Application of cross-flow microfiltration to semi-hard cheese production from milk retentates

In the cheese industry, the concentration of milk using ultrafiltration for continuous soft and fresh cheese production is standard technology. The object of the work presented here was to produce a semi-hard cheese of quality and composition comparable to that of traditionally made cheese from highly concentrated microfiltered milk retentate. Two different membrane systems were tested for the production of high viscous milk retentate with high dry matter content. For milk containing 3.2% fat and skim milk, a concentration factor of 6.6 and 9.1 respectively was obtained using the MF/UF/UF pilot plant fitted with cassette modules. Milk containing 3.2% fat was concentrated in batches by a factor of 5.7 in the pilot plant using a ceramic membrane. Using minimal curd separation, a semi-hard one day old cheese with a dry matter of 533 g/kg, moisture on a fat-free basis (MFFB) of 626 g/kg and fat on a dry basis (FDB) value of 478 g/kg was made from the milk retentate produced with the ceramic module. The ripened cheese fulfilled the legal requirements of a traditionally produced semi-hard cheese with superb sensory qualities. Using the MF/UF/UF plant, a dry matter of 495 g/kg (MFFB 669 g/kg, FDB 493 g/kg) was achieved in a semi-hard cheese made from skim milk retentate. Our results suggest that by using a larger spacer distance in the last loop of the MF/UF/UF plant, combined with new hybrid technologies, semi-hard cheese production from full concentrate milk will soon become possible.     

Selective separation of copper (II) and cobalt (II) from wastewater by using continuous cross‐flow micellar‐enhanced ultrafiltration and surfactant recovery from metal micellar solutions

Performance of continuous cross‐flow micellar‐enhanced ultrafiltration (MEUF) method was investigated for the selective separation of copper (Cu²⁺) and cobalt (Co²⁺) from the aqueous phase using sodium dodecyl sulfate (SDS) as an anionic surfactant and iminodiacetic acid (IDA) as a chelating agent. Operating parameters such as operating time (10–120 min), cross‐flow rate (100–250 mL/min), pH of the solution (2.8–5.6), molar concentration ratio of the chelating agent to metals (the C/M ratio, 0.5–2.5), molar concentration ratio of the surfactant to metals (the S/M ratio, 5–8) and mode of operation were studied to investigate the effectiveness of the process on selective separation. At optimal parameters, above 90% selective separation (Cu²⁺ in permeate and Co²⁺ in retentate) was achieved. Two methods were studied for the separation of Co²⁺ and SDS from retentate stream; acidification followed by UF and addition of chelating agent followed by UF with surfactant recovery of 75% and 83%, respectively, and Co going into the permeate.     

In situ pultrusion of urea–formaldehyde matrix composites. I. Processability,kinetic analysis,and dynamic mechanical properties

We conducted a feasibility study on the pultrusion of a glass‐fiber‐reinforced urea–formaldehyde (UF) composite using a proprietary method. The UF prepolymer synthesized in this study was prepared from blends of UF monomer and a curing agent (NH₄Cl).The process feasibility, kinetic analysis, and dynamic mechanical properties of the glass‐fiber‐reinforced UF composites by pultrusion were investigated. From investigations of the long pot life of the UF prepolymer, the high reactivity of the UF prepolymer, and excellent fiber wet‐out, we found that the UF resin showed excellent process feasibility for pultrusion. A kinetic model, dα/dt = A exp(?E/RT)α^m(1 ? α)ⁿ, is proposed to describe the curing behavior of a UF resin. Kinetic parameters for the model were obtained from dynamic differential scanning calorimetry scans with a multiple‐regression technique. The dynamic storage modulus of the pultruded‐glass‐fiber‐reinforced UF composites increased with increasing die temperature, filler content and glass‐fiber content and with decreasing pulling rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1242–1251, 2002     

