Extraordinary mass transfer phenomenon is usually found when the small molecules pass through a confined structure, whose effective size is commensurate with the mean free path of the molecules. Small changes in the c...Extraordinary mass transfer phenomenon is usually found when the small molecules pass through a confined structure, whose effective size is commensurate with the mean free path of the molecules. Small changes in the confined mass transfer structure(including size, morphology and properties) will lead to significant fluctuations of the mass transfer coefficient. The mass transfer of the penetrant molecules in the dense membranes for pervaporation, gas separation and so on, is located in the scope of confined mass transfer. Incorporating nanofillers into polymer matrix to construct mixed matrix membranes(MMMs) is an effective approach to tune the confined mass transfer structure and enhance the performance of the widely used polymeric membranes. This review focuses on the construction and manipulation of the confined structure in the polymeric membranes via incorporating one-dimensional(1D), two-dimensional(2D) and three-dimensional(3D) fillers.The comparison of the MMMs for pervaporation is summarized, and the research prospective of the MMMs is provided.展开更多
Hybrid membranes combining the merits of both polymer matrices and fillers have drawn extensive attention. The rational design of polymer–filler interface in hybrid membranes is vitally important for reducing the occ...Hybrid membranes combining the merits of both polymer matrices and fillers have drawn extensive attention. The rational design of polymer–filler interface in hybrid membranes is vitally important for reducing the occurrence of void defects. Herein, imine-type covalent organic frameworks(COFs) were selected as the fillers due to their totally organic nature and multi-functionalities. Mussel-inspired dopamine-modified sodium alginate(Alg DA) was synthesized as the polymer matrix. The dopamine modification significantly improves the Alg DA–COF compatibility,which enhances the COF content up to 50 wt% in the hybrid membranes. The improved interfacial compatibility enhances the membrane separation selectivity. Accordingly, when utilized for dehydration of ethanol/water mixed solution(water concentration of 10 wt%), the hybrid membrane reveals high water concentration of ~98.7 wt% in permeate, and stable permeation flux larger than 1500 g·m-2·h-1. This work might afford useful insights for fabricating hybrid membranes with high separation selectivity by optimizing the polymer–filler interface.展开更多
Crosslinking treatments for a commercially available aromatic polyamide reverse osmosis membrane were carried out to improve its chlorine resistance.The crosslinking agents including 1,6-hexanediol diglycidyl ether,ad...Crosslinking treatments for a commercially available aromatic polyamide reverse osmosis membrane were carried out to improve its chlorine resistance.The crosslinking agents including 1,6-hexanediol diglycidyl ether,adipoyl dichloride and hexamethylene diisocyanate ester with long flexible aliphatic chains and high reactivity with N-H groups were used in the experiments.Attenuated total reflective Fourier transform infrared spectra verified the successful preparation of highly crosslinked membranes by crosslinking treatments.It was suggested that the crosslinking agents were connected to membrane surface through the reactions with amine and amide Ⅱ groups,which is confirmed by surface charge measurements.Based on contact angle measurements,crosslinking treatments decreased membrane hydrophilicity by introducing methylene groups to membrane surface.With increasing amount of crosslinking agent molecules connected to membrane surface,the hydrolysis of unconnected functional groups of crosslinking agent produced polar groups and increased membrane hydrophilicity.The highly crosslinked membranes showed higher salt rejections and lower water fluxes as compared with the raw membrane.Since the active sites(N-H groups) vulnerable to free chlorine on membrane surface were eliminated by crosslinking treatments,the chlorine resistances of the highly crosslinked membranes were significantly improved by slighter changes in both water fluxes and salt rejections after chlorination.展开更多
This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–g...This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–gel method. The effects of calcinating temperature and the addition of CaCO_3 as a pore-enlarging agent on texture structure and catalytic performance in isobutane dehydrogenation to isobutene were investigated. Characterization of N_2 sorption,mechanical strength tests,and optical photographs confirmed that the obtained carbon materials had high mechanical strength,a good degree of sphericity,and a large surface area. Introducing CaCO_3 as a pore-enlarging agent during the preparation process promoted the formation of a mesoporous structure of carbon spheres and evidently increased the surface area and oxygen content,which can improve isobutane conversion and isobutene selectivity of these carbon spheres. The conversion of isobutane reached up to 28% for this spherical activated carbon,and the selectivity of isobutene reached up to 96%. Isobutane conversion increased with an increase in calcination temperature due to an increase in the oxygen content,whereas the selectivity of isobutene decreased due to the slight decrease in the specific surface area.展开更多
2,5-Furandicarboxylic acid (FDCA) is a potential biorenewable chemical for applications including plastics, polyamides, drugs, etc. The selective biosynthesis of FDCA from 5-hydroxymethylfurfural (HMF) by a speci c en...2,5-Furandicarboxylic acid (FDCA) is a potential biorenewable chemical for applications including plastics, polyamides, drugs, etc. The selective biosynthesis of FDCA from 5-hydroxymethylfurfural (HMF) by a speci c enzyme poses a great challenge. In this study, we reported an e cient strategy to produce FDCA from HMF by the tandem biocatalysis of laccase (CotA-TJ102@UIO-66-NH 2 ) and Novozym 435. For the rst step, a nanoparticle metal organic framework was synthesized as a carrier to immobilize CotA-TJ102@UIO-66-NH 2 , which was assigned for the production of 5-formyl-2-furancarboxylic acid (FFCA) and featured an enzyme loading of 255.54 mg/g, speci c activity of 135.90 U/mg, and solid loading ratio of 99.65%. Under optimal conditions, an ideal FFCA yield of 98.5% was achieved, and the CotA-TJ102@UIO-66-NH2 pre- sented a high recycling capacity after 10 cycles. For the second step, Novozym 435 was applied for the further conversion of FFCA into FDCA, presenting a high FDCA yield of 95.5% under the optimized conditions. Novozym 435 also exhibited a high recyclability after eight cycles. As a result, the tandem biocatalysis strategy provided a 94.2% FDCA yield from HMF, indicating its excellence as a method for FDCA production.展开更多
