反渗透处理煤层气产出水中试示范及其控制模型研究(英文)

This study presents the first demonstration project in China for treatment of coal-bed methane(CBM) co-produced water and recycling.The work aims to provide a research and innovation base for solving the pollution problem of CBM extraction water.The reverse osmosis(RO) unit is applied to the treatment of CBM co-produced water.The results indicate that system operation is stable,the removal efficiency of the total dissolved solids(TDS) is as high as 97.98%,and Fe,Mn,and F-are almost completely removed.There is no suspended solids(SS) detected in the treated water.Furthermore,a model for the RO membrane separation process is developed to describe the quantitative relationship between key physical quantities-membrane length,flow velocity,salt concentration,driving pressure and water recovery rate,and the water recovery restriction equation based on mass balance is developed.This model provides a theoretical support for the RO system design and optimization.The TDS in the CBM co-produced water are removed to meet the "drinking water standards" and "groundwater quality standards" of China and can be used as drinking water,irrigation water,and livestock watering.In addition,the cost for treatment of CBM co-produced water is assessed,and the RO technology is an efficient and cost-effective treatment method to remove pollutants.     

CFD simulation of flow field and resistance in a 19-core tandem ceramic membrane module

CFD simulation of the permeation process of a 19-core tandem ceramic membrane module was established to investigate flow field and resistance and its change in permeate flux to the membrane element position and the channel of each membrane element. The results show that when the volume flow rate changes from26 m~3·h~(-1) to 89 m~3·h~(-1), the resistance of each part of the membrane module increases gradually. The increase in resistance loss in the membrane element is faster than the plates and the bell mouths. In a single ceramic membrane module, the maximum difference in flow rate of each membrane tube is 7.23%. In a single membrane tube,the outer ring channels 3–5, 3–6, 3–7, 3–8 are relatively slow. The maximum mass flow deviation from the mean is 2.7%. This work helps to clarify the flow mechanism within the modules, optimize the structure of the equipment and provide a reliable basis for the improvement of industrial ceramic membrane modules.     

Gradient nanoporous phenolics as substrates for high-flux nanofiltration membranes by layer-by-layer assembly of polyelectrolytes

Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m~(-2)?h~(-1)?MPa~(-1), which is ～2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.     

Potential use of nanofiltration like-forward osmosis membranes for copper ion removal

The discharge of industrial effluent containing heavy metal ions would cause water pollution if such effluent is not properly treated. In this work, the performance of emerging nanofiltration(NF) like-forward osmosis(FO)membrane was evaluated for its efficiency to remove copper ion from water. Conventionally, copper ion is removed from aqueous solution via adsorption and/or ion-exchange method. The engineered osmosis method as proposed in this work considered four commercial NF membranes(i.e., NF90, DK, NDX and PFO) where their separation performances were accessed using synthetic water sample containing 100 mg·L~(-1) copper ion under FO and pressure retarded osmosis(PRO) orientation. The findings indicated that all membranes could achieve almost complete removal of copper regardless of membrane orientation without applying external driving force.The high removal rates were in good agreement with the outcomes of the membranes tested under pressuredriven mode at 1 MPa. The use of appropriate salts as draw solutes enabled the NF membranes to be employed in engineered osmosis process, achieving a relatively low reverse solute flux. The findings showed that the best performing membrane is PFO membrane in which it achieved N 99.4% copper rejection with very minimum reverse solute flux of 1 g·m~(-2)·h~(-1).     