Effect of nonsolvent additives on PES ultrafiltration membrane pore structure

Different nonsolvent additives, namely, diethylene glycol, n-butyl alcohol (NBA), and ethylene glycol monomethyl ether, were added into the casting solution (polyethersulfone/dimethylformamide/lithium chloride) to prepare ultrafiltration (UF) membrane via phase inversion. The effects of different additives and their concentration on the pore structure of the prepared UF membrane were studied. The cross-sectional morphology of the membrane was observed via scanning electron microscopy. The addition of nonsolvent additives improved the large-cavity structure of the membrane. When the additive was low-content NBA (1–3 wt %), the membrane pore structure transformed from large-cavity structure to fully sponge-like structure. When the content of additive NBA was 3 wt %, the flux of the prepared UF membrane was 130.45 L (m⁻² h⁻¹), the rejection of PEG20000 was 95.54% and the flux remained high at 4 bar in long-term stability test. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47525.     

Intermittent ultrasound-assisted ceramic membrane fouling control in ultrafiltration

In this study, remediation of ceramic membrane fouling by an in-line intermittent ultrasound system was investigated. A piezoelectric ultrasonic transducer was integrated into a membrane unit that provided ultrafiltration (UF) of a diluted skim milk solution containing 0.10 wt% of protein. The effects of ultrasound at varied frequencies (20, 28, and 40 kHz) and power intensities (1.44, 2.88, and 5.76 W/cm²) under continuous operation and intermittent mode at various intervals (0.50, 1.0, 1.5, 2.0, 2.5, and 3.0 minutes) on membrane fouling were studied. The quality and flow rate of the permeate stream were monitored for the evaluation of the UF process performance. Optimal conditions of continuous ultrasound were found at 28 kHz and 2.88 W/cm². Moreover, at optimal ultrasonic conditions, the optimal intermittent time was found at 0.50 minute. At optimal ultrasonic conditions, the permeate amount increased by 79.8% and 94.2% for 0.50 minute intermittent ultrasound and continuous ultrasound, respectively, as compared with that of the UF process without ultrasound. Also, intermittent ultrasound induced better fouling control at a lower protein concentration of 0.05% by weight. The cleaning effect of ultrasound could be attributed to the cavitation bubbles generated by the rarefaction and pressure cycles of the applied ultrasound.     

The aminolysis of styrene–maleic anhydride copolymers for a new modifier used in urea-formaldehyde resins

Styrene (St) and maleic anhydride (MA) alternating copolymers with different molecular weights (MW) were synthesized via radical copolymerization. The copolymers were subsequently transferred into water-soluble maleic amic acid derivatives (SMAA) via the aminolysis of anhydride groups using (NH₄)₂CO₃ as the ammonia sources. The synthesized polymers were applied as a new kind of macromolecular modifier and added into the reaction system during the synthesis of urea-formaldehyde (UF) resins via the traditional alkaline–acidic–alkaline three-step process. The UF resins modified with SMAA were characterized using Fourier Transform Infrared Spectroscopy (FT-IR), ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy, and thermal gravimetric analysis (TGA). All the results confirmed the successful incorporation of SMAA chains into the crosslinking network of the UF resins. The modified UF resins were further employed as wood adhesives and the effect of synthesis parameters on their performance was investigated. Meanwhile, the influence of SMAA molecular weight (MW) on the properties of the modified UF resins was also studied. When the UF resins were synthesized with a low molar ratio of formaldehyde/urea (F/U) and a predetermined amount of SMAA added into the reaction system at the second step, plywood bonded using these modified UF resins showed much improved bonding strength (BS) and depressed formaldehyde emission. Moreover, the as-modified UF resins showed good storage characteristics.     