A facile surface segregation method was utilized to fabricate poly（vinyl alcohol）-polyethersulfone （PVA-PES） composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide （DMSO）, then casted on a g...A facile surface segregation method was utilized to fabricate poly（vinyl alcohol）-polyethersulfone （PVA-PES） composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide （DMSO）, then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy （SEM）, X-ray photoelectron spectroscopy （XPS） and energy dispersive spectrometer （EDS） confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surtace by PVA reacned up to 86.8% when me PVA content m me membrane recipe was 16.7% （by mass）. The water contact angle decreased with the increase of PVA content. The effect of coagulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The membrane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.展开更多
A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese car...A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese carbonate were measured by SEM,XRD,TGA,BET and XPS. In this method,no harsh reaction conditions were required,and it was a simple and green process for the oxidation of 5-HMF into DFF. To achieve an optimum DFF yield,different reaction conditions,including reaction temperature,reaction time,catalyst amount,and solvents were investigated. Results from the experiments indicated that the highest DFF yield of 86.9% was obtained at 120 °C under atmospheric oxygen pressure after 6h. Finally,Mn CO_3 could be used at least five times with considerable stability.展开更多
Membrane technology features inspiring excellence from numerous separation technologies for CO_(2) capture from post-combustion gas.Polyvinylamine(PVAm)-based facilitated transport membranes show significantly high se...Membrane technology features inspiring excellence from numerous separation technologies for CO_(2) capture from post-combustion gas.Polyvinylamine(PVAm)-based facilitated transport membranes show significantly high separation performance,which has been proven promising for industrial scale-up.However,commercialized PVAm with low molecular weight and excessive crystallinity is not available to prepare high-performance membranes.Herein,the synthesis process of PVAm was optimized by regulating polymerization and acidic hydrolytic conditions.The membranes based on PVAm with a molecular weight of 154 kDa and crystallinity of 11.37%display high CO_(2) permeance of 726 GPU and CO_(2)/N_(2) selectivity of 55 at a feed gas pressure of 0.50 MPa.Furthermore,we established a PVAm synthesis reactor with an annual PVAm solution(1%(mass))capacity of over 7000 kg and realized the scaled-up manufacture of both PVAm and composite membranes.展开更多
In this work, the effects of support surface pore structures(including surface pore size, surface pore density and surface porosity) on the performance of thin film composite(TFC) gas separation membrane over a wide p...In this work, the effects of support surface pore structures(including surface pore size, surface pore density and surface porosity) on the performance of thin film composite(TFC) gas separation membrane over a wide pressure range(from 0.3 to 2.0 MPa) were studied. To fulfill it, the polysulfone(PSf) supports with different surface pore structures were prepared. Two kinds of wide-accepted polymeric membrane materials, i.e., polyvinylamine(PVAm) and Pebax 1657 copolymer, were used as skin layer materials. We pointed out for the first time that the support surface average pore size and pore density could affect the chain mobility of polymer of skin layer at the support surface pore entrance, then, can affect the TFC membrane performance. Besides, we also discussed the effects of support on the TFC membrane performance when the feed pressure changes for the first time. This work can provide guidance for choosing a suitable support for TFC gas separation membrane.展开更多
Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost target...Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost targets for CO2 capture. This study attempts to develop membranes with multiple permselective mechanisms in order to enhance CO2 separation performance of fixed carder membrane. In this study, a novel membrane with multiplepermselective mechanisms of solubility selectivity and reaction selectivity was developed by incorporating CO2-selective adsorptive silica nanoparticles in situ into the tertiary amine containing polyamide membrane formed by interfacial polymerization （IP）. Various techniques were employed to characterize the polyamide and polyam-ide-silica composite membranes. The TGA result shows that nanocomposite membranes exhlbit superior-thermal stability than pure polyamide membranes. In addition, gas permeation experiments show that both nanocomposite membranes have larger CO2 permeance than pure polyamide membranes. The enhanced CO2/N2 separation performance for nanocomposite membranes is mainly due to the thin film thickness, and multiple permselective mechanisms of solubility selectivity and reaction selectivity.展开更多
