Catalytic Behaviour of Lipase Free and Immobilized in Biphasic Membrane Reactor with Different Low Water-Soluble Substrates

The catalytic activity and reaction rate of lipase have been studied using the biocatalyst free in an organic/aqueous emulsion and immobilized in a biphasic organic/aqueous membrane reactor. The first reaction system was realized in a stirred tank reactor. The other was obtained by immobilizing the enzyme in the sponge layer of an asymmetric capillary membrane and recirculating the two phases along the two separate circuits of the membrane module. The performance of the reactors has been studied using two different low water-soluble substrates: triglycerides present in commercial olive oil and (R,S)-cyanomethyl-[2-(4-isobutylphenyl)propionate] (CNE). The effects of substrate viscosity and flow dynamics conditions, such as organic phase flow rate, on the biphasic membrane reactor performance have been evaluated on the basis of observed reaction rate and catalytic activity of free and immobilized lipase for both substrates. It has been observed that free lipase showed higher catalytic activity with olive oil, while immobilized lipase showed higher catalytic activity with CNE which has a lower viscosity than olive oil. The increase of organic phase flow rate negatively affected the reactor performance, with a minor effect when using CNE rather than olive oil. The influence of temperature on the biocatalyst performance with the two substrates has also been investigated. The optimal temperature value of lipase was different for the two substrates: 28°C with CNE and 40°C with olive oil. © 1997 SCI.     

Separation and purification of isobutanol from dilute aqueous solutions by a hybrid hydrophobic/hydrophilic pervaporation process

In this study, a hybrid hydrophobic/hydrophilic pervaporation process was employed to separate and purify isobutanol from its dilute aqueous solutions. For this purpose, composite polydimethylsiloxane membranes were initially used for the recovery of isobutanol by hydrophobic pervaporation. Then the hydrophilic pervaporation with a composite polyvinyl alcohol membrane was utilized to separate water from the organic phase of the permeate stream of the hydrophobic pervaporation. The effect of feed flow rate on the performance of pervaporation was investigated. The resistance in series model was also applied to calculate the transport resistances through the composite membranes. It was observed that an enhancement in the feed flow rate led to higher permeation flux and selectivity of the more permeable component, while the flux of the less permeable component was almost constant. Also, the ratio of liquid boundary layer resistance to membrane layer resistance decreased by an increase in the feed flow rate. The isobutanol with a purity of higher than 99 wt.% was produced by the hybrid hydrophobic/hydrophilic pervaporation technique from a 2 wt.% aqueous isobutanol solution.     

Dynamic enzymatic resolution of Naproxen methyl ester in a membrane bioreactor

A lipase‐catalyzed enantioselective continuous hydrolysis process under in situ racemization of substrate using sodium hydroxide as catalyst was developed for the production of (S)‐Naproxen from racemic Naproxen methyl ester in an aqueous–organic biphase system. Use of a tubular silicone rubber membrane in the stirred tank reactor to separate the chemical catalytic racemization and biocatalytic resolution processes, served to avoid the key problem associated with conventional dynamic resolution, viz the incompatibility of in situ chemical racemization with the presence of a biocatalyst. To overcome product inhibition and to facilitate product recovery from the aqueous–organic emulsion containing substrate and lipase, a hydrophilic porous semipermeable membrane was used in the stirred tank reactor. Greater than 60% conversion of the racemate with an enantiomeric excess of product (ee_p) greater than 96% was obtained. In addition, transformation of Candida rugosa lipase (CRL) isoenzymes was observed in the reaction process. © 2001 Society of Chemical Industry     

膜反应器包衣酶法水解橄榄油的研究

在聚丙烯腈中空纤维膜反应器油-水两相体系中,使用表面活性剂包衣酶催化水解橄榄油。含有橄榄油和包衣酶的油相(有机相)在中空纤维膜管束内循环流动,而在纤维膜管束外则是水相循环。实验表明橄榄油和油酸的截留率分别为91％和82％,包衣酶全部截留在管束内。在30℃、橄榄油浓度为0.62 mol/L时,包衣酶催化底物转化率为60％,是相应脂肪酶催化转化率的2倍。     

Amphiphilic poly(ether sulfone) membranes for oil/water separation: Effect of sequence structure of the modifier