Study of hybrid isocyanate and high-mono-hydroxymethyl urea content urea-formaldehyde resins

Based on the difference in the reaction rate of different groups of urea-formaldehyde resins and isocyanate resins, this study designed two different urea-formaldehyde resins: a normal urea-formaldehyde resin (UF) and one with high mono-hydroxymethylurea content (UF*) to react with polymeric methylene diphenyl diisocyanate (pMDI) resin. The difference in mono- and di-hydroxymethyl urea content between UF and UF* resins was analyzed by nuclear magnetic resonance (NMR) spectroscopy, and results showed that the mono-hydroxymethyl urea content of the UF* resin was much higher than that of the conventional UF resin. The fourier transform infrared spectrometer (FTIR) analysis of differences between UF* and UF resin showed that the UF* process did not change the main structure of the conventional urea formaldehyde resin. Differential scanning calorimeter (DSC) analysis showed that the curing temperature of the hybrid UF*-pMDI resin was reduced 27.3°C compared to that of the UF-pMDI resin. When these hybrid resins were used to bond plywood respectively, test results showed that the UF*-pMDI resin improved the dry and wet bonding strength by 2.6% and 3.9%, respectively, compared with the UF-pMDI resin under the condition of hot pressing time (3 min) and temperature (140°C), meeting the requirement of Chinese standard of GB/T 9846–2015 for Class III board. This study provides a new path for further improving the performance and design of hybrid resins based on isocyanate and urea-formaldehyde resin.     

The effect of hydrolyzed soy protein isolate on the structure and biodegradability of urea–formaldehyde adhesives

The hydrolyzed soy protein isolate (HSPI) was used to partially substitute urea to synthesis modified urea–formaldehyde (UF) adhesives via copolymerization process, in order to reduce the dependency on petroleum-based chemicals and mitigate possible environmental pollution. The soy protein isolate (SPI), HSPI, and modified UF adhesives were characterized by attenuated total reflection Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), and thermo-gravimetric analysis (TGA). The bonding strength, adhesive properties, biodegradability, and micrographs of the UF and HSPI-modified UF after degradation were also measured. The results show that the SPI native structure is unfolded during the treatment with sodium hydroxide. The thermal stability of HSPI is better than SPI. HSPI can incorporate into the structure of cured UF adhesives with three different feeding methods. And the best bonding strength of modified UF adhesives is 1.31?MPa when HSPI is added at the first step. The formaldehyde emission of modified UF adhesives is lower compared with UF. The earlier the HSPI is added, the better the properties for modified UF adhesives can be obtained. The degradation rate of modified UF adhesives improved nearly two times compared to the UF after six months of degradation in biologically active soil. There are microorganisms adhering to the surface of modified UF from the SEM micrographs.     

Determination of formaldehyde/urea molar ratio in amino resins by near‐infrared spectroscopy

New processes for synthesis of urea‐formaldehyde (UF) and melamine‐fortified urea‐formaldehyde (mUF) resins have been developed in the last years, motivated by the current concerns about the effects of formaldehyde on human health. All these formulations are quite susceptible to possible operation error, which can significantly influence the characteristics of the final product. The main objective of this work was to implement chemometric techniques for off‐line monitoring of the product's formaldehyde/urea (F/U) molar ratio using near infrared (NIR) spectroscopy. This allows the timely implementation of the necessary corrections in case the product is off‐specification. Calibration models for F/U molar ratio were developed taking into account the most relevant spectral regions for these resins, individually or in combination (7502–6098 cm^?1 and 5000–4246 cm^?1) and using different preprocessing methods. When the appropriate spectral range and preprocessing methods are selected, it is possible to obtain calibration models with high correlation values for these resins. The best preprocessing methods were identified for three cases: UF resin (produced by strongly‐acid process), mUF resin (alkaline‐acid process), and a combined model that involves both UF and mUF resins. It was concluded that significantly better accuracy is obtained when a new model is developed for each particular resin system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Differential scanning calorimetry characterization of urea–formaldehyde resin curing behavior as affected by less desirable wood material and catalyst content

Differential scanning calorimetry was applied to investigate the curing behavior of urea–formaldehyde (UF) resin as affected by the catalyst content and several less desirable wood materials (e.g., wood barks, tops, and commercial thinnings). The results indicate that the reaction enthalpy of UF resin increased with increasing catalyst content. The activation energy and peak temperature of the curing UF resin generally decreased with increasing catalyst content at lower levels of catalyst content. However, with further increases in catalyst content, the changes in the activation energy and peak temperature were very limited to nonexistent. The hydrolysis reaction of the cured UF resin occurred during the latter stages of the curing process at both lower level (<0.2%) and higher level (>0.7%) catalyst contents. This indicates that there existed an optimal range of catalyst content for the UF resin. The curing enthalpy of the UF resin decreased with increasing wood raw materials present due to the effect of diffusion induced by the wood materials and the changes in the phase of the curing systems. This suggests that the curing reactions reached a lower final degree of conversion for the wood–resin mixtures than for the UF resin alone. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2027–2032, 2005     