Gamma-aminobutyric acid(GABA)is a natural non-protein functio nal amino acid,which has potential for fermentation industrial production by Lactobacillus brevis.This work investigated the batch fermentation process and...Gamma-aminobutyric acid(GABA)is a natural non-protein functio nal amino acid,which has potential for fermentation industrial production by Lactobacillus brevis.This work investigated the batch fermentation process and developed a kinetic model based on substrate restrictive model established by experimental data from L25(5~6)orthogonal experiments.In this study,the OD600 value of fermentation broth was fixed to constant after reaching its maximum because the microorganism death showed no effect on the enzyme activity of glutamate decarboxylase(GAD).As pH is one of the key parameters in fermentation process,a pH-dependent kinetic model based on radial basis function was developed to enhance the practicality of the model.Furthermore,as to decrease the deviations between the simulated curves and the experimental data,the rolling correction strategy with OD600 values that was measured in real-time was introduced into this work to modify the model.Finally,the accu racy of the rolling corrected and pH-dependent model was validated by good fitness between the simulated curves and data of the initial batch fermentation(pH 5.2).As a result,this pH-dependent kinetic model revealed that the optimal pH for biomass growth is 5.6-5.7 and for GABA production is about 5,respectively.Therefore,the developed model is practical and convenient for the instruction of GABA fermentation production,and it has instructive significance for the industrial scale.展开更多
Polyamide(PA)thin-film composite(TFC)na nofiltration(NF)membrane has extremely broad application prospects in separation of monovalent/diva lent inorganic salts mixed solutio n.However,membrane fouling is the main obs...Polyamide(PA)thin-film composite(TFC)na nofiltration(NF)membrane has extremely broad application prospects in separation of monovalent/diva lent inorganic salts mixed solutio n.However,membrane fouling is the main obstacle to the application of PA,TFC and NF membrane.Streptomycin(SM)is a hydrophilic antibiotic containing a large number of hydroxyl and amino groups.In this work,the NF membrane was prepared via interfacial polymerization(IP)between trimesoyl chloride(TMC)in the organic phase and SM/piperazine(PIP)mixture in the aqueous phase.The NF membrane structure and performance were characterized in detail.The results showed that SM successfully participated in the IP.The negative charge and hydrophilicity of membrane surface were improved.The prepared membrane exhibited good anti-adhesion and anti-bacterial performance,Additionally,when the SM concentration was 2%,the prepared membrane exhibited the optimal permselectivity.The water permeance was 89.4L·m^(-2)·h^(-1)·MPa^(-1).The rejection of NaCl and Na_(2)SO_(4) were 17,17%and 97.84%,respectively.The NaCl/Na_(3)SO_(4) separation factor of the SM2-PIP/TMC membrane in 1000 mg·L^(-1) NaCl and 1000 mg·L^(-1)Na_(2)SO_(4) mixed solution was 40,which was 3.3 times that of PIP/TMC membrane.It indicated that SM2-PIP/TMC demonstrated excellent monovalent/divalent salts separation performance.This work provided an easy and effective approach to preparing anti-fouling NF membrane while possessing superior monovalent/divalent salts separation performance.展开更多
Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial ...Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline(PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope(SEM) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction(XRD) and differential scanning calorimetry(DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from α-phase to β-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials.展开更多
C.I. Acid Red 73(AR73)wastewater was treated by cross-flow nanofiltration coupling electro-catalytic oxidation using an NF90 membrane and a Ti/SnO_2–Sb anode prepared via electrodeposition.Experiments conducted for s...C.I. Acid Red 73(AR73)wastewater was treated by cross-flow nanofiltration coupling electro-catalytic oxidation using an NF90 membrane and a Ti/SnO_2–Sb anode prepared via electrodeposition.Experiments conducted for standard electrochemical degradation of AR73 studied the reaction rate ofremoving AR73 using the Ti/SnO _2–Sb anode.A computational fluid dynamics(CFD)model was developed to predict the permeate flux under a laminar flow regime,including the effects ofoperating pressure,applied potential,initial concentration,and cross-flow velocity on this coupling process.The variations of the membrane surface concentration and permeate flux along the length of the channel were quantified.The experimental results were compared with those predicted by the model,and they agreed well.展开更多
Recent advances on mixed matrix membrane for CO<sub>2</sub> separation are reviewed in this paper. To improve CO<sub>2</sub> separation performance of polymer membranes, mixed matrix membranes ...Recent advances on mixed matrix membrane for CO<sub>2</sub> separation are reviewed in this paper. To improve CO<sub>2</sub> separation performance of polymer membranes, mixed matrix membranes (MMMs) are developed. The concept of MMM is illustrated distinctly. Suitable polymer and inorganic or organic fillers for MMMs are summarized. Possible interface morphologies between polymer and filler, and the effect of interface morphologies on gas transport properties of MMMs are summarized. The methods to improve compatibility between polymer and filler are introduced. There are eight methods including silane coupling, Grignard treatment, incorporation of additive, grafting, in situ polymerization, polydopamine coating, particle fusion approach and polymer functionalization. To achieve higher productivity for industrial application, mixed matrix composite membranes are developed. The recent development on hollow fiber and flat mixed matrix composite membrane is reviewed in detail. Last, the future trend of MMM is forecasted.展开更多