Oil‐contaminated wastewater threatens our environment and health thus novel membrane materials with low or nonfouling properties are an immediate need for oily wastewater treatment in a cost‐effective and environmentally friendly manner. In this study, three types of amphiphilic random, gradient, and block copolymers with similar molecular weights and chemical compositions, based on poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate (TFOA), were synthesized by the reversible addition‐fragmentation chain transfer (RAFT) method. The amphiphilic Poly(ether sulfone) membranes were then fabricated by blending with these copolymers via a facile coupled process of nonsolvent induced phase separation and surface segregation. Accompanying the phase inversion process of polymer matrix, the hydrophilic and hydrophobic segments in the amphiphilic modifiers would migrate and immobilize onto the membrane surfaces. This surface segregation process leaded to a chemical heterogeneous membrane surface comprising both hydrophilic PEGMA and low surface energy PTFOA brushes, which was confirmed by X‐ray photoelectron spectroscopy (XPS) and surface wettability analyses. Oil‐in‐water emulsion filtration test of the membranes displayed a lower permeate flux decline and a higher flux recovery (as high as 99.8%), establishing their considerably elevated antifouling properties. Additionally, cyclic oil/water separation and long‐term underwater immersion tests demonstrated that the as‐prepared membranes modified by these amphiphilic additives possessed excellent antifouling stabilities. © 2016 American Institute of Chemical Engineers AIChE J, 63: 739–750, 2017     

Separation of Hydrocarbons by Liquid Surfactant Membrane with a Batch Stirred Vessel

Abstract

Extraction experiments on liquid membrane permeation were conducted in a batch stirred vessel to separate aromatics from an aromatics-nonaromatics binary mixture as an inner oil phase in the emulsion. The investigations were conducted under various material systems (hydrocarbon feeds, aqueous membrane phases) and the mass transfer coefficient in the emulsion (dispersed phase) was measured. Independently of the system of hydrocarbon feed and aqueous membrane solution, the mass transfer coefficient of the dispersed phase could be correlated with the dimensionless stirring time and the solubility of the aqueous membrane phase. The batchwise results agree fairly well with previous results reported for continuous operation.     

利用醋酸纤维/聚四氟乙烯复合膜中的微结构固定化脂肪酶

脂肪酶的固定化是降低其使用成本的有效途径之一.提出了利用亲水/疏水复合膜中的微结构固定化脂肪酶的新思路.首先制备由致密的亲水层和多孔的疏水层组成的醋酸纤维素/聚四氟乙烯（CA/PTFE）复合膜,然后利用复合膜的特殊微结构,用超滤的方法实现了脂肪酶的固定化.扫描电镜照片结果表明,大部分被截留的酶位于复合膜的界面处.制备得到的固定化酶膜应用于水解橄榄油的反应,其最高催化活力达到1.24 μmol FFA·min^-1·cm^-2,大大高于文献报道值.同时研究了固定化脂肪酶膜的催化动力学,考察了亲水层厚度和脂肪酶负载量对固定化效果的影响,优化了固定化条件.在经过10次（50 h以上）的重复使用后,固定化酶膜的活力仅降低了20%.     

Enzyme hydrolysis of babassu oil in a membrane bioreactor

This work deals with the enzymatic hydrolysis of babassu oil by immobilized lipase in a membrane bioreactor using unmixed aqueous and lipid streams. The experimental work was carried out in a flat plate membrane module with two different membranes: hydrophobic (nylon) and hydrophilic [mixed cellulose esters (MCE)], with different nominal pore sizes ranging from 0.10 to 0.65 μm. Candida cylindracea lipase was adsorbed on the membrane surface area, and the reactor was operated in batch mode. The initial enzymatic rate increased from 80 to 150 μmol H⁺/min when the organic phase velocity increased from 1.0×10⁻³ to 3.0×10⁻³ m/s, indicating that mass transfer in that phase was the process-limiting step. Calcium ions had a marked effect on immobilized lipase activity, increasing around twofold the lipolytic activity. Long-term experimental runs showed that the immobilized lipase remained stable for at least 8 d. The values for immobilized protein and maximal productivities observed for 0.45 μm membranes were: 1.01 g/m² and 193 μmol H⁺/m²·s for MCE membrane and 0.78 g/m² and 220 μmol H⁺/m²·s for nylon membrane. The productivities obtained are among the highest values reported in the technical literature.     

