via scanning electron microscopy (SEM) confirmed the beneficial effect of ultrasonication on the membrane permeate flux. These studies suggest that ultrasonic defouling may be a very useful approach for the future development of reverse membranes, especially as far as fouling with organic materials is concerned.     

Hydrogen Bonding and the Interfacial Component of Adhesion: Acid/Base Interactions of Corona-Treated Polypropylene

The effect of activation of the surface of polypropylene sheet, by a corona discharge, upon the contact angles of liquids and on the surface free energy parameters γ^LW, γ^⊕ and γ^⊖, was determined. Both advancing and retreating contact angles were measured. The “acid/base” theory of the components of surface free energy was employed.

The contact angles of water and glycerol were initially lower by as much as 30°, after treatment, and that of diiodomethane was lower by about 5°. With time, the advancing angles rose, and the γ^⊕ and γ^⊖ parameters fell, towards the values on the untreated solids, and attained more or less steady values after 5 to 10 days. The basic component, γ^⊖, was the most strongly affected by the corona treatment; it rose, typically, from 2.2 to as high as 25 mJ/m². The acidic component, γ^⊕, rose from zero to as high as 1.9 mJ/m². Its decay with time was only qualitatively the same as that of γ^⊖. The retreating angles, and the corresponding energy components, were changed in the same direction, and somewhat more strongly, than were the “advancing” data.

The well-known improvement in the property of forming strong joints or adherent coatings, after corona treatment, is no doubt due to the formation of sites or areas on the polymers where hydrogen bonds can be formed. The decay of the strength of adhesion with time is, no doubt, due to the decay of these sites or areas.     

Treatment of potato chips manufacturing wastewater by electrocoagulation

Treatment of wastewater from potato chips manufacturing by electrocoagulation (EC) was investigated. Experiments were conducted to determine the optimum operating conditions such as electrode type, pH, current density and retention time. Aluminium and iron electrodes were used, and aluminium electrodes were found to be more suitable since it had a higher removal rate of COD, turbidity and suspended solids than the iron electrode. The removal efficiencies of COD and turbidity were high, being 60% and 98%, respectively, with retention time < 40 min. 0.05–1.75 kg (per kg COD removed) of dried sludge was removed. COD removal kinetics during EC process was described by a macro-kinetics model. Results from the kinetic studies showed that the kinetic data fit the second-order kinetic model well. The operating costs investigated in the present study were the energy cost of EC and the material cost due to the consumption of aluminium electrode. Operating costs were varied in the range of 0.48 to 5.42 $/m³ and 0.62 to 6.32 $/m³ wastewater treated at 20–300 A/m² and 5–40 min, respectively. The energy consumption was 4 kWh/m³ for wastewater treated less than 8 min under typical operating conditions.     

生物甲烷膜分离提纯系统的设计与优化

以厌氧发酵生物气为原料生产压缩天然气是大规模利用生物质资源的重要途径。首先,在过程模拟软件UniSim Design中基于有限元方法建立了中空纤维膜的离散数值计算模型,适合于模拟渗透切割比非常高的生物甲烷膜分离过程。以单级聚酰亚胺膜分离系统为例研究了关键操作条件--膜的进料压力对处理能力、甲烷收率及压缩天然气生产单耗的影响。目前的评估体系下,提高进料压力有利于提高处理能力和甲烷回收率,而压缩天然气生产单耗在2.70 MPa时最低,为0.46 kW·h·m^-3压缩天然气。通过分析渗透气的甲烷浓度变化趋势,开发了一级二段气体膜分离系统,兼具流程简单、设备投资低、甲烷收率高、产值高的优点。以处理1000 m³·h^-1生物气为例,甲烷收率达95.0%,压缩天然气产量500 m³·h^-1。对应地,装置总投资为3.8×10⁶ CNY,年运行费用及设备折旧为1.5×10⁶ CNY,年经济效益（毛利）超过2.50×10⁶ CNY。     

Measurement of the Surface Free Energy of Amorphous Cellulose by Alkane Adsorption: A Critical Evaluation of Inverse Gas Chromatography (IGC)

Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γ^d_s and γ^d_l, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γ^d_s was determined to be 71.5 mJ/m², and its temperature dependence was 0.36 mJ m^-2 K^-1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γ^d_s)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γ^d_s and d(γ^d_s)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”.     