Membrane separation technology has popularized rapidly and attracts much interest in gas industry as a promising sort of newly chemical separation unit operation. In this paper, recent advances on membrane processes f...Membrane separation technology has popularized rapidly and attracts much interest in gas industry as a promising sort of newly chemical separation unit operation. In this paper, recent advances on membrane processes for CO_2 separation are reviewed. The researches indicate that the optimization of operating process designs could improve the separation performance, reduce the energy consumption and decrease the cost of membrane separation systems. With the improvement of membrane materials recently,membrane processes are beginning to be competitive enough for CO_2 separation, especially for postcombustion CO_2 capture, biogas upgrading and natural gas carbon dioxide removal, compared with the traditional separation methods. We summarize the needs and most promising research directions for membrane processes for CO_2 separation in current and future membrane applications. As the time goes by, novel membrane materials developed according to the requirement proposed by process optimization with increased selectivity and/or permeance will accelerate the industrialization of membrane process in the near future. Based on the data collected in a pilot scale test, more effort could be made on the optimization of membrane separation processes. This work would open up a new horizon for CO_2 separation/Capture on Carbon Capture Utilization and Storage(CCUS).展开更多
Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in...Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.展开更多
A high performance composite membrane was prepared under the inspiration of bioadhesion principles for pervaporative dehydration of ethanol.Chitosan(CS)and polyacrylonitrile(PAN)ultrafiltration membranes were used as ...A high performance composite membrane was prepared under the inspiration of bioadhesion principles for pervaporative dehydration of ethanol.Chitosan(CS)and polyacrylonitrile(PAN)ultrafiltration membranes were used as the active layer and the support layer,respectively.Guar gum(GG),a natural bioadhesive,was introduced as the intermediate bonding layer to improve the separation performance and stability of the fabricated CS/GG/PAN composite membranes.The contact angle of the GG layer was just between those of the CS layer and the PAN layer,minimizing the difference of hydrophilicity between the active layer and the support layer.The peeling strength of the composite membrane was significantly enhanced after the introduction of the GG layer.The effects of preparation conditions and operation conditions including GG concentration,operating temperature and ethanol concentration in feed on the pervaporation performance were investigated.The as-fabricated CS/GG/PAN composite membrane showed the optimum performance with a permeation flux of up to804 g·m-2·h-1and a separation factor higher than 1900.Besides,the composite membranes exhibited a desirable long-term operational stability.展开更多
After years of research,the energy efficiency of energy recovery device has been raised to a high level,but the salinity mixing has not been effectively improved.Mixing will lead to a rise of highpressure seawater sal...After years of research,the energy efficiency of energy recovery device has been raised to a high level,but the salinity mixing has not been effectively improved.Mixing will lead to a rise of highpressure seawater salinity,which will increase the operating cost.In this paper,the computational fluid dynamics(CFD)simulation of the rotary energy recovery device(RERD)is carried out.It is found that the unstable flow caused by the nonparallel between the channel and the flow direction of fluid is an important reason for mixing.After the inclined channel structure is adopted,the nonparallel problem is improved.The formation of unstable flow is effectively controlled.Under the commercial product operating conditions,the volumetric mixing of the optimized device is reduced from 3.34%to 1.29%,showing the effectiveness of the structure.展开更多
Isobaric vapor-liquid equilibrium (VLE) data were measured for binary mixtures of toluene+N- formylmorpholine, toluene+3-methylthiophene and 3-methylthiophene+N-formylmorpholine at 101.33 kPa. The VLE data of the bina...Isobaric vapor-liquid equilibrium (VLE) data were measured for binary mixtures of toluene+N- formylmorpholine, toluene+3-methylthiophene and 3-methylthiophene+N-formylmorpholine at 101.33 kPa. The VLE data of the binary systems were found to be thermodynamically consistent. The saturated vapor pressure calculated by CSGC-PR equation of the pure component had higher accuracy than that calculated by Antoine equation. The liquid- phase activity coefficients of the binary systems were calculated by the Wilson, NRTL and UNIFAC models, and the binary interaction parameters of the three models were determined by the VLE data. The Wilson model was selected as the most suitable model to predict the VLE data of the ternary system of toluene+3-methylthiophene+N- formylmorpholine. The relative volatility between toluene and 3-methylthiophene was also calculated. Moreover, the effect of N-formylmorpholine as solvent was studied. When the molar ratio of solvent to feed (S/F) was 7, the relative volatility reached 1.904, which is almost twice the relative volatility without solvent. Therefore, N-formylmorpholine can be considered as an effective extracting agent for the separation of the close-boiling mixture of toluene+3- methylthiophene by extractive distillation.展开更多
基金Supported by the National Natural Science Foundation of China(21490583 and21621004)the National Science Fund for Distinguished Young Scholars(21125627)+1 种基金Tianjin Application Foundation and Research in Cutting-edge Technology Plan(15JCQNJC43300)the Programme of Introducing Talents of Discipline to Universities(B06006)
文摘Extraordinary mass transfer phenomenon is usually found when the small molecules pass through a confined structure, whose effective size is commensurate with the mean free path of the molecules. Small changes in the confined mass transfer structure(including size, morphology and properties) will lead to significant fluctuations of the mass transfer coefficient. The mass transfer of the penetrant molecules in the dense membranes for pervaporation, gas separation and so on, is located in the scope of confined mass transfer. Incorporating nanofillers into polymer matrix to construct mixed matrix membranes(MMMs) is an effective approach to tune the confined mass transfer structure and enhance the performance of the widely used polymeric membranes. This review focuses on the construction and manipulation of the confined structure in the polymeric membranes via incorporating one-dimensional(1D), two-dimensional(2D) and three-dimensional(3D) fillers.The comparison of the MMMs for pervaporation is summarized, and the research prospective of the MMMs is provided.
