Removal of phosphate with a polyacrylonitrile composite functionalized by a metal organic framework-enhanced layered double hydroxide.

Excessive phosphorus causes eutrophication problems. The adsorptive removal of phosphate is prevalent and practical in large-scale applications, such as column adsorption. A metal organic framework (MOF)-enhanced layered double hydroxide (LDH) adsorbent material was developed and studied for batch adsorption and then combined with polyacrylonitrile (PAN) to form MOF/LDH/PAN composite beads working as a functional material for columns. Scanning electron microscopy (SEM) images showed the well-dispersed adsorbent powder in porous composite beads. The Fowler-Guggenheim isotherm model described the phosphate adsorption behavior of the MOF/LDH powder with a maximum capacity of 74.96 mg P/g. Mass transfer in the composite beads was successfully described with the Fickian diffusion model. The composite-packed fixed bed treated 37.95 BVs of the influent (55.51 mg P/L phosphate solution) and achieved an uptake of 18.92 mg P/g, with a removal efficiency of 96.42%, before the breakthrough point in the column study. The phosphate-loaded composite bed was regenerated with 0.1 M NaOH to 70% efficiency within 30 BVs. The polymer composite can be considered a practical solution for adsorption-based water treatment applications in tank and column processes where powder adsorbents cannot be applied.

Effects of Anthocyanin Extracts from Bilberry (Vaccinium myrtillus L.) and Purple Potato (Solanum tuberosum L. var. 'Synkeä Sakari') on the Plasma Metabolomic Profile of Zucker Diabetic Fatty Rats.

This study compared the effects of the nonacylated and acylated anthocyanin-rich extracts on plasma metabolic profiles of Zucker diabetic fatty rats. The rats were fed with the nonacylated anthocyanin extract from bilberries (NAAB) or the acylated anthocyanin extract from purple potatoes (AAPP) at daily doses of 25 and 50 mg/kg body weight for 8 weeks. 1H NMR metabolomics was used to study the changes in plasma metabolites. A reduced fasting plasma glucose level was seen in all anthocyanin-fed groups, especially in the groups fed with NAAB. Both NAAB and AAPP decreased the levels of branched-chain amino acids and improved lipid profiles. AAPP increased the glutamine/glutamate ratio and decreased the levels of glycerol and metabolites involved in glycolysis, suggesting improved insulin sensitivity, gluconeogenesis, and glycolysis. AAPP decreased the hepatic TBC1D1 and G6PC messenger RNA level, suggesting regulation of gluconeogenesis and lipogenesis. This study indicated that AAPP and NAAB affected the plasma metabolic profile of diabetic rats differently.

Anthocyanin-rich extract from purple potatoes decreases postprandial glycemic response and affects inflammation markers in healthy men.

Our recent clinical study suggested that polyphenol-rich purple potatoes lowered postprandial glycemia and insulinemia compared to yellow potatoes. Here, 17 healthy male volunteers consumed yellow potatoes with or without purple potato extract (PPE, extracted with water/ethanol/acetic acid) rich in acylated anthocyanins (152 mg) and other phenolics (140 mg) in a randomized cross-over trial. Ethanol-free PPE decreased the incremental area under the curve for glucose (p = 0.019) and insulin (p = 0.015) until 120 min after the meal, glucose at 20 min (p = 0.015) and 40 min (p = 0.004), and insulin at 20 min (p = 0.003), 40 min (p = 0.004) and 60 min (p = 0.005) after the meal. PPE affected some of the studied 90 inflammation markers after meal; for example insulin-like hormone FGF-19 levels were elevated at 240 min (p = 0.001). These results indicate that PPE alleviates postprandial glycemia and insulinemia, and affects postprandial inflammation.

Chromatographic Recovery of Monosaccharides and Lignin from Lignocellulosic Hydrolysates.

The chromatographic recovery of monosaccharides and lignin from lignocellulosic hydrolysates was studied at laboratory and pilot scale. A weak cation-exchange resin in sodium form and a water eluent gave good separation efficiency. Scale-dependent phenomena, especially viscous fingering resulting from the large viscosity and density differences between the hydrolysate feed and eluent, were observed. The issue was resolved in the pilot scale with appropriate selection of the flow direction, and a high productivity was achieved at 95 % recovery yield. The pH value of the feed was found to have no effect on the actual separation; however, the resin was significantly less colored at a higher pH value.