Effect of physical parameters on the microfiltration of wine on a flat polymeric membrane

This paper investigates the microfiltration of unfiltered red and white wines through organic polyvinylidene difluoride membranes in plate and frame systems. Various pore sizes between 0.1 and 3 μm were first tested using a small laboratory unit and it was found that 0.4 μm pores gave the best comprise between turbidity and flux requirements. Tests with membrane areas between 1 and 2 m² were carried out i a modular plate and frame system in which both gasket thickness and parallel vs. series arangements of compartments can be modified. With red wine the permeate flux is almost independent of fluid velocity but increases linearly with transmembrane pressure, reaching 50 1 h⁻¹ m⁻² at 3 bar. The permeate flux is larger in a turbulent regime than in a laminar one at the same velocity. With white wine, the permeate flux is higher and increases almost linearly with velocity reaching 170 1h⁻¹ m⁻² at 2 bar and 3.6 m s⁻¹. The turbidity of the permeate was generally below 0.5 NTU for both white and red wines while initial turbidity was above 150 NTU for red and above 50 NTU for white. When several membrane compartments are placed in series, the output of the downstream compartment is reduced by 10%–15% compared with that of the upstream one owing to the drop in transmembrane pressure.     

DIFFUSIVITY DETERMINATION FROM THE RESPONSE TO INJECTION INTO LAMINAR LIQUID FLOW IN A CAPILLARY

A method for the determination of diffusivities in liquids is described; the method is based on measurements of the response to injection in a laminar flow of liquid in a capillary. By injection of δ-type, the component whose diffusivity is to be measured is introduced into the inlet part of a capillary of internal diameter 1.6 mm. The response to the injection is measured at the end of the capillary by a flow-through refractometer, the output signal of which is recorded on tape at 16-s intervals. The output signal is compared with a theroetical model of the time dependence of the response, based on Taylor's analysis of the dispersion of an injected component in laminar flow. The diffusivity is calculated from one of the model parameters, which were evaluated by the method of maximum likelihood. The calibration of the instrument was performed by measuring the diffusivity of KC1 in aqueous solution. The following diffusivities at 25°C were determined: n-butanol 971 μm²/s, dioxane 1093μm²/s, caprolactame 948 μm²/s, Na₂SO₄, 1126 μm²/s, salicylaldoxime 895 μm²/s, cyclohexanone 960 μm²/s, acetone 1316μm²/s, oxine 820.5 μm²/s, all in water; caprolactame in trichlorethylene 1958μm²/s, caprolactame in 10% aqueous (NH₄4)₂,SO₄ solution 1148 μm²/s, salicylaldoxime in chloroform 1878 μm²/S.     

外驱旋转式能量回收装置的设计和性能测试

旋转式能量回收装置（RERD）作为反渗透海水淡化系统的节能设备,对于降低系统能耗和产水成本具有重要意义。设计和加工了一套新的外驱旋转式能量回收装置,建立了满足其性能评测要求的一套完整的反渗透海水淡化系统。当装置的性能很好地满足工业化运用需求时,对RERD与反渗透淡化系统的耦合运行性能进行了现场测试。实验结果表明：反渗透膜的操作压力为6.0 MPa、RERD的处理量为13 m³/h及转子转速为500 r/min时,装置的泄漏量为0.57 m³/h,能量回收效率达到91.2%。保持反渗透膜的操作压力和装置转速不变,当装置的处理量为16 m³/h时,进出RERD的4股流体的流量和压力波动较小,装置的能量回收效率略有提高,达到92.5%。     

Development of energy-saving spinning membrane systemand negatively charged ultrafiltration membranes for recovering oil from waste machine cutting fluid

Membranes with hydrophobic surfaces have higher tendency for protein adsorption and bacteria attachment.As a result, these membranes foul rapidly in cross-flow filtration processes. Changing the membrane surface properties can slow down the membrane fouling process. For difficult membrane separation processes like oilwater emulsion separation, changing membrane properties alone cannot slow down the membrane fouling process. The ordinary cross-flow filtration system cannot be successfully employed for this kind of separation, and the spinning membrane disc system could be considered. The conventional spinning membrane disc system however is not energy efficient due to the centrifugal force acting against the permeate flow; this reduces the effective filtration pressure during the separation operation. Efforts were undertaken to develop a group of negatively charged ultrafiltration membranes, prepared from polyacrylonitrile-vinyl acetate-sodium p-sulfophenyl methallyl ether (CP-24) with polyacrylonitrile-vinyl acetate (CP-16), to be used in an energy-saving design of spinning membrane disc separation system. Our experimental results clearly demonstrate the energy saving benefit of our design; at filtration pressure of 276 kPa and at membrane disc spinning velocity of 1,000 rpm without sacrificing the oil rejection (>98% for 1,000 ppm oil-in-water) by our membrane, the permeate velocity was increased as high as 132% by our energy-saving system over conventional spinning membrane disc separation system.     

