Sustainable biopolymer synthesis via superstructure and multiobjective optimization

Sustainable polymers derived from biomass have great potential to replace petrochemical based polymers and fulfill the ever‐increasing market demand. To facilitate their industrialization, in this research, a comprehensive superstructure reaction network comprising a large number of reaction pathways from biomass to both commercialized and newly proposed polymers is constructed. To consider economic performance and environmental impact simultaneously, both process profit and green chemistry metrics are embedded into the multiobjective optimization framework, and MINLP is used to enable the effective selection of promising biopolymer candidates. Through this proposed approach, this study identifies the best biopolymer candidates and their most profitable and environmentally friendly synthesis routes under different scenarios. Moreover, the stability of optimization results regarding the price of raw materials and polymers and the effect of process scale on the investment cost are discussed in detail. These results, therefore, pave the way for future research on the production of sustainable biopolymers. © 2017 American Institute of Chemical Engineers AIChE J, 63: 91–103, 2018     

Performance analysis of integrated biomass gasification fuel cell (BGFC) and biomass gasification combined cycle (BGCC) systems

Biomass gasification processes are more commonly integrated to gas turbine based combined heat and power (CHP) generation systems. However, efficiency can be greatly enhanced by the use of more advanced power generation technology such as solid oxide fuel cells (SOFC). The key objective of this work is to develop systematic site-wide process integration strategies, based on detailed process simulation in Aspen Plus, in view to improve heat recovery including waste heat, energy efficiency and cleaner operation, of biomass gasification fuel cell (BGFC) systems. The BGFC system considers integration of the exhaust gas as a source of steam and unreacted fuel from the SOFC to the steam gasifier, utilising biomass volatilised gases and tars, which is separately carried out from the combustion of the remaining char of the biomass in the presence of depleted air from the SOFC. The high grade process heat is utilised into direct heating of the process streams, e.g. heating of the syngas feed to the SOFC after cooling, condensation and ultra-cleaning with the Rectisol^® process, using the hot product gas from the steam gasifier and heating of air to the SOFC using exhaust gas from the char combustor. The medium to low grade process heat is extracted into excess steam and hot water generation from the BGFC site. This study presents a comprehensive comparison of energetic and emission performances between BGFC and biomass gasification combined cycle (BGCC) systems, based on a 4th generation biomass waste resource, straws. The former integrated system provides as much as twice the power, than the latter. Furthermore, the performance of the integrated BGFC system is thoroughly analysed for a range of power generations, ～100–997 kW. Increasing power generation from a BGFC system decreases its power generation efficiency (69–63%), while increasing CHP generation efficiency (80–85%).     

Preparation of hydrophilic polysulfone membrane using polyacrylic acid with polyvinyl pyrrolidone

This study examined the consequences of the addition of polyvinyl pyrrolidone (PVP) of different molecular weights with constant molecular weight of polyacrylic acid (PAA) on the morphology and permeation properties of polysulfone (PSF) membranes. The asymmetric polymeric membranes were prepared by phase inversion process using PSF in N‐methyl‐2‐pyrrolidone (NMP) as a solvent. The surface structure and morphology of the prepared membranes were analyzed by field‐emission scanning electron microscope (FESEM) and atomic force microscopy (AFM). The pore number, average pore size and area of pores for all the membranes were determined by permeability method. These ultrafiltration membranes were subjected to characterizations such as measurement of pure water flux (PWF), compaction factor (CF), bovine serum albumin (BSA) rejection for finding the permeability performance, whereas equilibrium water content, contact angle, porosity, hydraulic resistance, and ion exchange capacity (IEC) are measured for evaluating the hydrophilicity. Results demonstrate that the flux performance of the membranes and morphological parameters own a crucial inter‐relationship with the molecular weight of PVP. The membrane pore area and pore number were found to be increased by increasing molecular weight of PVP with constant molecular weight of PAA. A detailed comparative study was done with Chakrabarty et al. (J. Membr. Sci. 2008, 309, 209) and found better in almost all the aspects. All the resulting parameters were compared and concluded with the fact that addition of small amount of PAA in PSF/PVP/NMP casting solution can be better than addition of PVP alone. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41964.     