Influence of acrylamide copolymerization of urea–formaldehyde resin adhesives to their chemical structure and performance

To lower the formaldehyde emission of wood‐based composite panels bonded with urea–formaldehyde (UF) resin adhesive, this study investigated the influence of acrylamide copolymerization of UF resin adhesives to their chemical structure and performance such as formaldehyde emission, adhesion strength, and mechanical properties of plywood. The acrylamide‐copolymerized UF resin adhesives dramatically reduced the formaldehyde emission of plywood. The ¹³C‐NMR spectra indicated that the acrylamide has been copolymerized by reacting with either methylene glycol remained or methylol group of UF resin, which subsequently contributed in lowering the formaldehyde emission. In addition, an optimum level for the acrylamide for the copolymerization of UF resin adhesives was determined as 1%, when the formaldehyde emission and adhesion strength of plywood were taken into consideration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Sulfonated poly(ether ether ketone)‐induced porous poly(ether sulfone) blend membranes for the separation of proteins and metal ions

Asymmetric ultrafiltration (UF) membranes were prepared by the blending of poly(ether sulfone) (PES) and sulfonated poly(ether ether ketone) (SPEEK) polymers with N,N′‐dimethylformamide solvent by the phase‐inversion method. SPEEK was selected as the hydrophilic polymer in a blend with different composition of PES and SPEEK. The solution‐cast PES/SPEEK blend membranes were homogeneous for all of the studied compositions from 100/0 to 60/40 wt % in a total of 17.5 wt % polymer and 82.5 wt % solvent. The presence of SPEEK beyond 40 wt % in the casting solution did not form membranes. The prepared membranes were characterized for their UF performances, such as pure water flux, water content, porosity, and membrane hydraulic resistance, and morphology and melting temperature. We estimated that the pure water flux of the PES/SPEEK blend membranes increased from 17.3 to 85.6 L m^?2 h^?1 when the concentration of SPEEK increased from 0 to 40 wt % in the casting solution. The membranes were also characterized their separation performance with proteins and metal‐ion solutions. The results indicate significant improvement in the performance characteristics of the blend membranes with the addition of SPEEK. In particular, the rejection of proteins and metal ions was marginally decreased, whereas the permeate flux was radically improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of nano ZnO toughed phenol–urea-formaldehyde foam

Urea formaldehyde (UF) and phenol formaldehyde (PF) foam possess outstanding flame-retardant properties, excellent insulation, and low thermal conductivity. These properties make them suitable for thermal insulation in buildings. However, the mechanical properties still need to be improved. In this study, orthogonal test was designed to optimize the level components of PF/UF composite foam first, then nano ZnO was added to the PF/UF composite foam to improve its toughness. The effects of nano ZnO on the morphology, apparent density, pulverization rate, thermal conductivity and thermal degradation property, flame retardancy, and mechanical properties of the ZnO/PF/UF nanocomposite foam were studied. The addition of nano ZnO improved the bending and compressive strength and decreased the pulverization rate of the composite foam significantly. The ZnO/PF/UF nanocomposite foam also presented better flame retardant properties than PF/UF composite foam. The largest oxygen index values of ZnO/PF/UF nanocomposite foam could reach 39.31%, while the thermal conductivity and the maximum rate of weight loss temperature were increased to 0.036 W/(m∙K) and 279°C, respectively. Moreover, ZnO/PF/UF nanocomposite foam showed low apparent density property (0.27 g/cm³).     