Reverse osmosis of diluted skim milk: Comparison of results obtained from vibratory and rotating disk modules

This paper investigates the reduction of ionic concentration and carbon oxygen demand (COD) in dairy process waters modelled by one volume of skim milk diluted with two volumes of water using shear-enhanced reverse osmosis. Initial COD and conductivity were, respectively, 36,000 mg O₂ L⁻¹ and 2000 μS cm⁻¹. We have compared the performances of a VSEP vibratory pilot and of a single rotating disk-stationary membrane module equipped with the same Desal AG membrane (Osmonics). Membrane shear rates were varied by changing the vibration frequency in the VSEP and the disk rotation speed or adding radial vanes in the other module. In all tests the permeate COD was reduced below 15 mg O₂ L⁻¹. Permeate fluxes reached a maximum of 180 L h⁻¹ m⁻² at a transmembrane pressure (TMP) of 4 MPa at initial concentration with the VSEP at its resonant frequency and with the disk equipped with 6 mm high vanes rotating at 2000 rpm. Permeate conductivity fell from 60 μS cm⁻¹ at 1 MPa to about 18 μS cm⁻¹ at 4 MPa. In concentration tests, corresponding permeate fluxes at the maximum volume reduction ratio reached (VRR = 8), were 55 L h⁻¹ m⁻² for the VSEP and 60 L h⁻¹ m⁻² for the rotating disk at a TMP of 4 MPa. Permeate conductivities increased exponentially with VRR from 18 to 210 μS cm⁻¹ for the rotating disk and to 250 μS cm⁻¹ for the VSEP. However the mean conductivity of collected permeate varied from 38 μS cm⁻¹at highest shear rate to 60 at lower shear rates. This study shows that these filtration systems permit to obtain reusable water from this high initial COD model effluent with one single reverse osmosis step.     

Oxidative coupling of methane in a mixed-conducting perovskite membrane reactor

Ionic-electronic mixed-conducting perovskite-type oxide La_0.6Sr_0.4Co_0.8Fe_0.2O₃ was applied as a dense membrane for oxygen supply in a reactor for methane coupling. The oxygen permeation properties were studied in the p_O2-range of 10⁻³−1 bar at 1073–1273 K, using helium as a sweeping gas at the permeate side of the membrane. The oxygen semi-permeability has a value close to 1 mmol m⁻² s⁻¹ at 1173 K with a corresponding activation energy of 130–140 kJ/mol. The oxygen flux is limited by a surface process at the permeate side of the membrane. It was found that the oxygen flux is only slightly enhanced if methane is admixed with helium. Methane is converted to ethane and ethene with selectivities up to 70%, albeit that conversions are low, typically 1–3% at 1073–1173 K. When oxygen was admixed with methane rather than supplied through the membrane, selectivities obtained were found to be in the range 30–35%. Segregation of strontium was found at both sides of the membrane, being seriously affected by the presence of an oxygen pressure gradient across it. The importance of a surface limited oxygen flux for application of perovskite membranes for methane coupling is emphasized.     

Energy production at the Dead Sea by pressure-retarded osmosis: challenge or chimera?

In recent years two types of very large-scale plants have been proposed for handling seawater brought to the Dead Sea, both processes taking advantage of the 400 m drop to Dead Sea level and both sized to replenish the 3,000,000 m³/d evaporation rate of the Dead Sea. Pressure-retarded osmosis (PRO), the process discussed herein, would use the replenishment stream to produce an appreciable amount of benign and renewable electric power. If the seawater plant prior to PRO would be reverse osmosis (RO), handling 5,000,000 m³/d to produce 2,000,000 m³/d of fresh water, PRO could produce 48,000 kW from the RO-concentrated seawater feed at a capital cost for power of about $4,000 per kilowatt and a PRO plant cost of $190,000,000. The electrical energy would be produced at a cost of about $0.07/kWh. The PRO plant would use a DuPont B-9 type or similar hollow fiber modified to have 110 and 320 micron internal and outer diameters (instead of 40 and 90). Osmotic permeation of half of the 3,000,000 m³/d RO reject brine into Dead Sea brine would produce 35 atmospheres of hydrostatic pressure relieved by passage of an equivalent volumetric rate of diluted Dead Sea brine through a hydroturbine/generator set. The second type of plant prior to PRO would use 3,000,000 m³/d of seawater to produce hydropower, estimated at about 130,000 kW. The permeation rate in PRO could then be 2,000,000 m³/d enabling power production in PRO of 70,000 kW at a capital cost for power of $3,300 per kilowatt and a PRO plant cost of $230,000,000. The cost of produced energy in PRO would be $0.058/kWh. It is believed that the Great Salt Lake should also be examined as a site for PRO.     

