Economy, environmental assessment and energy conservation for separation of isopropanol/diisopropyl ether/water multi-azeotropes via extractive distillation coupled pervaporation process

This wok proposed the extraction distillation coupled pervaporation(ED+PV) technology process using two different solvents to separate isopropanol(IPA) and diisopropyl ether(DIPE) from DIPE/IPA/H_(2)O ternary heterogeneous azeotropes in industrial wastewater from the synthesis of isopropanol in this study.Based on strict design specifications, simulation and sequential iteration methods are used for process design and optimization. Compared to the ethylene glycol(EG)-EG+H_(2)O process and the 1,3-propanediol(PDO)-IPA+H_(2)O process, the total annual cost(TAC) of the EG-IPA+H_(2)O process decreased by 20.76% and 7.86%(PDO). Compared to the EG-EG+H_(2)O process, the TAC of the PDO-IPA+H_(2)O process reduced 14%, but the global warming potential(GWP) and human toxicity of the PDO-IPA+H_(2)O process increased 11.3% and 4.07% respectively. Compared to the PDO-IPA+H_(2)O process, the EG-IPA+H_(2)O process saves 7.86%(TAC), 9.78%(GWP) and 9.85%(human toxicity). The ED+PV process with EG is superior to PDO in factors of TAC, energy consumption, human toxicity and environment. The EG-IPA+H_(2)O process changed the separation order of the products of the multi-azeotropic system, reduced the cost and energy conservation of the system, and enhanced the environmental protection evaluation of the process, is the best process through life cycle assessment for analyzing the economy, energy conservation, environmental assessment and human toxicity, designing cleaner products, controlling waste discharge, and promoting the chemical purification industry. This work provides a new process design and optimized separation ideas, will have a good guiding significance for the research and application separation of multi-azeotropic mixture with mixed solvents in organic wastewater from the cleaner chemical production, has been up to standard wastewater discharge process, and realized the development goal of carbon peak and carbon neutrality in the sustainable development of chemical clean industry.

Graphene quantum dots doped poly(vinyl alcohol)hybrid membranes for desalination via pervaporation

Pervaporation desalination by highly hydrophilic materials such as poly(vinyl alcohol)(PVA)based separation membrane is a burgeoning technology of late years.However,the improvement of membrane flux in pervaporation desalination has been a difficult task.Here,a novel hybrid membrane with doped graphene oxide quantum dots(GOQDs)which is rich in hydrophilic groups and small size into the matrix of PVA was prepared to improve the membrane flux.The membranes structures were described by field emission scanning electron microscopy(FESEM),atomic force microscopy(AFM),Fourier transform infrared(FT-IR),differential scanning calorimetry(DSC),thermogravimetric analysis(TGA)and X-ray diffraction(XRD).And more,Water contact angle,swelling degree,and pervaporation properties were carried out to explore the effect of GOQDs in PVA matrix.In addition,GOQDs content in the hybrid membrane,NaCl concentration,and feed temperature were investigated accordingly.Moreover,the hydrogen bonds between PVA chains were weakened by the interaction between GOQDs and PVA chains.Significantly,the hybrid membrane with optimized doped GOQDs content,200 mg·L^(-1),displays a high membrane flux of 17.09 kg·m^(-2)·h^(-1)and the salt rejection is consistently greater than 99.6%.

Comprehensive analysis on the economy and energy demand of pressure-swing distillation and pervaporation for separating waste liquid containing multiple components

A large amount of waste liquids containing methanol/acetone/water mixtures are produced in the synthesis of methyl methacrylate(MMA).Under the advocacy of green chemical industry,it is urgent to develop an efficient,economic and energy-saving mixture separation process.Through thermodynamic azeotropic behavior and pressure sensitivity analysis,pressure-swing distillation was determined and the optimal separation pressure of each column in the process was obtained.Due to the composition of waste liquids produced were quite different in MMA production,the pressure-swing distillation separation process was designed to fully achieve the accurate waste liquids treatment.Taking the total annual cost(TAC)as the target,the sequential iteration method was used to optimize the process,and the impact of composition on economy was compared.In order to further realize the energy-saving of the separation process,the pervaporation membrane module was introduced to pretreat the waste liquid in the pressure-swing distillation.The results showed that the TAC of the coupling process was 46% higher than that of the pressure-swing distillation process,and the thermodynamic efficiency was 30% higher.This study provides waste liquid treatment technology for enterprises and analyzes its economic and energy efficiency,which has reference significance for the development of coupled separation technology.

