3^rd International Conference on Chemical Engineering October 2-4, 2017
Chicago, Illinois ,USA

Igor Zhitomirsky is a Distinguished Engineering Professor at the Department of Materials Science and Engineering, Faculty of Engineering of McMaster University, Hamilton, Ontario, Canada. He is a primary author of more than 230 papers in peer-reviewed journals and 8 patents. His major research interests are in electrochemical nanotechnology, colloidal nanotechnology and surface modifi cation techniques. He has developed advanced materials and manufacturing techniques for the fabrication of electrochemical supercapacitors for energy storage. His approach is focused on the advanced surface modifi cation techniques, development of advanced dispersing and capping agents for colloidal processing of nanoparticles, development of redox binders, liquid-liquid extraction techniques for agglomerate free processing of nanoparticles, electrostatic heterocoagulation and Schiff base reactions for design of advanced nanocomposites, polymermediated electrosynthesis and electrophoretic deposition techniques.

Statement of the Problem: Th e success of the supercapacitor technology will depend largely on the ability to achieve strong electrochemical performance of advanced electrode materials at practically important high active mass loadings and high chargedischarge rates. Th e purpose of this study is the development of advanced composite metal oxide-carbon nanotube and metal oxide graphene electrodes for electrochemical supercapacitors with high active mass loading, high areal and gravimetric capacitances, good cyclic stability and low impedance. Methodology & Theoretical Orientation: The approach is based on the development of new dispersing and capping agents for synthesis and colloidal processing of oxide nanoparticles, new dispersing agents for carbon nanotube and graphene and new techniques for composite design. Findings: Chelating organic molecules with strong polydentate bonding to metal oxide surface were used as capping and dispersing agents with superior control of nanoparticle size and dispersion. Small aromatic molecules and materials from bile acid family allowed excellent dispersion of carbon nanotubes and graphene.

                 

New chelating polymers and chelating polymer complexes with redox properties allowed superior co-dispersion of electrode components and were utilized as advanced redox-active binders for electrodes. Liquid-liquid extraction techniques, extraction strategies and extractors were developed for agglomerate free nanoparticle processing. Electrostatic heterocoagulation techniques were developed for the design of advanced electrodes. Conclusion & Signifi cance: Advanced supercapacitor electrodes were developed with areal capacitance of 8 F cm-2, capacitance retention at high charge-discharge rate above 50%, low impedance, good cyclic stability and high power-energy characteristics.

Daniela Almeida Streitwieser has her expertise in the development of new technologies for the utilization of biomass and residues as alternative energy sources and alternative materials with value added to its components. Her passion is the creation process of new ideas to solve traditional problems in creative and innovative manners, such as the conversion of raw materials into value product, especially if the raw materials come from alternative sources, like residues from former processes or the agribusiness. She returned to Ecuador in 2007 after completing her PhD and gathering experience in the Waste Management and Renewable Energy sector in Germany and joined immediately the Faculty at the Department of Chemistry and Chemical Engineering at the University San Francisco de Quito, Ecuador. In 2008, she created the Laboratory for Development of Alternative Energies at USFQ, which becomes IDEMA in 2016. Since 2015, she is the Head of the Department of Chemical Engineering at USFQ.

Oil, gas and coal have been used as raw materials for the production chain of most materials in our modern society. The development of petrochemical industries and processes has developed at an incredible trace. Considering that chemical

industries in general have less than 150 years of existence and petrochemistry has developed only since the beginning of the XIX century, the chemical engineering professionals can be very proud of the astonishing job done to change the world we live in. The available materials nowadays like plastics, fi bers, fuels, solvents and many others are mainly produced by the chemical industries from crude oil, carbon or gas. Its usage has been so wide, that even food or nature like products are being synthetized from fossil hydrocarbons, without forgetting the importance of the production of liquid fuels and other energy forms. This very wide range of applications has made mankind dependent of its extraction and the global economy is based on its price. Therefore, it is important that the chemical engineers apply the same concepts that have been applied for the conversion of oil into products and liquids, to the conversion of biomass and organic residues into the production of value added materials of our daily life.

                  

This can be accomplished by the development of bio-refi neries, where the biomass is converted by thermochemical or biochemical ways into new products or precursors for the manufacturing industries. Th e processes that are need to be implemented for the conversion and separation of valuable products ranges from alternative synthesis pathways, chemical or biological, to new extraction and separation methods. In this study the main technologies that are being developed for the utilization of biomass for the production of chemical precursors and products are being presented and its state of the art evaluated.