基金Supported by the National Natural Science Foundation of China(21621004,21490583,21878215,21878216)the Program of Introducing Talents of Discipline to Universities(B06006)the State Key Laboratory of Organic–Inorganic Composites(oic-201801003).
文摘Hybrid membranes combining the merits of both polymer matrices and fillers have drawn extensive attention. The rational design of polymer–filler interface in hybrid membranes is vitally important for reducing the occurrence of void defects. Herein, imine-type covalent organic frameworks(COFs) were selected as the fillers due to their totally organic nature and multi-functionalities. Mussel-inspired dopamine-modified sodium alginate(Alg DA) was synthesized as the polymer matrix. The dopamine modification significantly improves the Alg DA–COF compatibility,which enhances the COF content up to 50 wt% in the hybrid membranes. The improved interfacial compatibility enhances the membrane separation selectivity. Accordingly, when utilized for dehydration of ethanol/water mixed solution(water concentration of 10 wt%), the hybrid membrane reveals high water concentration of ~98.7 wt% in permeate, and stable permeation flux larger than 1500 g·m-2·h-1. This work might afford useful insights for fabricating hybrid membranes with high separation selectivity by optimizing the polymer–filler interface.
基金Supported by the National Natural Science Foundation of China （20676095）the Program of Introducing Talents of Discipline to Universities （B06006）
文摘Crosslinking treatments for a commercially available aromatic polyamide reverse osmosis membrane were carried out to improve its chlorine resistance.The crosslinking agents including 1,6-hexanediol diglycidyl ether,adipoyl dichloride and hexamethylene diisocyanate ester with long flexible aliphatic chains and high reactivity with N-H groups were used in the experiments.Attenuated total reflective Fourier transform infrared spectra verified the successful preparation of highly crosslinked membranes by crosslinking treatments.It was suggested that the crosslinking agents were connected to membrane surface through the reactions with amine and amide Ⅱ groups,which is confirmed by surface charge measurements.Based on contact angle measurements,crosslinking treatments decreased membrane hydrophilicity by introducing methylene groups to membrane surface.With increasing amount of crosslinking agent molecules connected to membrane surface,the hydrolysis of unconnected functional groups of crosslinking agent produced polar groups and increased membrane hydrophilicity.The highly crosslinked membranes showed higher salt rejections and lower water fluxes as compared with the raw membrane.Since the active sites(N-H groups) vulnerable to free chlorine on membrane surface were eliminated by crosslinking treatments,the chlorine resistances of the highly crosslinked membranes were significantly improved by slighter changes in both water fluxes and salt rejections after chlorination.
基金supported by the Natural Science Foundation of Tianjin, China (no. 15JCYBJC20900)
文摘This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–gel method. The effects of calcinating temperature and the addition of CaCO_3 as a pore-enlarging agent on texture structure and catalytic performance in isobutane dehydrogenation to isobutene were investigated. Characterization of N_2 sorption,mechanical strength tests,and optical photographs confirmed that the obtained carbon materials had high mechanical strength,a good degree of sphericity,and a large surface area. Introducing CaCO_3 as a pore-enlarging agent during the preparation process promoted the formation of a mesoporous structure of carbon spheres and evidently increased the surface area and oxygen content,which can improve isobutane conversion and isobutene selectivity of these carbon spheres. The conversion of isobutane reached up to 28% for this spherical activated carbon,and the selectivity of isobutene reached up to 96%. Isobutane conversion increased with an increase in calcination temperature due to an increase in the oxygen content,whereas the selectivity of isobutene decreased due to the slight decrease in the specific surface area.
基金supported by the National Key R&D Program of China (No. 2017YFB0306502)the Science Fund for Creative Research Groups (No. 21621004)+2 种基金the Project funded by China Postdoctoral Science Foundation (2019)the Key Project of Tianjin Science and Technology Committee (No. 17YFZCSY01080)the Program of Beiyang Young Scholar of Tianjin University (2012)
文摘2,5-Furandicarboxylic acid (FDCA) is a potential biorenewable chemical for applications including plastics, polyamides, drugs, etc. The selective biosynthesis of FDCA from 5-hydroxymethylfurfural (HMF) by a speci c enzyme poses a great challenge. In this study, we reported an e cient strategy to produce FDCA from HMF by the tandem biocatalysis of laccase (CotA-TJ102@UIO-66-NH 2 ) and Novozym 435. For the rst step, a nanoparticle metal organic framework was synthesized as a carrier to immobilize CotA-TJ102@UIO-66-NH 2 , which was assigned for the production of 5-formyl-2-furancarboxylic acid (FFCA) and featured an enzyme loading of 255.54 mg/g, speci c activity of 135.90 U/mg, and solid loading ratio of 99.65%. Under optimal conditions, an ideal FFCA yield of 98.5% was achieved, and the CotA-TJ102@UIO-66-NH2 pre- sented a high recycling capacity after 10 cycles. For the second step, Novozym 435 was applied for the further conversion of FFCA into FDCA, presenting a high FDCA yield of 95.5% under the optimized conditions. Novozym 435 also exhibited a high recyclability after eight cycles. As a result, the tandem biocatalysis strategy provided a 94.2% FDCA yield from HMF, indicating its excellence as a method for FDCA production.