Fabrication of graphene oxide composite membranes and their application for pervaporation dehydration of butanol

As a new kind of 2D nanomaterials, graphene oxide (GO) with 2–4 layers was fabricated via a modified Hummers method and used for the preparation of pervaporation (PV) membranes. Such GO membranes were prepared via a facile vacuum-assisted method on anodic aluminium oxide disks and applied for the dehydration of butanol. To obtain GO membranes with high performance, effects of pre-treatments, including high-speed centrifugal treat-ment of GO dispersion and thermal treatment of GO membranes, were investigated. In addition, effects of oper-ation conditions on the performance of GO membranes in the PV process and the stability of GO membranes were also studied. It is of benefit to improve the selectivity of GO membrane by pre-treatment that centrifuges the GO dispersion with 10000 r·min?1 for 40 min, which could purify the GO dispersion by removing the large size GO sheets. As prepared GO membrane showed high separation performance for the butanol/water system. The separation factor was 230, and the permeability was as high as 3.1 kg·m?2·h?1 when the PV temperature was 50 °C and the water content in feed was 10%(by mass). Meanwhile, the membrane still showed good stabil-ity for the dehydration of butanol after running for 1800 min in the PV process. GO membranes are suitable candidates for butanol dehydration via PV process.     

Performance evaluation of polyamide nanofiltration membranes for phosphorus removal process and their stability against strong acid/alkali solution

In this study,a quantitative performance of three commercial polyamide nanofiltration(NF) membranes(i.e.,NF,NF90,and NF270) for phosphorus removal under different feed conditions was investigated.The experiments were conducted at different feed phosphorus concentrations(2.5,5,10,and 15 mg·L~(-1)) and elevated pHs(pH 1.5,5,10,and 13.5) at a constant feed pressure of 1 MPa using a dead-end filtration cell.Membrane rejection against total phosphorus generally increased with increasing phosphorus concentration regardless of membrane type.In contrast,the permeate flux for all the membranes only decreased slightly with increasing phosphorus concentration.The results also showed that the phosphorus rejections improved while water flux remained almost unchanged with increasing feed solution pH.When the three membranes were exposed to strong pHs(pH 1.5 and 13.5) for a longer duration(up to 6 weeks)it was found that the rejection capability and water flux of the membranes remained very similar throughout the duration,except for NF membrane with marginal decrement in phosphorus rejection.Adsorption study also revealed that more phosphorus was adsorbed onto the membrane structure at alkaline conditions(pH 10 and 13.5) compared to the same membranes tested at lower pHs(pH 1.5 and 5).In eonelusion,NF270 membrane outperformed Nf and NF90 membranes owing to its desirable performance of water flux and phosphorus rejection particularly under strong alkali solution.The NF270 membrane achieved 14.0 L·m~(-2)·h~(-1) and 96.5% rejection against 10 mg·L~(-1) phosphorus solution with a pH value of 13.5 at the applied pressure of 1 MPa.     

Scaling salts removal in RO concentrates by inorganic induced method

Scaling on heat transfer surface and reverse osmosis （RO） membrane surface is one of the main problems in desalination processes. To mitigate scales, anti-scalants are often used. For RO system, membrane concentrates contain high amounts of dissolved salts and anti-scalants. Commonly, concentrates are discharged directly. In fact, concentrates are high quality water due to the strict pre-treatment of RO feed water.     

纳滤/反渗透膜处理重金属废水的性能

The performance of different nanofiltration （NF） and reverse osmosis （RO） membranes was studied in treating the toxic metal effluent from metallurgical industry. The characteristics and filtration behavior of the processes including the wastewater flux, salt rejection and ion rejection versus operating pressure were evaluated. Then the wastewater flux of RO membrane was compared with theoretical calculation using mass transfer models, and good consistency was observed. It was found that a high rejection rate more than 95% of metal ions and a low Chemical Oxygen Demand （COD） value of 10 mg·L^-1 in permeate could be achieved using the RO composite membrane, while the NF rejection of the salt could be up to 78.9% and the COD value in the permeate was 35 mg·L^-1. The results showed that the product water by both NF and RO desalination satisfied the State Reutilization Qualification, but NF would be more suitable for large-scale industrial practice, which offered significantly higher permeate flux at low operating pressure.     