Role of silane grafting in the development of a superhydrophobic clay-alumina composite membrane for separation of water in oil emulsion

Hydrophobic composite kaolin-coated clay-alumina membranes are unique choices for water in oil emulsion separation. In this work, a membrane fabrication approach is presented using kaolin clay coating in the clay-alumina tubular composite support tube and subsequently grafting by different concentrations of fluoroalkyl silane (FAS: 1H, 1H, 2H, 2H, -Perfluorooctyltriethoxysilane) on the membrane surface. Different concentrations of fluoroalkyl silane formed distinctive hierarchical structures which exhibited hydrophobicity of the membrane surface. The pore property, surface roughness properties, and thermogravimetric properties can be suitably tailored by tuning the silane concentration in the grafting solution. The surfaces of comparatively higher silane content grafted (M50 and M100) composite membranes were found to be superhydrophobic. Comparably, our optimal composite membrane (M100) displayed a moderate steady flux rate of 80-100LMH (Lm^?2h ^?1) and excellent water rejection (>99%) properties during the separation of water in hexane and toluene emulsion at a cross-flow transmembrane pressure of 1 bar. The role of silane concentration on permeated hexane and toluene flux rate, water rejection rate, surface wettability, microstructure, and hydrophobic stability reveals new distinguishing insights into the hydrophobic clay-alumina composite membrane fabrication.     

Membrane degumming of crude soybean and rapeseed oils

Membrane separation in edible oil processing is a potential area for energy savings. However, technical and operating-cost-related barriers have impeded the successful application of membrane separation in food processing. Studies were undertaken with soybean and rapeseed oils in a magnetically stirred flat-membrane batch cell with two types of composite polymeric membranes at 3 MPa pressure and at a constant temperature of 40°C. The membranes were NTGS-1100 and NTGS-2100, and used silicon as the active layer and polysulfone and polyimide as support layers, respectively. The membrane selectively rejected phospholipids, the content being less than 240 mg/kg in the permeate without any pretreatment or dilution of crude oil with organic solvent. Long-term studies up to 97 days with soybean oil at two different pressures, 2 and 3 MPa, showed that the rejection of phosphatides was above 96% in most permeates. The permeate flux remained nearly constant but must be improved.     

疏水性油水分离膜及其过程研究进展

油水分离是治理含油废水和含水油液的重要工业过程。本文概括了疏水性油水分离膜的类型与制备方法,包括常规分离膜和高度疏水/超亲油分离膜。前者为常规微滤、超滤及纳滤过程用膜;后者由构筑高度疏水（水滴接触角≥120°）表面方法得到,形式有金属网膜、纤维膜、滤纸、复合膜及不对称膜,其为制备耐污染的疏水性油水分离膜提供了新思路。指出了疏水性膜用于油水分离的过程原理及应用现状：含油废水除油中,疏水性膜可实现O/W乳液的破乳、粗粒化油滴、滤除油滴及吸附油分子几方面的功能;含水油液除水中,膜被用来截留水滴,可直接得到净化的油品。最后,指出了其过程规模化应用前尚需解决的重要问题,特别是高度疏水/超亲油分离膜的制备、相关过程研究的深入及其规模化试验等方面需着力加强。     

Hierarchical amphiphilic high-efficiency oil–water separation membranes from fermentation derived cellulose and recycled polystyrene

A high-efficiency separation of oil and water can be achieved by using specially designed amphiphilic porous membrane. However, the preparation of such membranes often involves complex multistep chemical processes. Herein, we report an amphiphilic composite membrane (polystyrene [PS]/bacterial cellulose [BC] membrane) consisting of hydrophobic recycled PS and hydrophilic BC, fabricated by a facile in situ fermentation process. Not only these membranes exhibit a combination of contrasting wettability but also comprise of a hierarchical network of microfibers and nanofibers, which makes them ideal for oil–water separation. The structural and morphological properties of as-produced BC, recycled PS membrane, and PS/BC composite membrane were studied by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The ability of the membranes to separate oil and water was tested by using an emulsion of hexane-in-water as the feed and the collected filtrates were characterized by optical microscopy and UV–Vis spectroscopy. PS membranes were unable to separate oil and water, while the PS/BC membrane efficiently separated water from the emulsion. PS/BC composite membranes showed a high water recovery of more than 90%, against only 57% recovery shown by BC. Mechanisms of oil–water separation for each membrane are discussed. The reusability of the PS/BC composite membrane was also demonstrated.     