基金Supported by the State Key Development Program for Basic Research of China (2009CB623404)Program for New Century Excellent Talents in University,the Programme of Introducing Talents of Discipline to Universities (B06006)State KeyLaboratory for Modification of Chemical Fibers and Polymer Materials (Dong Hua University)
文摘A facile surface segregation method was utilized to fabricate poly（vinyl alcohol）-polyethersulfone （PVA-PES） composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide （DMSO）, then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy （SEM）, X-ray photoelectron spectroscopy （XPS） and energy dispersive spectrometer （EDS） confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surtace by PVA reacned up to 86.8% when me PVA content m me membrane recipe was 16.7% （by mass）. The water contact angle decreased with the increase of PVA content. The effect of coagulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The membrane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.
基金supported by the Natural Science Foundation of Tianjin (No. 16JCYBJC19600)the National Natural Science Foundation of China (No. 21621004)the Beiyang Young Scholar of Tianjin University (2012)
文摘A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese carbonate were measured by SEM,XRD,TGA,BET and XPS. In this method,no harsh reaction conditions were required,and it was a simple and green process for the oxidation of 5-HMF into DFF. To achieve an optimum DFF yield,different reaction conditions,including reaction temperature,reaction time,catalyst amount,and solvents were investigated. Results from the experiments indicated that the highest DFF yield of 86.9% was obtained at 120 °C under atmospheric oxygen pressure after 6h. Finally,Mn CO_3 could be used at least five times with considerable stability.
基金supported by the National Key Research and Development Program of China(2021YFB3801200)the National Natural Science Foundation of China(21938007)the Natural Science Foundation of Hebei Province(E2020402036)。
文摘Membrane technology features inspiring excellence from numerous separation technologies for CO_(2) capture from post-combustion gas.Polyvinylamine(PVAm)-based facilitated transport membranes show significantly high separation performance,which has been proven promising for industrial scale-up.However,commercialized PVAm with low molecular weight and excessive crystallinity is not available to prepare high-performance membranes.Herein,the synthesis process of PVAm was optimized by regulating polymerization and acidic hydrolytic conditions.The membranes based on PVAm with a molecular weight of 154 kDa and crystallinity of 11.37%display high CO_(2) permeance of 726 GPU and CO_(2)/N_(2) selectivity of 55 at a feed gas pressure of 0.50 MPa.Furthermore,we established a PVAm synthesis reactor with an annual PVAm solution(1%(mass))capacity of over 7000 kg and realized the scaled-up manufacture of both PVAm and composite membranes.
基金Supported by the National Natural Science Foundation of China(21436009)the National High-tech Research and Development Program(2012AA03A611)the Program of Introducing Talents of Discipline to Universities(B06006)
文摘In this work, the effects of support surface pore structures(including surface pore size, surface pore density and surface porosity) on the performance of thin film composite(TFC) gas separation membrane over a wide pressure range(from 0.3 to 2.0 MPa) were studied. To fulfill it, the polysulfone(PSf) supports with different surface pore structures were prepared. Two kinds of wide-accepted polymeric membrane materials, i.e., polyvinylamine(PVAm) and Pebax 1657 copolymer, were used as skin layer materials. We pointed out for the first time that the support surface average pore size and pore density could affect the chain mobility of polymer of skin layer at the support surface pore entrance, then, can affect the TFC membrane performance. Besides, we also discussed the effects of support on the TFC membrane performance when the feed pressure changes for the first time. This work can provide guidance for choosing a suitable support for TFC gas separation membrane.
基金Supported by the National Natural Science Foundation of China （20836006）, the National Basic Research Program （2009CB623405）, the Science ＆ Technology Pillar Program of Tianjin （10ZCKFSH01700）, the Programme of Introducing Talents of Discipline to Universities （B06006）, and the Cheung Kong Scholar Program for Innovative Teams of the Ministry of Education （IRT0641）.