Effects of ion-exchange on the pervaporation performance and microstructure of NaY zeolite membrane

Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),KNO_(3),and AgNO_(3),have great effects on the channel structure and water affinity of the NaY zeolite membrane.When the concentration of nitrate salt,ion-exchange temperature and time are 0.1 mol·L^(-1),50℃and 2 h,the ion-exchange degree order of NaY zeolites is Ag^(+)>K^(+)>Ca^(2+)>Zn^(2+)>>Co^(2+)>Mg^(2+).Especially,Ag^(+)and K^(+)cation exchange degree of NaY zeolites are achieved to 96.54% and 82.77% in this work.BET surface,total pore capacity,pore size distribution and water contact angle of the ion-exchanged NaY zeolites are all disordered by mono-and di-valent cations.Di-valent nitrate salt is favor for increasing the dehydration performance of NaY zeolite membranes by ion-exchange.When the ion-exchange solution is Zn(NO_(3))_(2),the total flux variation and separation factor variation of the NaY membrane(M-5)are -45% and 230% for separation of 10%(mass)H_(2)O/EtOH mixture by pervaporation,and the ion-exchanged membranes showed good reproducibility.

Mass transfer model,preparation and applications of zeolite membranes for pervaporation dehydration:A review

Pervaporation(including vapor permeation) is a kind of new membrane separation technology, possessing the advantages of high efficiency, energy saving and convenient operation. It has promising application in the separation and purification of organic solvents. Dehydration is an important step in the production and recovery of organic solvents. Zeolite membranes have attracted wide attention for pervaporation dehydration due to their high separation performance and good thermal/chemical stability. So far, zeolite membranes have been preliminarily industrialized for dehydration of organic solvents. This paper reviews the recent development of zeolite membranes for pervaporation dehydration, including mass transfer models, preparation and applications of zeolite membranes. The review also discusses the current industrial applications of zeolite membranes and their future development in pervaporation.

Manipulation of confined structure in alcohol-permselective pervaporation membranes

Alcohol-permselectivity pervaporation has been arousing increasingly more attention in bioalcohol production due to the advantages of environmental friendliness, low energy consumption and easy coupling with fermentation process. With the intrinsic feature of larger molecules preferentially permeating and the consequent inferiority in selective diffusion, the development of alcohol-permselective membrane is relatively retarded compared with water-permselective membrane. This review presents the prevalent membrane materials utilized for alcohol-permselective pervaporation and emphatically expatiates the representative and important developments in the past five years from the aspect of tuning confined structure in membranes. In particular, the diverse structure tuning methods are described with the classifications of physical structure and chemical structure. The corresponding structure-performance relationships in alcohol-permselective pervaporation membranes are also analyzed to identify the objective of structure optimization. Furthermore, the tentative perspective on the possible future directions of alcohol-permselective pervaporation membrane is briefly presented.

PERVAPORATION PROPERTIES OF PDMS MEMBRANES CURED WITH DIFFERENT CROSS-LINKING REAGENTS FOR ETHANOL CONCENTRATION FROM AQUEOUS SOLUTIONS

Ethanol perm-selective PDMS/PVDF composite membranes were prepared by curing polydimethylsiloxane (PDMS) with various cross-linking reagents,such as tetraethoxylsilane(TEOS),γ-aminopropyltriethoxylsilane(APTEOS), phenyltrimethoxylsilane(PTMOS) and octyltrimethoxylsilane(OTMOS) as well.The cross-linking density and surface properties of the PDMS active layer were adjusted by varying cross-linking reagents.The pervaporation performance of PDMS membranes cured with different cross-linking reagents was investig...