Effect of Cross-flow Velocity on the Critical Flux of Ceramic Membrane Filtration as a Pre-treatment for Seawater Desalination

Pre-treatment, which supplies a stable, high-quality feed for reverse osmosis (RO) membranes, is a critical step for successful operation in a seawater reverse osmosis plant. In this study, ceramic membrane systems were employed as pre-treatment for seawater desalination. A laboratory experiment was performed to investigate the effect of the cross-flow velocity on the critical flux and consequently to optimize the permeate flux. Then a pilot test was performed to investigate the long-term performance. The result shows that there is no significant effect of the cross-flow velocity on the critical flux when the cross-flow velocity varies in laminar flow region only or in turbulent flow region only, but the effect is distinct when the cross-flow velocity varies in the transition region. The membrane fouling is slight at the permeate flux of 150 L穖^-2穐^-1 and the system is stable, producing a high-quality feed (the turbidity and silt density index are less than 0.1 NTU and 3.0, respectively) for RO to run for 2922.4 h without chemical cleaning. Thus the ceramic membranes are suitable to filtrate seawater as the pre-treatment for RO.     

Superhydrophobic modification of ceramic membranes for vacuum membrane distillation

The hydrophobically modified ceramic membranes have great potential for energy-efficient membrane distillation.In this work,flat-sheet ceramic membranes with a superhydrophobic surface were fabricated by grafting 1H,1H,2H,2H-perfluorooctyltrichlorosilane or 1H,1H,2H,2H-perfluorodecyltriethoxysilane and followed by ultraviolet irradiation.The surface water contact angle was improved from 46° of original ceramic membrane to 159°,which exhibited a stable and excellent superhydrophobic effect.The modified membranes showed a high flux of 27.28 kg· m-2.h-1 and simultaneously maintained an excellent retention rate of 99.99％,when used in vacuum membrane distillation process for treatment ofa 1 wt％ NaCl (75 °℃) aqueous solution.These results suggested that superhydrophobic modification of ceramic surface is a facile and cost-effective way to achieve higher membrane distillation performance.The superhydrophobically-modified ceramic membrane with an excellent desalination capacity would show considerable potential in practical membrane distillation utilizations.     

Effects of Sn residue on the high temperature stability of the H_2-permeable palladium membranes prepared by electroless plating on Al_2O_3 substrate after SnCl_2–PdCl_2 process: A case study

The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.     

Purification and concentration of gluconic acid from an integrated fermentation and membrane process using response surface optimized conditions

A response surface method was used to optimize the purification and concentration of gluconic acid from fermentation broth using an integrated membrane system. Gluconobacter oxydans was used for the bioconversion of the glucose in sugarcane juice to gluconic acid (concentration 45 g·L^-1) with a yield of 0.9 g·g^-1. The optimum operating conditions, such as trans-membrane pressure (TMP), pH, cross-flow rate (CFR) and initial gluconic acid concentration, were determined using response surface methodology. Five different types of polyamide nanofiltration membranes were screened and the best performing one was then used for downstream purification of gluconic acid in a flat sheet cross-flow membrane module. Under the optimum conditions (TMP=12 bar and CFR=400 L·h^-1), this membrane retained more than 85% of the unconverted glucose from the fermentation broth and had a gluconic acid permeation rate of 88% with a flux of 161 L·m^-2·h^-1. Using response surface methods to optimize this green nanofiltration process is an effective way of controlling the production of gluconic acid so that an efficient separation with high flux is obtained.     

Optimization of the fuel rod's arrangement cooled by turbulent nanofluids flow in pressurized water reactor (PWR)

In this paper, response surface methodology(RSM) based on central composite design(CCD) is applied to obtain an optimization design for the fuel rod's diameter and distance cooled by turbulent Al_2O_3–water nanofluid for a typical pressurized water reactor(PWR). Fuel rods and nanofluid flow between them are simulated 3D using computational fluid dynamics(CFD) by ANSYS-FLUNET package software. The RNG k–ε model is used to simulate turbulent nanofluid flow between the rods. The effect of different nanoparticles concentration is also investigated on the Nusselt number from heat transfer efficiency view point. Results reveal that when distance parameter(a) is in the minimum level and diameter parameter(r) is in the maximum possible level, cooling the rods will be better due to higher Nusselt number in this situation. Also, using the different nanoparticles on the cooling process confirms that Al_2O_3 averagely 17% and TiO_2 10% improve the Nusselt numbers.     