Sensory profile of ethyl ß-d-glucopyranoside and its contribution to quality of sea buckthorn (Hippophaë rhamnoides L.).

The contribution of ethyl ß-d-glucopyranoside (EG) to sensory profile of sea buckthorn (Hippophaë rhamnoides ssp. rhamnoides) was studied. The content of natural existing EG varied between 0.6 and 19.8g/L in the sea buckthorn studied. The taste threshold of pure EG was estimated in water solution as 1.1±1.3g/L, and the suprathreshold aqueous EG solution (5.0g/L) was perceived mainly as bitter. In aqueous sugar-acid mixtures, acids were the major contributors to sourness and astringency, whereas the added EG or sugars showed little impact on the overall sensory profile. EG addition increased the bitterness of sea buckthorn juice. The sensory profiles of the juices were dominated by intense sourness correlating with the malic acid content. The bitterness of the juices correlated with the EG content as well as the ratios EG/acids and EG/sugars. EG content shall be considered when selecting raw materials for industrial processing.

Robustness of steady state recycling chromatography with an integrated solvent removal unit.

The robustness of a hybrid separation process where the performance of mixed-recycle steady state recycling chromatography is enhanced by integrating it with a solvent removal unit is analysed theoretically and by means of numerical simulations. The equilibrium theory of chromatography is applied to derive equations for boundaries of feasible operating parameters in such a hybrid process. Visualization of the feasible operating parameter ranges helps in analysing the influence of various physical and process parameters of robustness of an operating point. It is observed that process robustness can be improved by adjusting the solvent removal capacity or the cut times. When the solvent removal capacity increases, the region of feasible cut times becomes narrower due to increased non-linearity of the system. This makes it more difficult to maintain robust operation.

Effect of template ion-ligand complex stoichiometry on selectivity of ion-imprinted polymers.

In order to highlight the importance of the complex stoichiometry during ion imprinted polymer (IIP) synthesis, we investigated the effect of the complex structure on IIPs selectivity by adjusting the complex stoichiometry before polymerization. 2-(aminomethyl)pyridine monomer (amp) was chosen as a functionalized ligand for nickel(II) ions and a polymerizable vinylbenzyl derivative (Vbamp) was prepared. Complex formation was studied by varying the nickel/Vbamp ratio and recording absorption spectra of the complexes at the polymerization conditions. Using a least-squares minimization scheme, the complex species distribution was successfully established. From these results, it was possible to choose the metal/ligand stoichiometry in the complex (1:1; 1:2 or 1:3) by adjusting the initial metal/ligand ratio. IIPs were then prepared by inverse suspension copolymerization of Vbamp with ethyleneglycol dimethacrylate (EDMA). Highly porous particles with good nickel binding capacity and good Ni/Zn selectivity even at acidic conditions were obtained. Equilibrium uptake of Ni(II) at pH 7 ranged from 0.12 to 0.2 mmol g(-1) and relative selective coefficient was as high as 260 for the IIP prepared using the Ni(Vbamp)2 complex.

Evolutionary multi-objective optimization based comparison of multi-column chromatographic separation processes for a ternary separation.

Performance characteristics of two advanced multi-column chromatographic separation processes with discontinuous feed, Multi-Column Recycling Chromatogrphy (MCRC) and Japan Organo (JO), were investigated for a ternary separation using multi-objective optimization with an evolutionary algorithm. Conventional batch process was used as a reference. Fractionation of a concentrated acid hydrolysate of wood biomass into sulfuric acid, monosaccharide, and acetic acid fractions was used as a model system. Comparison of the separation processes was based on selected performance parameters in their optimized states. Flow rates and step durations were taken as decision variables whereas the column configuration and dimensions were fixed. The MCRC process was found to be considerably more efficient than the other processes with respect to eluent consumption. The batch process gave the highest productivity and the JO process the lowest. Both of the multi-column processes gave significantly higher monosaccharide yield than the batch process. When eluent consumption and monosaccharide yield are taken into account together with productivity, the MCRC process was found to be the most efficient in the studied case.

Steady state recycling chromatography with solvent removal-effect of solvent removal constraints on process operation under ideal conditions.