Study of glycidyl ether as a new kind of modifier for urea‐formaldehyde wood adhesives

In this work, the multiepoxy functional glycidyl ether (GE) modified urea‐formaldehyde (UF) resins were synthesized via a traditional alkaline‐acid process under low formaldehyde/urea (F/U) molar ratio. The synthesized resins were characterized by ¹³C magnetic resonance spectroscopy (¹³C‐NMR), indicating that GE can effectively react with UF resins via the ring‐opening reaction of epoxy groups. Moreover, the residual epoxy groups of GE could also participate in the curing reaction of UF resins, which was verified by Fourier transform infrared spectroscopy. The storage stability of GE‐modified UF resins and the thermal degradation behavior of the synthesized resins were evaluated by using optical microrheology and thermogravimetric analysis, respectively. Meanwhile, the synthesized resins were further employed to prepare the plywood with the veneers glued. For the modification on bonding strength and formaldehyde emission of the plywood, the influences of addition method, type, and amount of GE were systematically investigated. The performance of UF adhesives were remarkably improved by the modification of GE around 20–30% (weight percentage of total urea) in the acidic condensation stage during the resin synthesis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improvement of storage stability of UF resins by adding caprolactam

During storage, the structure of urea-formaldehyde (UF) resins suffers modifications due to reactions between monomers, oligomers, polymer and free formaldehyde, leading to increase in viscosity and decrease in pH. Eventually, viscosity reaches a value that renders the resin unusable, and it must be disposed off. This aging process is accelerated if storage temperature increases.The aim of this work is to obtain UF resins with long storage stability, even when exposed to relatively high temperatures, such as 40 °C. The main strategy adopted was the addition of a chain growth blocker, caprolactam. This monofunctional compound reacts with end groups, blocking them and therefore reducing the polymer's reactivity. In addition, a weak base was added to adjust the pH value, instead of the traditional strong base, sodium hydroxide, therefore hindering the Cannizzaro reaction.The storage stability of UF resins with formaldehyde to urea molar ratio of 1.6–2.0 was monitored by pH and viscosity measurements. Caprolactam was added in different amounts and at different reaction stages. It was found that 10% addition at the beginning of condensation led to the best results, giving a much higher storage stability at 40 °C (2 months when compared to 4 days for a commercial UF resin with low F/U molar ratio). As expected, the resin reactivity decreased with caprolactam addition, demanding for longer pressing times for wood-based panel manufacture. These verified the internal bond strength specification for EN 312 - P2 standard class. Formaldehyde content in the panels was above the E1 class limit when fresh or one month old modified resins were used, implying addition of formaldehyde scavengers. The resin stored for 2 months allowed producing panels within E1 limit. These preliminary results demonstrate the concept that addition of an end-group blocker during UF synthesis is an effective strategy for improving storage stability, encouraging future work on alternative compounds and synthesis conditions optimization.     

Integration of immersed membrane ultrafiltration with the reuse of PAC and alum sludge (RPAS) process for drinking water treatment

Effects of PAC and alum sludge generated from water treatment process on the effluent quality and fouling of immersed UF membrane were systematically investigated with representative source of natural water and the efficiency of coagulation, PAC adsorption and RPAS to treat natural surface water prior to UF were compared. It was found that the average turbidity removal by RPAS could reach up to 80.2%, and the turbidity removal of immersed membrane UF was independent of the influent, which could be kept at 99%. Particulates were reduced after being pre-treated by different processes, and particles with sizes ranging from 0.5 to 3.5 μm and larger than 13.5 μm were effectively removed by RPAS. UF coupled with RPAS pre-treatment got the best removal for DOM compared to other processes with average DOC and UV₂₅₄ removal 54.1% and 47.2% due to the high removal in the influent of UF. The residual alum content in the effluent of RPAS with UF was less than coagulation and bacteria were almost all removed by membrane. The membrane-fouling was mitigated by pre-treatment processes at different degrees, TMP of UF coupled with RPAS process was relatively stable in 15 d of run, the adsorption of PAC and large number of Al(OH)₃ complexes and precipitates for the foulant molecules might be an important mechanism.     