Adsorptive removal kinetics of anionic dye onto chitosan films doped with graphene oxide: An in situ fluorescence monitoring

The aqueous adsorption of a fluorescent dye (pyranine) onto crosslinked chitosan-graphene oxide composite films was studied. In situ fluorescence monitoring technique is introduced as easy and fast experimental technique to select optimal adsorbent conditions. The effect of ionic crosslinker on adsorption was studied with sodium tripolyphosphate, trisodium citrate, and sodium sulfate, respectively. Among the crosslinkers, it was realized that sodium sulfate crosslinked films showed a greater adsorption rate for pyranine than the other two types of crosslinked films. Recently, graphene oxide is of interest as a filler compound for many biopolymer applications due to its favorable thermal, mechanical and surficial properties. In the present study, graphene oxide incorporation increased adsorption rate of the dye and the mechanical strength of ionically crosslinked chitosan films. The adsorption behavior of the adsorbent was explained by a kinetic model. Samples were characterized using scanning electron microscopy, thermogravimetric analysis, swelling experiments and tensile testing method.     

Evolution of a Nanocrystalline (Co,Ni)Al2O4 Spinel Phase from Quasicrystalline Precursor

This work reports on the synthesis of a spinel phase from a thermodynamically stable decagonal quasicrystalline Al₇₀Co₁₅Ni₁₅ alloy. The Al₇₀Co₁₅Ni₁₅ alloy, synthesized through slow cooling of the molten alloy, was subjected to milling in an attritor ball mill at 400 rpm for 5, 10, 20, 30, and 40 h with a ball to powder ratio of 20:1 in the hexane medium. The differential thermal analysis, X-ray diffraction, scanning, and transmission electron microscopy techniques have been used for characterization of milled as well as annealed powders. The Voigt function analysis has been used for calculation of the effective crystallite size and relative strain of ball-milled samples. The crystallite size has been found to be ∼14 nm after 40 h of milling along with a lattice strain of 8.1%. The annealing experiments have been carried out under two different conditions: (i) in vacuum and (ii) in air. The results of the present investigation clearly revealed that the nano-decagonal phase was stable in vacuum while annealing at 600°C for 40 h. However, during annealing under a similar condition in air, the formation of a nanospinel of (Ni,Co)Al₂O₄ of size ∼60 nm was identified. The possible structural evolution of the spinel from the quasicrystalline phase has been discussed.     

Calculating minimum energy urban layouts with mathematical programming and Monte Carlo analysis techniques

Cities consume significant amounts of energy and improving their efficiency is an integral part of tackling global climate change. As existing urban layouts can be difficult to change, new developments offer significant opportunities for demonstrating low energy urban forms. However the limits of these improvements are not well known and so this paper presents an optimization tool for designing minimum energy urban layouts, considering both the transport and building sectors. Our work builds upon the excess commuting and sketch modelling literatures, with a greater focus on energy consumption as a specific objective and improved model performance. After validating the model with the case of a UK eco-town, Monte Carlo analysis is used to assess how the minimum energy benchmark varies in response to planning constraints on high-density housing and car ownership. The methodology presented here therefore offers a new tool for calculating absolute minimum urban energy benchmarks, which can be used early in the planning process to complement more behaviourally-realistic land-use transportation models.     