Steady state recycling chromatography (SSR) offers a means to reduce eluent consumption and increase productivity in preparative and production scale chromatographic separations. Even better performance is obtained with an integrated process by coupling solvent removal unit to the chromatographic separation unit. Here a design method for SSR with an integrated solvent removal unit (SSR-SR) is presented. The method is more practical than previous work as the effect of physical constraints, such as solubility or viscosity, imposed on the amount of solvent removed is included. The method holds under ideal conditions for binary systems with competitive Langmuir isotherm model. The design equations allow calculation of the regions of feasible operating parameters when either the maximum concentrations in the solvent removal unit or of the solution fed into the chromatographic column is restricted. The method was applied to analyze the performance of different SSR-SR configurations in two case studies: the separation of mandelic acid enantiomers and the separation of EMD 53986 enantiomers. The benefits of SSR-SR are relatively small under ideal conditions but the design method developed here can give a good starting point for designing SSR-SR processes under non-ideal conditions.

Enhanced membrane filtration of wood hydrolysates for hemicelluloses recovery by pretreatment with polymeric adsorbents.

In this study adsorption of foulants from birch and pine/eucalyptus wood hydrolysates on two polymeric adsorbents was studied aiming to reduce the membrane fouling. The effect of the pretreatment of hydrolysate on polyethersulphone membrane performance was studied in dead-end filtration experiments. Adsorption pretreatment improved significantly filtration capacity and decreased membrane fouling. Especially high-molecular weight lignin was efficiently removed. A multistep adsorption pretreatment was found to reduce the amount of adsorbent required. While large adsorbent amount was shown to increase flux in filtration, it was found also to cause significant hemicellulose losses.

Design of batch chromatography for separation of binary mixtures under reduced purity requirements.

Two methods are presented for designing separation of binary mixtures in a batch chromatography column under reduced purity requirements such that no waste or recycle fractions are generated. The first one is based on the equilibrium theory of chromatography and requires adsorption isotherm parameters. The second one is a shortcut method that uses a single experimental or simulated design chromatogram as input and is recommended under strongly non-ideal conditions with significant dispersive effects. Both approaches allow prediction of the injection volume and the cut position that lead to given target purities. In principle, they apply for all systems with convex or concave isotherms. The applicability of the design methods is evaluated by using numerical simulations. Both design methods work the better the higher the column efficiency and the lower the purity constraints are.

Production and recovery of monosaccharides from lignocellulose hot water extracts in a pulp mill biorefinery.

Processing of hemicelluloses obtained with pressurized hot water extraction (PHWE) from Scots pine to monosaccharides and other chemicals was investigated experimentally. A process scheme consisting of ultrafiltration, acid hydrolysis, and chromatographic separation was proposed and evaluated. A two-stage ultrafiltration was found necessary for efficient fractionation of the wood extract. It was shown that the monosaccharides can be released from a concentrated hemicellulose fraction with sulfuric acid hydrolysis without a significant loss of yield due to decomposition of monosaccharides. Acid hydrolysate was successfully fractionated with ion exchange chromatography and the hydrolysis acid was recovered for reuse. The product fractions obtained include polyphenols and high molar mass hemicelluloses (from UF stage 1), arabinose (from UF stage 2), as well as acetic acid and a mixture of monosaccharides (xylose, galactose, mannose, glucose) from chromatography.

Steady state recycling chromatography with an integrated solvent removal unit - separation of glucose and galactose.

A process concept where a solvent removal unit is integrated to a steady-state recycling chromatography process (SSR-SR) offers a possibility to significantly increase the performance of single column chromatographic separation. The advantages of solvent removal for a difficult separation task at conditions typical for industrial scale chromatography were demonstrated by investigating the performance of SSR-SR in separation of glucose and galactose. Two limits for the extent of solvent removal were imposed: maximum total concentration of the solution fed into the column (viscosity limit) and the maximum total concentration achievable in the solvent removal unit (solubility or osmotic pressure limit). The process was optimized using numerical simulation. Three SSR-SR configurations with different positions of the solvent removal unit were compared with (1) the conventional batch process, (2) SSR without solvent removal, and (3) batch process with solvent removal. SSR-SR was found to always improve the productivity. In addition, solvent removal reduced eluent consumption in most cases. The concentration limits and the concentration of the fresh feed were shown to determine which SSR-SR configuration yields the best performance.

Bypass chromatography--design and analysis of an improved strategy for operating batch chromatography processes.