PERVAPORATION OF ETHANOL/WATER MIXTURES WITH HIGH FLUX BY ZEOLITE-FILLED PDMS/PVDF COMPOSITE MEMBRANES

Thin-film zeolite-filled silicone/PVDF composite membranes were fabricated by incorporating zeolite particles into PDMS(poly(dimethylsiloxane)) membranes.The morphology of zeolite particles and zeolite filled silicone composite membranes were characterized by SEM.The zeolite-filled PDMS/PVDF composite membranes were applied for the pervaporation of ethanol/water mixtures and showed higher flux compared with that reported in literatures.The effect of zeolite loading and Si/Al ratio of zeolite particles on pe...

Fabrication of high-performance PVA/PAN composite pervaporation membranes crosslinked by PMDA for wastewater desalination

The pyromellitic dianhydride（PMDA） crosslinked poly（vinyl alcohol）（PVA） was coated on top of the PAN ultrafiltration membrane to form a PVA/PAN composite PV membranes for wastewater desalination. The composite membranes have high application value in industrial wastewater treatment. By varying the membrane fabrication parameters including the weight percent（wt%） of the PMDA, the crosslink temperature and duration, membrane with the best desalination performance was obtained. The composite membrane with a 2-lm-thick PVA selective layer containing 20 wt% of PMDA and being crosslinked at 100 °C for 2 h showed the highest Na Cl rejection of 99.98% with a water flux of 32.26 L/（m^2 h）at 70 °C using the 35,000 ppm Na Cl aqueous solution as feed. FTIR spectroscopy, wide-angle X-ray diffraction, thermogravimetric analysis and scanning electron microscope have been used to characterize the structures and properties of both the crosslinked PVA dense films and PVA/PAN composite membranes. The effects of the concentrations of PMDA,the crosslinking time and temperature to the membrane water contact angle, swelling degree, salt rejection and water flux were systematically studied.

The potential of pervaporation for biofuel recovery from fermentation:An energy consumption point of view

Recovering alcohols from dilute fermentation broth is an emergent task in bio-fuel production process. Since they are primary planned for fuels, energy required to separate these alcohols should be considered in evaluating the potential of a separation technology. A membrane-based process, pervaporation, is of special interest because of its environmental friendliness and easy integrating character. This review probes into the fundamentals of pervaporation especially in terms of the heat required for evaporation. Meanwhile, the separation data of the most representative alcohol-selective pervaporation membranes reported in the literatures are collected and compared with the vapor–liquid equilibrium curve, which represents the distillation selectivity. They include:inorganic membranes, silicon rubber based membranes, Mixed Matrix Membranes and some other special materials. By doing so, the status of alcohol recovery via pervaporation would be more clear for researchers.For ethanol recovery, it is selectivity rather than flux that is in urgent need of solution. While for butanol recovery,membranes with satisfactory selectivity have been developed, increasing the separation capacity would be more pressing.

Process operation performance of PDMS membrane pervaporation coupled with fermentation for efficient bioethanol production

There would be strong product inhibition on ethanol fermentation process if ethanol is not removed in situ from broth. PDMS membrane pervaporation coupled with fermentation is a promising process for efficient bioethanol production since ethanol inhibition is relieved or eliminated. From the perspective of process operation, membrane separation performance, ethanol fermentation performance and the subsequent processing on membrane downstream are the three key issues. This review aims at contributing a comprehensive overview on the operation performance of the integrated process. The state-of-the-art of the three key issues related to the operation performance is focused. Finally, the tentative perspective on the possible future prospects of the integrated process is briefly presented.