Antibody purification using porous metal–chelated monolithic columns

A novel monolithic material was developed to obtain efficient and cost‐effective purification of IgG from human plasma. The porous monolith was obtained by bulk polymerization in a glass tube of 2‐hydroxyethyl methacrylate (HEMA) and N‐methacryloyl‐(L )‐histidine methyl ester (MAH). The poly(HEMA‐MAH) monolith had a specific surface area of 214.6 m²/g and was characterized by swelling studies, porosity measurement, FTIR, scanning electron microscopy, and elemental analysis. Then the monolith was loaded with Cu²⁺ ions to form the metal chelate. Poly(HEMA‐MAH) monolith with a swelling ratio of 74% and containing 20.9 μmol MAH/g was used in the adsorption/desorption of IgG from aqueous solutions and human plasma. The maximum adsorption of IgG from an aqueous solution in phosphate buffer was 10.8 mg/g at pH 7.0. Higher adsorption was obtained from human plasma (up to 104.2 mg/g), with a purity of 94.1%. It was observed that IgG could be repeatedly adsorbed and desorbed with the poly(HEMA‐MAH) monolith without significant loss of adsorption capacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 395–404, 2006     

Optimization methods for petroleum fields development and production systems: a review

In this review, we survey the widespread use of numerical optimization or mathematical programming approaches to develop and produce petroleum fields for design and operations; lift gas and rate allocation; and reservoir development, planning, and management. Early applications adopted linear programming alongside heuristics. With continuous advancements in computing speed and algorithms, we have been able to formulate more complex and meaningful models including nonlinear programs and mixed-integer linear and nonlinear programs. Various formulations and solution strategies have been used including continuous and discrete optimization, stochastic programming to handle uncertainty, and metaheuristics such as genetic algorithms to increase solution quality while reducing computational load.     

Radionuclides and heavy metals concentrations in Turkish market tea

Tea is one of the most popular beverages in the world. The Eastern Black Sea Region of Turkey is one of the main tea producers in Turkey and the fifth in the world. Thus, the chemical components in tea have received great interest because they are related to health. Since this region was contaminated by the Chernobyl accident in 1986, a comprehensive study was planned and carried out to determine the radioactivity level in the tea growing region. The activity concentrations of ²³²Th, ²³⁸U, ⁴⁰K and ¹³⁷Cs were measured in 29 black tea and one green tea samples from local Turkish markets using gamma spectrometry with an HpGe detector. The average activity concentration of ²³²Th, ²²⁶Ra, ⁴⁰K and ¹³⁷Cs were found 3.2 ± 0.6 Bq/kg, 6.4 ± 0.7 Bq/kg, 445.6 ± 17.8 Bq/kg and 42.0 ± 1.4 Bq/kg in tea samples, respectively.In addition, the concentration of five heavy metals including Fe, Mn, Zn, Cu and Pb were determined by inductively coupled plasma spectroscopy (ICP/OES) on tea samples. Among the investigated metals, Mn was the highest levels. The levels of manganese were in the range of 1850.75–292.65 μg/g (mean: 1286.35 ± 0.58 μg/g). Levels of Pb in the tea samples analyzed were below the detection limits. The concentrations of all elements for daily intake are below safety levels for human consumptions.     

PHEMA cryogel for in-vitro removal of anti-dsDNA antibodies from SLE plasma

Supermacroporous poly(2-hydroxyethyl methacrylate) (PHEMA) cryogel carrying DNA was used in the removal of anti-dsDNA antibodies from systemic lupus erythematosus (SLE) patient plasma. The PHEMA cryogel was prepared by bulk polymerization which proceeds in an aqueous solution of monomer frozen inside a plastic syringe. After thawing, the PHEMA cryogel contains a continuous matrix having interconnected macropores of 10–200 μm size. Pore volume in the PHEMA cryogel was 67.5%. Ester groups in the PHEMA structure were converted to imine groups by reacting with poly(ethyleneimine) (PEI) in the presence of NaHCO₃. Amino (? NH₂) content of PEI-modified PHEMA cryogel was determined as 82 mg PEI/g. Then, DNA was attached onto the PHEMA cryogel via amino groups (53.4 mg DNA/g cryogel). Anti-dsDNA-antibody concentration declined significantly from 780 IU/ml to 80 IU/ml with the time. The maximum anti-dsDNA-antibody adsorption amount was 70 × 10³ IU/g. Anti-dsDNA-antibodies could be repeatedly adsorbed and eluted without noticeable loss in the anti-dsDNA-antibody adsorption amount.