The possibility to improve the performance of batch chromatographic separations by using so-called bypass method is analyzed for the first time. In bypass chromatography, only a part of the feed is introduced into the column and purified to purity larger than the desired value. The resulting fractions are then blended with fresh feed to match the given purity constraints. A general approach is presented for designing bypass batch chromatography. Analytical design equations, based on equilibrium theory of chromatography, are presented for the case of binary systems with linear or competitive Langmuir adsorption isotherms under ideal conditions. The approach allows direct calculation of optimal loading and amount of bypass so that arbitrary purity requirements are satisfied without waste streams. It is shown that the bypass strategy enhances productivity of batch chromatography without an increase in the eluent consumption. In the case of a Langmuir isotherm, maximum productivity and minimum eluent consumption are always obtained when the less retained component is collected from the column at 100% purity. In contrast, the optimal purity of the second fraction from the column is typically less than 100% and depends on the purity constraint of the more retained component. In the case of linear isotherms, operation with touching bands is preferred.

Explicit equations for the height and position of the first component shock for binary mixtures with competitive Langmuir isotherms under ideal conditions.

Explicit equations for the height c(1)(S) and retention time t(R,1) of the pure first component shock in the case of a narrow rectangular injection pulse of a binary mixture with competitive Langmuir isotherms were derived within the frame of the equilibrium theory. The height of the first shock is obtained as an only positive root of a quartic equation. Hence, it was shown that, for binary Langmuir systems, the individual concentration profiles at the column outlet can be expressed entirely in closed-form. In addition, a novel, simple parametric representation that gives the trajectory of the first shock in the distance-time diagram as a function of c(1)(S) was derived. The practical relevance of the new equations was demonstrated by utilizing them for optimization of batch chromatography. It was shown that c(1)(S) increases and t(R,1) decreases with increasing duration of injection for given feed concentrations when the pure first component plateau is eroded during elution. The derivative of the cycle time with respect to the duration of injection is always more than unity. For this reason, the maximum productivity of more retained component is obtained when the duration of injection is selected so that the purity constraint can be fulfilled by having 100% yield. For the less retained component, an implicit expression for the maximum productivity was derived. When the injected loadings are constant, t(R,1) decreases with increasing feed concentrations while c(1)(S) and the cycle time are independent of them. In addition, the productivities of both components always increase with increasing feed concentrations.

Adsorptive removal of fermentation inhibitors from concentrated acid hydrolyzates of lignocellulosic biomass.

Adsorptive purification of concentrated acid hydrolyzate of lignocellulose was investigated. Cation exchange resin (CS16GC), neutral polymer adsorbent (XAD-16), and granulated activated carbon (GAC) were studied to remove furfural, HMF, and acetic acid from a synthetic hydrolyzate containing 20 wt.% H(2)SO(4). Adsorption isotherms were determined experimentally. Loading and regeneration were investigated in a laboratory scale column. GAC has the highest adsorption capacity, but regeneration with water was not feasible. XAD-16 and CS16GC had lower adsorption capacities but also shorter cycle times due to easier regeneration. Productivity increased when regenerating with 50 wt.% EtOH(aq) solution. To compare adsorbents, process performance was quantified by productivity and fraction of inhibitors removed. GAC yields highest performance when high purity is required and ethanol can be used in regeneration. For lower purities, XAD-16 and GAC yield approximately equal performance. When using ethanol must be avoided, CS16GC offers highest productivity.

Co-eluent effect in partition chromatography. Rhamnose-xylose separation with strong and weak cation-exchangers in aqueous ethanol.

The effect of ethanol in aqueous eluent on the chromatographic separation was studied at 298 K. Two sugars, L-rhamnose and D-xylose, were separated by using strong and weak cation-exchangers as a stationary phase. The ionic form of the resins was Na+ or Ca2+. The separations were carried out with sugar feed concentrations up to 35 wt% and with both low (about 1%) and high (about 10%) feed volume to bed volume ratios. The separation of the sugars was improved by adding ethanol into the eluent. The separation was also significantly enhanced when the weak cation-exchangers with the greatest affinity for water were used instead of strong cation-exchangers as a separation medium for the sugars having different hydrophilicities. The experimental data were successfully explained with a rate-based column model, which accounted for the volume changes of the stationary phase. A thermodynamic sorption model was utilized in column calculations.