Influence of adsorption and concentration polarisation on membrane performance during ultrafiltration of a non-ionic surfactant

Surfactants are present in almost all aqueous solutions — either as additives for different purposes, or because they occur naturally. Because of the common occurrence of surfactants in process water it is important to know how they behave in membrane processes. Ultrafiltration membranes allow almost complete passage of surfactant monomers, but reject micelles almost completely. Concentration polarisation during ultrafiltration of surfactant solutions is therefore mainly influenced by the presence of micelles. Operating parameters, e.g. the transmembrane pressure and the concentration of surfactant, as well as the pure water flux of the membrane, have a marked influence on the performance of hydrophilic membranes, as shown in this investigation. A distinct difference between the interaction of a non-ionic surfactant with hydrophilic and hydrophobic membranes was observed. The hydrophobic membrane showed a flux reduction already at concentrations below the critical micelle concentration (CMC), whereas no flux reduction was observed for a hydrophilic membrane with the same nominal molecular weight cut-off, below the CMC.     

Tuning the morphology of PVDF membranes using inorganic clusters for oil/water separation

Polyvinylidene fluoride (PVDF) membranes with modified membrane morphology were prepared by phase inversion process using iron alkoxide as a novel pore-forming additive (PFA). Higher pure water flux was observed for PVDF/PFA (iron alkoxide) membranes treated with 5% HCl, due to higher porosity produced by the leaching out of the iron alkoxide additive. The untreated membrane containing 0.04% iron alkoxide showed ~99% efficiency oil removal from a surfactant-stabilized oil–water emulsion. After acid treatment, there was a slight decrease in the rejection efficiency (~96.5%); however, this membrane still exhibited the highest emulsion flux. The fouling propensity of the membrane with 0.04 wt % iron alkoxide tested in a crossflow condition decreases indicating a lower amount of oil adsorbed onto the surface and a greater flux recovery ratio. The treated membranes showed appreciable anti-biofouling property when the membranes were challenged with Escherichia coli and Bacillus subtilis obtained from freshwater and/or seawater. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47641.     

Separation of Ethyl Esters of Eicosapentaenoic Acid and Docosahexaenoic Acid by Circulating Liquid Membranes Using Silver Nitrate as a Carrier. Uphill Transport by Use of Temperature and Solvent Dependencies of Distribution Ratio

Abstract

Experiments on the separation of ethyl ester of eicosapentaenoic acid (EPA-Et) and that of docosahexaenoic acid (DHA-Et) contained in ethyl ester of bonito oil (bonito oil-Et) were performed using circulating liquid membranes (CIRLMs) containing sliver nitrate as a carrier. In this liquid membrane system an aqueous silver nitrate solution was circulated between a stirred vessel containing an organic solution of bonito oil-Et and another stirred vessel containing a receiving organic solvent. Using the CIRLM, two types of uphill facilitated transport of EPA-Et and DHA-Et in bonito oil-Et were demonstrated. The first type utilizes the distribution ratio of EPA-Et and DHA-Et, defined as the ratio of the concentration in the aqueous phase to that in the organic phase at equilibrium, which is remarkably dependent on the temperature, and the second uphill transport was based on the fact that the distribution ratio is considerably dependent on the solvent of the organic phase. A model of permeation through the circulating liquid membrane was proposed to explain the experimental results.     

Innovative hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride (PVDF) composite membrane for vacuum membrane distillation

Though membrane distillation (MD) has gained more and more attention in the field of desalination, the wetting phenomenon was still a non-negligible problem. In this work, a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride composite membranes. This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane. In terms of anti-wetting properties, contact angle and liquid entry pressure of all composite membranes (except for those based on 0.45 μm) exceeded 160° and 0.3 MPa, respectively. In particular, the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5% (mass) saline solution (NaCl) at 60 ℃. The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux. And for stability tests (testing the 0.22 μm membrane coated by 5% (mass) PFPE), the highest MD flux 29.08 kg·m^-2·h^-1 and stable salt rejection (over 99.99%) during the period. Except that, the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography, porosity, mechanical strength and pore size characteristics. This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.     