Dr. Valentino Tiangco has over 30 years of broad experience in engineering, program & project management, energy specialist, designer, test engineer, professor and researcher. He is currently the Biomass Program Manager at Sacramento Municipal Utility District (SMUD), Energy Research & Development Department. He leads, plans, and coordinates the biomass activities that include research, development, demonstration, deployment and commercial applications of biomass for power and with co-production of value-added products. His other responsibilities include RD&D efforts in geothermal, hydro, hybrid solar and other renewable and distributed generation technologies. Prior to his job at SMUD, he was a Program Manager of Advanced Generation Program with over $100 million budget over the last ten years in service at the Public Interest Energy Research (PIER) Program.

Statement of the Problem: Th e internal combustion (IC) engine exhaust contains harmful pollutants such as NOx, CO, and VOCs. These air pollutants need to be removed to comply with air quality control regulations. Th is project used pre-and post-combustion NOx control to reduce air pollutants in the exhaust from biogas powered IC engine. Th e pre-combustion NOx control system has a microwave hydrogen sulfi de (H₂S) removal unit followed by a microwave steam reformer. Approximately 10% of the biogas used to fuel the engine is process to generate hydrogen (H₂). Th e H₂ is injected back into the fuel stream prior to combustion to create H2 enriched fuel gas. Hydrogen Assisted Lean Operation (HALO) is used to ignite ultra-lean air-fuel mixtures. It reduces the peak flame temperatures and signifi cantly decreases NO_x emissions. Pre-combustion NO_x control using HALO, followed by post-combustion NO_x removal with carbon adsorption is the best approach to ensure that the CARB 2007 NO_x emission standards will be consistently met. HALO, may not meet emission standards alone, but will reduce the NOx concentration in the engine exhaust signifi cantly to minimize the amount of NO_x that must be removed by adsorption. Th e post-combustion NOx removal system consists of an exhaust cooler and two carbon adsorbers in series. Th ese adsorbers are fi lled with granular activated carbon (GAC) to remove NOx and VOCs from the exhaust. The beds are operated in a standard Lead-Lag cycle. When the average NOx concentration in the exhaust leaving the Lag bed reaches 5 ppm, the saturated GAC is replaced with the newly regenerated GAC. Th en that adsorber is switched to the Lag bed. Th e saturated GAC is transported to the microwave facility for processing. We expect the adsorbent will be replaced and regenerated once every 2-3 months. An additional benefi t is that the GAC also removes sulfur dioxide (SO2) and VOCs from exhaust. Under the grant awarded by California Energy Commission, CHA Corp built and fi eld tested this pre-and post-combustion NOx control system at Clean World’s Bio Digester Facility at SATS in Sacramento. A six-month long field-testing was successfully completed in January 2017. Throughout the field-testing period, the average NO_x emission did not exceed 5 ppm to confi rm that pre-and post-combustion NO_x control would meet not only the Rule 1110.2 but also CARB 2007 NO_x control standards. Th e result from this fi eld demonstration will be presented.

Ying Liu has obtianed her BS in Engineering Mechanics from Tsinghua University in 2001 and her PhD in Chemical Engineering from Princeton University in 2007. She is a tenured Associate Professor at the University of Illinois at Chicago. Her research group is interested in understanding the competitive kinetics during material self assembly. She has developed a scalable, reproducible process to generate drug-delivery nanoparticles, based on comprehensive understanding of the competitive kinetics and molecular dynamics during nanoprecipitation.

One of the biggest advantages of polymeric nanoparticles is the increase in solubility of hydrophobic compounds that they facilitate. Nearly 40% of all pharmaceutical compounds on the market (such as paclitaxel, rifampicin, digoxin and estrone) and 90% of newly developed compounds are hydrophobic and therefore diffi cult to deliver and maintain at suffi cient bioavailability. Drugs requires toxic solvents and surfactants such as Cremophor and Tween, which oft en impair drug distribution and are associated with severe side eff ects. Nanomedicines, which do not require the use of toxic solvents, off er clear advantages. However, in over more than two decades, very few nanomedicines have been successfully developed and approved for clinical use. Th ose already on the market are either liposome based (such as Doxil® and Myocet®) or a protein-drug complex (such as Abraxane®). Although biodegradable and biocompatible polymers have signifi cant advantages over liposome and protein delivery vehicles, such as better stability and robust molecular structure, polymeric nanoparticles have not been used beyond animal tests.

 

                     

 

The major diffi culty is to completely control the physicochemical properties of the nanoparticles especially producing them in a large quantity. Th e Liu research group has developed a process of manipulating non-equilibrium structures of the polymeric nanoparticles via kinetic control by a sophisticated combination of mixing and spray drying. The Liu research group combined experimental and simulation tools to elucidate the selfassembly kinetics of polymeric micelles that control pharmaceutical nanoparticle physicochemical properties at multiple time scale

form 100 ns to 10 s.