Treatment of effluents from the regeneration of ion exchangers using the MD process

The membrane distillation (MD) process for the treatment of wastewater from ion-exchanger regeneration was proposed. The precipitation of salt deposits on the membrane surface was observed when such wastewater was directly used as a feed. A rapid decline of the permeate flux from 532 to 410 dm³/m²d was found. The problem of fouling was significantly diminished by the addition of Ca(OH)₂ to the wastewater followed by filtration. The improvement of MD module performance was achieved after such pretreatment. The degree of water recovery equal to 50% was obtained without significant variations of the permeate flux. However, when the pretreated feed was subjected to two-fold concentration, precipitation of the silicon compounds was observed. The deposit caused clogging of the inlets of capillary membranes and resulted in a gradual decline of the module efficiency. The two-fold concentrated feed was then treated by sedimentation and filtration, which permitted a further concentration of obtained retentate and enhanced the degree of water recovery to 75%.     

Microwave-enhanced catalytic degradation of phenol over nickel oxide

A mix-valenced nickel oxide, NiO_x, was prepared from nickel nitrate aqueous solution through a precipitation with sodium hydroxide and an oxidation by sodium hypochlorite. Further, pure nickel oxide was obtained from the NiO_x by calcination at 300, 400 and 500 °C (labeled as C300, C400 and C500, respectively). They were characterized by thermogravimetry (TG), X-ray diffraction (XRD), nitrogen adsorption at −196 °C and temperature-programmed reduction (TPR). Their catalytic activities towards the degradation of phenol were further studied under continuous bubbling of air through the liquid phase. Also, the effects of pH, temperature and kinds of nickel oxide on the efficiency of the microwave-enhance catalytic degradation (MECD) of phenol have been investigated. The results indicated that the relative activity affected significantly with the oxidation state of nickel, surface area and surface acidity of nickel oxide, i.e., NiO_x (>+2 and S_BET = 201 m² g⁻¹)  C300 (+2 and S_BET = 104 m² g⁻¹) > C400 (+2 and S_BET = 52 m² g⁻¹) > C500 (+2 and S_BET = 27 m² g⁻¹). The introduction of microwave irradiation could greatly shorten the time of phenol degradation.     

Experiment and calculation of filtration processes in an external-loop airlift ceramic membrane bioreactor

Air sparging is recognized as an effective way to increase permeate flux in membrane filtration processes. The application of air sparging with an external-loop airlift ceramic membrane bioreactor was studied at different gas flow rates, biomass concentrations and suction pressures. A 180% increase in permeate flux was obtained while filtering a 2 g/L activated sludge wastewater suspension with the airlift cross-flow operation for U_g=0.21 m/s. The mechanism of flux enhancement in the case of slug flow in tubular membrane was discussed. The region near the gas slug was divided into three different zones: falling film zone, wake zone and remaining liquid slug zone. Air sparging significantly lowered cake thickness and consequently cake resistances for the wake region and the falling film region. A novel model combining hydrodynamic of gas-liquid two-phase flow and cake resistance was developed to simulate the process. The model was validated with experimental data with an error of 8.3%.     

一体化笼式生物脱氮反应器水力特性

水力特性是生物脱氮反应器高效稳定运行的基础,采用脉冲刺激响应技术研究了一体化笼式生物脱氮反应器的水力特性。试验结果表明:在水力停留时间为4 h,水力负荷为6.0 m³·m^-3·d^-1,表面流速0.145 m·h^-1的条件下,该反应器的流态趋于全混流。以多釜串联模型表征,供气量为1.714、3.214、6.429、8.571 m³·m^-3·h^-1时的串联釜数依次为1.55、1.56、1.54和1.55;以轴向扩散模型表征,对应的Peclet数分别为1.479、1.503、1.466和1.478;两个模型预测结果一致。反应器总死区的均值为41.63%,其中水力死区的均值为21.99%。在所试范围内,供气量对其水力特性的影响较小。