茶叶废料在脲醛树脂中的应用研究

将不同颗粒度的茶叶废料粉添加到脲醛树脂胶中,研究了茶叶废料的颗粒度、加入量等对脲醛树脂胶黏剂的游离甲醛含量、黏接胶合板的甲醛释放量及胶合强度的影响。实验结果表明,茶叶废料作为填料添加到脲醛树脂胶黏剂中,能够降低其游离甲醛含量以及其黏接胶合板的甲醛释放量;茶叶废料颗粒度越小,与脲醛树脂混合性越好,消除甲醛效果越显著;茶叶废料的适量加入不会降低胶合板胶合强度。     

Preparation and characterization of a poly(vinyl alcohol)/tetraethoxysilane ultrafiltration membrane by a sol–gel method

Using poly(vinyl alcohol) (PVA) with highly hydrophilic properties as membrane material and poly(ethylene glycol) (PEG) as an additive, we prepared PVA/tetraethoxysilane (TEOS) ultrafiltration (UF) membranes with good antifouling properties by a sol–gel method. The PVA/TEOS UF membranes were characterized by X‐ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron microscopy, and static contact angle of measurement of water. The hybridization of TEOS to PVA for preparing the PVA/TEOS UF membranes achieved the required permeation performance and good antifouling behaviors. The morphology and permeation performance of the PVA/TEOS membranes varied with the different TEOS loadings and PEG contents. The pure water fluxes (J_W) increased and the rejections (Rs) decreased with increasing TEOS loading and PEG content. The PVA/TEOS UF membrane with a PVA/TEOS/PEG/H₂O composition mass ratio of 10/3/4/83 in the dope solution had a J_W of 66.5 L m^?2 h^?1 and an R of 60.3% when we filtered it with 300 ppm of bovine serum albumin aqueous solution at an operational pressure difference of 0.1 MPa. In addition, the filtration and backwashing experiment proved that the PVA/TEOS membranes possessed good long‐term antifouling abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4066–4074, 2013     

Ultrafiltration Based Process for the Recovery of Polysaccharides and Polyphenols from Winery Effluents

Winery effluents have a high pollution potential, especially those effluents that are obtained from the second racking. However, these effluents are rich in phenolic compounds and polysaccharides and can be potential sources for the recovery of these compounds. Therefore, a process was developed in this study to reduce the pollution potential of the winery effluents from the second racking and to recover the polyphenols and polysaccharides from the effluents by utilizing ultrafiltration (UF) and sedimentation operations. The sedimentation was optimized by varying the pH from 3.8 to 8.0, while the UF experiments were optimized by varying the transmembrane pressure from 0.5 to 4.0 bar and the feed circulation velocity from 0.44 to 0.87 ms^?1. This process provided a permeate stream with a reduction in the TOC content by 56.6%, while the polyphenols and the polysaccharides in the concentrate stream were concentrated by 6 times and 5 times, respectively.     

Intercalation structure and toughening mechanism of graphene/urea‐formaldehyde nanocomposites prepared via in situ polymerization

Based on the industrialized graphene (GN) product, a series of graphene/urea‐formaldehyde nanocomposites were synthesized via in situ polymerization by incorporation of silicon coupling agent with terminal amino groups (SA) as the compatibilizer. The results showed that addition of SA coupling agent led to much more efficient grafting of UF molecules on the GN surface with high layer thickness by formation of hydrogen bonding, and thus complete exfoliation and uniform dispersion of GN were achieved for the composites. Compared with neat UF, the addition of 1.0 wt% GN resulted in a roughly 25% increase in tensile strength and 12% increase in impact strength; meanwhile the impact fracture surfaces of the composite showed obvious ductile fracture characteristics, indicating the reinforcing and toughening effect of GN on the UF matrix. With increasing GN content, the storage modulus, glass transition temperature and crosslinking density of UF increased, while the tan δ_max decreased, suggesting that a double crosslinking network structure with GN centered crosslinking point and chemical crosslinking point of UF molecular chains formed, leading to improvement in the stiffness of the composites. The present work showed promising potential for developing high performance UF resin on an industrial scale. © 2017 Society of Chemical Industry