PDMS/ZIF-8 coating polymeric hollow fiber substrate for alcohol permselective pervaporation membranes

In order to develop high performance composite membranes for alcohol permselective pervaporation(PV),poly(dimethylsiloxane)/ZIF-8(PDMS/ZIF-8)coated polymeric hollow fiber membranes were studied in this research.First,PDMS was used for the active layer,and Torlon?,PVDF,Ultem?,and Matrimid?with different porosity were used as support layer for fabrication of hollow fiber composite membranes.The performance of the membranes varied with different hollow fiber substrates was investigated.Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers.The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated.The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect.Based on the result,ZIF-8 was introduced to prepare more selective separation layer,in order to improve the PV performance.The PDMS/ZIF-8/Torlon?membrane had a separation factor of 8.9 and a total flux of 847 g·m-2·h-1.This hollow fiber PDMS/ZIF-8/Torlon?composite membrane has a great potential in the industrial application.

VOC removal from contaminated groundwater through membrane pervaporation. (Ⅱ): 1,1,1-trichloroethane-SDS surfactant solution system

The conventional “pump-and-treat' technology for subsurface remediation of groundwater contaminated with volatile organic compounds(VOCs) such as 1,1,1-trichloroethane(TCA), a common chlorinated organic solvent, has limitation of prohibitively long treatment time due to extremely low water solubility of the VOCs. Surfactant-based soil remediation has emerged as the effective technology that substantially reduces the treatment time. In order to make the whole process economical, the surfactant used in soil washing has to be recovered and reused. This study examined the recovery of anionic surfactant, sodium dodecyl sulfate(SDS), from soil remediation fluids containing TCA, using a bench-scale membrane pervaporation unit. The effects of high TCA concentration, surfactant dosage, and flow rate on permeation flux and selectivity(α value) of the process were evaluated. In general, higher surfactant concentration yielded lower TCA flux and constant water flux, resulting in declining α values; higher flow rate of TCA feed stream results in higher VOC flux and selectivity, an indication of the effect of concentration polarization; higher TCA feed concentration produces higher TCA permeation across the membrane, however, the selectivity was virtually unchanged unless the total TCA concentration exceeded 2000 ppm.

PERVAPORATION SEPARATION FOR TOLUENE/n-HEPTANE MIXTURE BY POLYIMIDE MEMBRANES CONTAINING FLUORINE

Five kinds of polyimides were synthesized using five dianhydrides (including 2,2-bis[4-(3,4-dicarboxyphenoxy)- phenyl] propane dianhydride (BPADA),3,3 ,4,4 -diphenylsulfone-tetracarboxylic dianhydride (DSDA),4,4 - (hexafluoroisopropylidene)-diphthalic anhydride (6FDA),1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA), and 4,4 -oxydiphthlic dianhydride (ODPA)) and 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (BDAF) via the two- step method that included polyaddition to form the polyamic acid a...

Synthesis of HTPB based PU-PS IPN Membrane for Pervaporation Recovery of Butanol

Hydroxyl terminated polybutadiene（HTPB） based polyurethane（PU）-polystyrene（PS） interpenetrating polymer network（IPN） was prepared and characterized by FTIR, TGA, WCA, swelling experiments, and SEM. The IPN was used for pervaporation（PV） recovery of butanol. Both the permeation flux and separation factor increased with feed temperature, and both water and butanol fluxes increased with feed concentration while no obvious effect of concentration on separation factor was found. Through the formation of IPN structure, the total flux of HTPB based PU increased greatly with the decrease of separation factor. At the feed temperature of 60 °C, the IPN membrane obtained a total flux of 613.3 g/m^2 h with a separation factor of 6.15.

VOC removal from contaminated groundwater through membrane pervaporation. (Ⅰ): Water-1,1,1-trichloroethane system

trichloroethane(TCA), a common chlorinated organic solvent and volatile organic compound(VOC), was removed from contaminated groundwater by using a bench-scale membrane pervaporation unit. The effects of TCA concentration, temperature, and flow rate on permeation flux and selectivity(α value) of the process were evaluated. In general, higher temperature leads to higher VOC flux but lower selectivity; higher flow rate of TCA feed stream results in higher VOC flux and selectivity, an indication of the effect of concentration polarization; higher TCA feed concentration produces higher TCA permeation, however, the selectivity was virtually unchanged.