混凝耦合多孔陶瓷膜净化河水简

Membrane filtration technology combined with coagulation is widely used to purify river water. In this study, micro filtration （MF） and ultrafiltration （UF） ceramic membranes were combined with coagulation to treat local river water located at Xinghua, Jiangsu province, China. The operation parameters, fouling mechanism and pilot-scale tests were investigated. The results show that the pore size of membrane has small effect on the pseudo-steady flux for dead-end filtration, and the increase of flux in MF process is more than that in UF process for cross-flow filtration with the same increase of cross-flow velocity. The membrane pore size has little influence on the water quality. The analysis on membrane fouling mechanism shows that the cake filtrationhas significant in fluence on the pseudo-steady flux and water quality for the membrane with pore size of 50, 200 and 500 nm. For the membrane with pore size of 200 nm and backwashing employed in our pilot study, a constant flux of 150 L-m^-2-h^-1 was reached during stable operation, with the removal efficiency of turbidity, total organic carbon （TOC） and UV254 higher than 99%, 45% and 48%, respectively. The study demonstrates that coagulation-porous ceramic membrane hybrid process is a reliable method for river water purification.     

ABSTRACTS

Design Summary for 10 kt/a Acid Production from Phosphorus Mud
Abstract： For the fact that there is large amount of by-product phosphorus mud from electric furnace phosphorus production in China, and problems of low phosphorus recovery and secondary pollution in many ways for recovery for element phosphorus in it, and based on the actual design of a 10 kt/a acid production plant from phosphorus mud of a yellow phosphorus production enterprise, the process flow, control system, equipment selection and technical features of acid production from phosphorus mud are introduced. The process offers features like high phosphorus recovery, free of secondary pollution, high level of automation, and the ability for continuous production, which is worth of promotion.     

硅橡胶膜用于植物油/己烷胶团中溶剂回收的研究

Traditional solvent recovery in the extraction step of edible oil processing is distillation, which consumes large amounts of energy. If the distillation is replaced by membrane process, the energy consumption can be reduced greatly. In this work, two kinds of membrane, PDMS (polydimethylsiloxane) composite membrane and Zeolite filled PDMS membrane were prepared, in which asymmetric microporous PVDF (polyvinylidenefluoride) membrane prepared with phase inversion method was functioned as the microporous supporting layer in the flat-plate composite membrane. The different function compositions of the PDMS/PVDF com-posite membranes were characterized by reflection Fourier transform infrared (FTIR) spectroscopy. The surface and section of PDMS/PVDF composite membranes were investigated by scanning electron microscope (SEM). The PDMS NF (nanofiltration) membranes were then applied in the recovery of hexane from soybean oil/hexane miscellas (1︰3, mass ratio). The effects of pres-sure (0.5-1.5 MPa), cross-linking temperature and PDMS layer thickness on membrane performances were investigated. The results indicated that both two kinds of NF membranes were promising for solvent recovery, and zeolite filled in PDMS NF membrane could enhance the separation performance.     