文摘Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost targets for CO2 capture. This study attempts to develop membranes with multiple permselective mechanisms in order to enhance CO2 separation performance of fixed carder membrane. In this study, a novel membrane with multiplepermselective mechanisms of solubility selectivity and reaction selectivity was developed by incorporating CO2-selective adsorptive silica nanoparticles in situ into the tertiary amine containing polyamide membrane formed by interfacial polymerization （IP）. Various techniques were employed to characterize the polyamide and polyam-ide-silica composite membranes. The TGA result shows that nanocomposite membranes exhlbit superior-thermal stability than pure polyamide membranes. In addition, gas permeation experiments show that both nanocomposite membranes have larger CO2 permeance than pure polyamide membranes. The enhanced CO2/N2 separation performance for nanocomposite membranes is mainly due to the thin film thickness, and multiple permselective mechanisms of solubility selectivity and reaction selectivity.
基金supported by the National Natural Science Foundation of China(21621004,22078239)the Beijing-Tianjin-Hebei Basic Research Cooperation Project(B2021210008)+1 种基金Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project(TSBICIP-KJGG-004)the Tianjin Development Program for Innovation and Entrepreneurship(2018)。
文摘Gamma-aminobutyric acid(GABA)is a natural non-protein functio nal amino acid,which has potential for fermentation industrial production by Lactobacillus brevis.This work investigated the batch fermentation process and developed a kinetic model based on substrate restrictive model established by experimental data from L25(5~6)orthogonal experiments.In this study,the OD600 value of fermentation broth was fixed to constant after reaching its maximum because the microorganism death showed no effect on the enzyme activity of glutamate decarboxylase(GAD).As pH is one of the key parameters in fermentation process,a pH-dependent kinetic model based on radial basis function was developed to enhance the practicality of the model.Furthermore,as to decrease the deviations between the simulated curves and the experimental data,the rolling correction strategy with OD600 values that was measured in real-time was introduced into this work to modify the model.Finally,the accu racy of the rolling corrected and pH-dependent model was validated by good fitness between the simulated curves and data of the initial batch fermentation(pH 5.2).As a result,this pH-dependent kinetic model revealed that the optimal pH for biomass growth is 5.6-5.7 and for GABA production is about 5,respectively.Therefore,the developed model is practical and convenient for the instruction of GABA fermentation production,and it has instructive significance for the industrial scale.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U2006220)。
文摘Polyamide(PA)thin-film composite(TFC)na nofiltration(NF)membrane has extremely broad application prospects in separation of monovalent/diva lent inorganic salts mixed solutio n.However,membrane fouling is the main obstacle to the application of PA,TFC and NF membrane.Streptomycin(SM)is a hydrophilic antibiotic containing a large number of hydroxyl and amino groups.In this work,the NF membrane was prepared via interfacial polymerization(IP)between trimesoyl chloride(TMC)in the organic phase and SM/piperazine(PIP)mixture in the aqueous phase.The NF membrane structure and performance were characterized in detail.The results showed that SM successfully participated in the IP.The negative charge and hydrophilicity of membrane surface were improved.The prepared membrane exhibited good anti-adhesion and anti-bacterial performance,Additionally,when the SM concentration was 2%,the prepared membrane exhibited the optimal permselectivity.The water permeance was 89.4L·m^(-2)·h^(-1)·MPa^(-1).The rejection of NaCl and Na_(2)SO_(4) were 17,17%and 97.84%,respectively.The NaCl/Na_(3)SO_(4) separation factor of the SM2-PIP/TMC membrane in 1000 mg·L^(-1) NaCl and 1000 mg·L^(-1)Na_(2)SO_(4) mixed solution was 40,which was 3.3 times that of PIP/TMC membrane.It indicated that SM2-PIP/TMC demonstrated excellent monovalent/divalent salts separation performance.This work provided an easy and effective approach to preparing anti-fouling NF membrane while possessing superior monovalent/divalent salts separation performance.
基金Supported by the Science and Technology Project of Tianjin(Grant No.12ZCZDSF02200)the Innovation Service Platform Project of Desalination and Comprehensive Utilization(Grant No.CXSF2014-34-C)
文摘Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline(PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope(SEM) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction(XRD) and differential scanning calorimetry(DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from α-phase to β-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials.
基金supported by the National Natural Science Foundation of China (No.21276177)Science and Technology Program of Tianjin as “Innovation Fund for Small and MediumSized Technology-Based Firms” (No.14ZXCXGX00335)
文摘C.I. Acid Red 73(AR73)wastewater was treated by cross-flow nanofiltration coupling electro-catalytic oxidation using an NF90 membrane and a Ti/SnO_2–Sb anode prepared via electrodeposition.Experiments conducted for standard electrochemical degradation of AR73 studied the reaction rate ofremoving AR73 using the Ti/SnO _2–Sb anode.A computational fluid dynamics(CFD)model was developed to predict the permeate flux under a laminar flow regime,including the effects ofoperating pressure,applied potential,initial concentration,and cross-flow velocity on this coupling process.The variations of the membrane surface concentration and permeate flux along the length of the channel were quantified.The experimental results were compared with those predicted by the model,and they agreed well.