Clean Synthesis of Fatty Acids in an Intensive Lipase-Catalysed Bioreactor

The operation and performance of a laboratory-scale catalytic bioreactor used for the hydrolysis of mixed natural oils into free fatty acids in the presence of free lipase (triacylglycerol ester hydrolase, EC 3.1.1.3) is described. The novelty of the reactor system is the intensification of the reaction kinetics by electrostatic spraying of the lipase as a dispersion of very fine droplets into the oil phase. The effect of phase ratio and field strength on the kinetics were measured for a simple batch type spray reactor. Coalescence rates within the electrostatic spray reactor were shown to be significantly higher than conventional stirred systems. The kinetic data were compared with a control experiment in which the free lipase suspension and oil were contacted by mechanical mixing in the absence of any externally applied electrical field. © 1997 SCI.     

超亲水SiO2修饰膜的构建及其油水乳液分离性能

采用硅溶胶和多巴胺作为修饰剂,通过一步反应在微孔聚丙烯膜(MPPM)表面构建了SiO₂修饰层。利用FTIR、ESEM和EDX对膜进行了表征,发现膜表面SiO₂颗粒分布非常均匀。水/油接触角及纯水通量实验结果表明,修饰膜具有超亲水性及水下超疏油性,透水能力强,水通量大[在0.1 MPa时,水通量高达(5100±500)L·m^-2·h^-1]。油水乳液分离结果表明,修饰膜能有效分离油水乳液,在0.05 MPa时,油水乳液水通量达2830 L·m^-2·h^-1,油截留率达99.8%以上,即使过膜压力增大到0.15 MPa,油截留率也能保持在99%以上,且膜表面的油污可用水清洗除去,展现出很好的应用前景。     

Characteristics and performance of new types of ultrafiltration membranes with chemically modified surfaces

A special “quo;coating”quo; technique for making new types of surface modified ultrafiltration membranes has been developed and evaluated. The preparation procedure comprises the following principle:

A suitable ultrafiltration support membrane made by the traditional phase inversion process is surface coated with an aqueous solution containing a hydrophilic polymer and/or monomer having reactive groups and a catalyst (the coating step). The membrane material is selected from the class of fluorine containing polymers. By raising the temperature, the hydrophilic components are chemically bonded to the membrane material at the exposed surface by an addition reaction (the curing step).

Using this method you can impart hydrophilic properties to an otherwise hydrophobic, high resistant synthetic polymeric ultrafiltration membrane.

The properties of the final membrane depend on the characteristics of the support membranes, the composition of the coating solution and the amount applied and the reaction conditions. The technique seems more or less universal - e.g. it is possible to make a series of membranes with different cut-off values.

Results from measurements on different test solutions and on relevant industrial products are described. Characterization is done by measuring hydraulic permeability and rejection of dextrans and proteins. Flux stability and fouling tendency have been examined using different model foulants.

Membrane surface structures are characterized by SEM-studies. Analytical investigations using infrared spectroscopy (FTIR/ATR) and X-ray photoelectron spectroscopy (ESCA) have been tried to get some information about the chemistry of the coating.

The main advantages of the new membranes are that higher flux values compared to a standard polyethersulfone UF membrane are generally obtained - e.g. on whey flux improvements in the order for 20 – 50% have been observed and for fermentation broths fluxes can be several times greater compared to results using the standard membrane.

Some of these new membranes are now commercially available and are supplied by DDS FILTRATION, designated ETNA series.     

Membrane‐Based Conditioning of an Innovative Oil‐Based Preservative for Food Technology

Demulsification of emulsions is of great interest for industrial applications. For developing a new, alternative preservation process, investigations are conducted for separating a mixture of water and an oil‐based preservative by membrane technology. Using a water‐in‐oil emulsion, the conventional membrane separation with hydrophobic membranes does not show a reasonable result. It was found that the oil‐based preservative leads to a hydrophilization of the membrane by its amphipathic character. Subsequently, a possible separation with a hydrophilic membrane system as a coalescing system was investigated. Different parametric studies were performed. The efficiency of the coalescence depends on the membrane material, the pore size, the transmembrane pressure, and the temperature during membrane passage as well. Best results so far have been achieved by using a polyethersulfone membrane with a pore size of 0.6 μm.