A stepwise optimal design of water network☆

In order to take full advantage of regeneration process to reduce fresh water consumption and avoid the accumu-lation of trace contaminants, regeneration reuse and regeneration recycle should be distinctive. A stepwise opti-mal design for water network is developed to simplify solution procedures for the formulated MINLP problem. In this paper, a feasible water reuse network framework is generated. Some heuristic rules from water reuse net-work are used to guide the placement of regeneration process. Then the outlet stream of regeneration process is considered as new water source. Regeneration reuse network structure is obtained through an iterative optimal procedure by taking the insights from reuse water network structure. Furthermore, regeneration recycle is only utilized to eliminate fresh water usage for processes in which regeneration reuse is impossible. Compared with the results obtained by relevant researches for the same example, the present method not only provides an appro-priate regeneration reuse water network with minimum fresh water and regenerated water flow rate but also sug-gests a water network involving regeneration recycle with minimum recycle water flow rate. The design can utilize reuse, regeneration reuse and regeneration recycle step by step with minor water network structure change to achieve better flexibility. It can satisfy different demands for new plants and modernization of existing plants. ? 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. Al rights reserved.     

Concentration of mixed acid by electrodialysis for the intensification of absorption process in acrylic acid production

The absorption process in acrylic acid production was water-intensive. The concentration of acrylic acid before distillation process was low, which induced to large amount of wastewater and enormous energy consumption.In this work, a new method was proposed to concentrate the side stream of absorption column and thus increase the concentration in bottom product by electrodialysis. The influence of operating conditions on concentration rate and specific energy consumption were investigated by a laboratory-scale device. When the voltage drop was 1 V·cP~(-1)(1 cP=10~(-3) Pa·s), flow velocity was 3 cm·s~(-1) and the temperature was 35 °C, the concentration rates of acrylic acid and acetic acid could be 203.3% and 156.6% in the continual-ED process. Based on the experimental data, the absorption process combined with ED was simulated, in which the diluted solution from ED process was used as spray water and the concentrated solution was feed back to the absorption column. The results shown that the flow rate of spray water was decreased by 37.1%, and the acrylic acid concentration at the bottom of the tower was increased by 4.56%. The ions exchange membranes before and after use 1200 h were tested by membrane surface morphology(scanning electron microscope), membrane chemical groups(infrared spectra), ion exchange capacity, and membrane area resistance, which indicated the membrane were stable in the acid system. This method provides new method for energy conservation and emission reduction in the traditional chemical industry.     

添加剂和凝结剂温度对用无溶剂致相位分离法生产高性能PVDF/聚醚F127混合中空光纤膜的影响(英文)

Poly(vinylidene fluoride)(PVDF) has become one of the most popular materials for membrane prepara-tion via nonsolvent induced phase separation(NIPS) process.In this study,an amphiphilic block copolymer,Plu-ronic F127,has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fiber membranes to enhance the membrane permeability and hydrophilicity.The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F127 membranes have also been investigated.The as-spun hollow fibers were characterized in terms of cross-sectional morphology,pure water permeation(PWP),relative molecular mass cut-off(MWCO),membrane chemistry,and hydrophilicity.It was observed that the addition of Pluronic F127 significantly increased the PWP of as-spun fibers,while the membrane contact angle was reduced.However,the size of macrovoids in the membranes was undesirably large.The addition of a 2nd additive,including lithium chlo-ride(LiCl) and water,or an increase in coagulant temperature was found to effectively suppress the macrovoid for-mation in the Pluronic-containing membranes.In addition,the use of LiCl as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes,while the surface pore size became smaller.PVDF hollow fiber with a PWP as high as 2530 L?m?2?h?1?MPa?1,a MWCO of 53000 and a contact angle of 71° was successfully fabricated with 3%(by mass) of Pluronic F127 and 3%(by mass) of LiCl at a coagulant temperature of 25 °C,which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.     

REMOVAL OF ETHANOL FROM CONTINUOUS FERMENTATION BROTH BY PERVAPORATION

In the process of continuous fermentation with pervaporation(PVAP),ethanol can be removed and concentrated simultaneously from the broth. In this work, two kinds of modified PDMS (polydimethylsiloxane) membranes used for PVAP have been tested, the characteristics and kinetics of the process were investigated, and a set of kinetic equations has been derived along with the experimental results. The results show some major advantages of this process over that with ultrafiltration, more concentrated ethanol can be obtained from the broth directly; no appreciable fouling on the membrane and the process can be controlled steadily.