基金Supported by the National Natural Science Foundation of China(21436009)the Program of Introducing Talents of Discipline to Universities(B06006)
文摘Recent advances on mixed matrix membrane for CO<sub>2</sub> separation are reviewed in this paper. To improve CO<sub>2</sub> separation performance of polymer membranes, mixed matrix membranes (MMMs) are developed. The concept of MMM is illustrated distinctly. Suitable polymer and inorganic or organic fillers for MMMs are summarized. Possible interface morphologies between polymer and filler, and the effect of interface morphologies on gas transport properties of MMMs are summarized. The methods to improve compatibility between polymer and filler are introduced. There are eight methods including silane coupling, Grignard treatment, incorporation of additive, grafting, in situ polymerization, polydopamine coating, particle fusion approach and polymer functionalization. To achieve higher productivity for industrial application, mixed matrix composite membranes are developed. The recent development on hollow fiber and flat mixed matrix composite membrane is reviewed in detail. Last, the future trend of MMM is forecasted.
基金Supported by the National Key R&D Program of China(No.2017YFB0603400)the National Natural Science Foundation of China(No.21436009)Tianjin Research Program of Basic Research and Frontier Technology(No.15JCQNJC43400)
文摘Membrane separation technology has popularized rapidly and attracts much interest in gas industry as a promising sort of newly chemical separation unit operation. In this paper, recent advances on membrane processes for CO_2 separation are reviewed. The researches indicate that the optimization of operating process designs could improve the separation performance, reduce the energy consumption and decrease the cost of membrane separation systems. With the improvement of membrane materials recently,membrane processes are beginning to be competitive enough for CO_2 separation, especially for postcombustion CO_2 capture, biogas upgrading and natural gas carbon dioxide removal, compared with the traditional separation methods. We summarize the needs and most promising research directions for membrane processes for CO_2 separation in current and future membrane applications. As the time goes by, novel membrane materials developed according to the requirement proposed by process optimization with increased selectivity and/or permeance will accelerate the industrialization of membrane process in the near future. Based on the data collected in a pilot scale test, more effort could be made on the optimization of membrane separation processes. This work would open up a new horizon for CO_2 separation/Capture on Carbon Capture Utilization and Storage(CCUS).
基金supported by the National Key Research&Development Program of China(2017YFB0603400)the National Natural Science Foundation of China(21938007)。
文摘Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.
基金Supported by the New Century Excellent Talents in University(NCET-10-0623)the National Natural Science Foundation for Distinguished Young Scholars(21125627)+1 种基金the National Basic Research Program of China(2009CB623404)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials(Dong Hua University)
文摘A high performance composite membrane was prepared under the inspiration of bioadhesion principles for pervaporative dehydration of ethanol.Chitosan(CS)and polyacrylonitrile(PAN)ultrafiltration membranes were used as the active layer and the support layer,respectively.Guar gum(GG),a natural bioadhesive,was introduced as the intermediate bonding layer to improve the separation performance and stability of the fabricated CS/GG/PAN composite membranes.The contact angle of the GG layer was just between those of the CS layer and the PAN layer,minimizing the difference of hydrophilicity between the active layer and the support layer.The peeling strength of the composite membrane was significantly enhanced after the introduction of the GG layer.The effects of preparation conditions and operation conditions including GG concentration,operating temperature and ethanol concentration in feed on the pervaporation performance were investigated.The as-fabricated CS/GG/PAN composite membrane showed the optimum performance with a permeation flux of up to804 g·m-2·h-1and a separation factor higher than 1900.Besides,the composite membranes exhibited a desirable long-term operational stability.
基金he National Key Research and Devel-opment Program of China(2017YFC0403800)the State Key Laboratory of Chemical Engineering(SKL-ChE-17T02).
文摘After years of research,the energy efficiency of energy recovery device has been raised to a high level,but the salinity mixing has not been effectively improved.Mixing will lead to a rise of highpressure seawater salinity,which will increase the operating cost.In this paper,the computational fluid dynamics(CFD)simulation of the rotary energy recovery device(RERD)is carried out.It is found that the unstable flow caused by the nonparallel between the channel and the flow direction of fluid is an important reason for mixing.After the inclined channel structure is adopted,the nonparallel problem is improved.The formation of unstable flow is effectively controlled.Under the commercial product operating conditions,the volumetric mixing of the optimized device is reduced from 3.34%to 1.29%,showing the effectiveness of the structure.
文摘Isobaric vapor-liquid equilibrium (VLE) data were measured for binary mixtures of toluene+N- formylmorpholine, toluene+3-methylthiophene and 3-methylthiophene+N-formylmorpholine at 101.33 kPa. The VLE data of the binary systems were found to be thermodynamically consistent. The saturated vapor pressure calculated by CSGC-PR equation of the pure component had higher accuracy than that calculated by Antoine equation. The liquid- phase activity coefficients of the binary systems were calculated by the Wilson, NRTL and UNIFAC models, and the binary interaction parameters of the three models were determined by the VLE data. The Wilson model was selected as the most suitable model to predict the VLE data of the ternary system of toluene+3-methylthiophene+N- formylmorpholine. The relative volatility between toluene and 3-methylthiophene was also calculated. Moreover, the effect of N-formylmorpholine as solvent was studied. When the molar ratio of solvent to feed (S/F) was 7, the relative volatility reached 1.904, which is almost twice the relative volatility without solvent. Therefore, N-formylmorpholine can be considered as an effective extracting agent for the separation of the close-boiling mixture of toluene+3- methylthiophene by extractive distillation.