Graphene-based membranes for pervaporation processes

Two-dimensional graphene and its derivatives exhibiting distinct physiochemical properties are intriguing building blocks for researchers from a large variety of scientific fields.Assembling graphene-based materials into membrane layers brings great potentials for high-efficiency membrane processes.Particularly,pervaporation by graphene-based membranes has been intensively studied with respect to the membrane design and preparation.This review aims to provide an overview on the graphene-based membranes for pervaporation processes ranged from fabrication to application.Physical or chemical decoration of graphene-based materials is elaborated regarding their effects on the microstructure and performance.The mass transport of pervaporation through graphene-based membranes is introduced,and relevant mechanisms are described.Furthermore,performances of state-of-the-art graphene-based membranes for different pervaporation applications are summarized.Finally,the perspectives of current challenges and future directions are presented.

STUDY OF COMPOSITE MEMBRANE OF CELLULOSE ACETATE OR POLYVINYL ALCOHOL BLENDED WITH METHYLMETHACRYLATE-ACRYLIC ACID COPOLYMER FOR PERVAPORATION SEPARATION

In this paper, methylmethacrylate-acrylic acid MMA-AA hydrophilic and hydrophobic copolymers were prepared by copolymerization for preparing membrane materials. The composite membrane of cellulose acetate (CA) blended with MMA-AA hydrophobic copolymer was used for the separation of methanol from pentane-methanol mixture. When the methanol concentration was only 1 wt%, the permeate flux still maintained at 350 g/m(2)h and separation factor was as big as 800. The composite membrane of PVA (polyvinyl alcohol) blended with MMA-AA hydrophilic copolymer was used for the separation of ethanol-water mixture. The permeate flux was increased to 975 g/m(2)h at 74 degrees C and the separation factor reached 3000 at 25 degrees C. The PVA/MMA-AA blended membrane surface modified by ammonia plasma was also investigated for separating ethanol-water mixture. Both permeate flux and separation factor of the membrane was improved. However, there was no obvious difference of plasma treatment time in the interval of 20 similar to 40 min.

Pervaporation Characteristics in Removal of Benzene from Water through Polystyrene-Poly (Dimethylsiloxane) IPN Membranes

This paper focuses on the effects of the PSt content of polystyrene (PSt)-poly (dimethylsiloxane) (PDMS) interpenetrateing network (IPN) polymer membranes, on the pervaporation (PV) characteristics during the removal of benzene from an aqueous solution of dilute benzene. When an aqueous solution of 0.05wt% benzene was permeated through the PSt-PDMS IPN membranes, they showed high benzene/water selectivity. Both the permeability and the benzene/water selectivity of the membranes were enhanced with increasing PSt content in the PSt-PDMS IPN membrane. The physicochemical mechanism of permeation and separation through the PSt-PDMS IPN membranes during PV is also discussed. The best normalized permeation rate, separation factor for benzene selectivity, and PV separation index of the PSt-PDMS IPN membrane were 1.27 × 10-6 kgm (m2hr)-1, 3293, and 41821, respectively. These PV characteristics are discussed from the viewpoint of the chemical and physical structure of the PSt-PDMS IPN membranes.

Fabrication and Characterization of Pulp/Chitosan Composite Membranes Crosslinked with 3-Methylglutaric Anhydride for Pervaporation of Ethanol/Water Mixture

Chitosan/Cellulose (CTS/CL) composite membranes were prepared by cross-linking reaction with 3-methy- lglutaric anhydride (3MGA). The cross-linked membranes with CTS/CL were obtained at different CTS con- tents in variations from 50 to 100 wt%, and these membranes were applied in the dehydration of ethanol/wa- ter mixtures. Especially, it was observed that in the case of a composite membrane containing chitosan 80% (CTS/CL-80/20) showed a performance with a separation factor of α = 17.1 and a total permeation flux of J = 326 g/(m2h). It was observed that the total permeation flux decreased when the cross-linking increased and the increase in the ethanol content in the feed solution showed an increase in the separation factor. The CTS/ CL-80/20 showed excellent performance with good mechanical strength and dehydration performance in the ethanol/water mixture separation.