Eri Yoshida is an Associate Professor of Toyohashi University of Technology, Japan. She has received her PhD in Polymer Engineering from Tokyo Institute of Technology and Bachelor’s degree in Education from Tokyo Gakugei University. She has worked at Kyoto Institute of Technology as an Assistant Professor. She was also a Visiting Scientist at University of North Carolina at Chapel Hill. She has more than 100 peer reviewed scientifi c publications and obtained over 20 patents. She is a Member of the Editorial Board of several international peer reviewed journals. Her research interests include molecular self-assembly of polymer amphiphilies, controlled/living radical polymerization, molecular design of functional polymers and polymer syntheses using supercritical carbon dioxide.

Microsized giant vesicles comprised of an amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-randommethacrylic acid) diblock copolymer, PMA-b-P(MMA-r-MA), are possible artifi cial models of biomembrane for cells and organelles based on the similarities in their size and structure. Th e similarities include morphological variation based on critical packing shape of the diblock copolymer, membrane fusion and fission and stimulus-responsiveness. Th is paper describes the morphological changes in the vesicles by incorporation of ionic segments into the hydrophilic PMA block and the transformation by electrostatic interaction with a polyelectrolyte on the hydrophilic surface of the vesicles. Th e permeability enhancement of the vesicle bilayer by incorporation of the ionic segments into the hydrophobic P(MMA-r-MA) block is also described. Th e morphological changes in the spherical vesicles were investigated by incorporation of the 3-sulfopropyl methacrylate potassium salt (SpMA) into the hydrophilic PMA block. Th e vesicles were reduced in size as the SpMA units increased due to the expansion of the hydrophilic surface area for critical packing shape of the copolymer by the incorporation of the more hydrophilic ionic segments. Th e increase in the SpMA units delayed the transition from the spherical vesicles to a sheet-like bilayer. Th e SpMA-containing vesicles were disrupted into a nonspecifi c form by the electrostatic interaction with poly(allylamine hydrochloride) (PAH). A large excess of the polyelectrolyte caused partial fusion of the vesicles rather than disruption (Figure-1).

 

            

 

The vesicles with the SpMA incorporated into the hydrophobic P(MMA-r-MA) block also changed from spherical to sheet-like as the SpMA units increased. Th e SpMA units enhanced the permeability of Rhodamine B (Rh) into the vesicle bilayer, whereas the vesicles without SpMA captured no Rh molecules. It was demonstrated that this permeability enhancement was attributed to the pore formation in the bilayer by the capture and release of the Rh by the SpMA units in the hydrophobic phases.

Problem Statement: The objective of this work was to develop a systematic strategy for generating efficient, alternate reaction paths that could be used to manufacture the top 100 industrial chemicals, currently produced from crude oil, using renewable feed-stocks. All organic chemicals play a vital role in synthesis of polymers, solvents, food products and fi bers, manufacturing these chemicals from oil, coal or natural gas results in increasing carbon dioxide levels in the atmosphere, responsible for global climate change.

Aim: The aim of this study was to use the existing knowledge on the conversion of carbon-neutral feed-stocks, like biomass, wood, etc., to suitable precursor raw materials and the known industrial reaction paths, currently used for manufacturing the top 100 industrial organic chemicals, to systematically develop and evaluate alternate carbon-effi cient reaction paths.

Methodology: A matrix model is generated that consists of 96 biomass sources and 105 major industrial chemicals, in which each element shows either the amount of chemical (represented by the matrix column) that is produced from a unit amount of biomass or the amount of carbon that is present in the chemical, represented by the matrix column, divided by the amount of carbon in the

chemical, represented by the row of the matrix, i.e., fractional carbon economy for the conversion of the chemical in the row to the chemical, represented by the column. The fractional carbon economy was determined from a comprehensive listing of industrial reactions paths, which also gives the yields and effi ciencies of these industrial reaction paths, currently being practiced in the chemical industry.

 

 

Result: Conclusion & Significance: This methodology allows a systematic generation of viable reaction paths for manufacturing industrial chemicals from renewable, carbon-neutral feed-stocks. An example of a chemical pathway generated by this methodology is shown in Figure 1.

Sabine Enders leads the Institute of Technical Thermodynamics and Refrigeration Technology at the Karlsruhe Institute of Technology in Germany. Her scientific

expertise lies in the fi eld of phase behaviors and interfacial properties of complex mixtures, such as mixtures containing polymers, crude oil, pharmaceuticals or

surfactants.

Polymeric carries, which physically entrap molecules of interest (pharmaceutical active ingredient, API) and polymer conjugates, to which such molecules are chemically bound, play an important role in modern pharmaceutical technology. Macromolecular architecture is receiving increasing interest as the search for new tailor-made polymeric materials with strictly specifi ed properties intensifiers. Th erefore, the molecular architecture must be taken into account in the thermodynamic framework. Th e lattice cluster theory (LCT), developed by Dudowicz and Freed, allows the calculation of the thermodynamic properties of a molecule having an arbitrary structure and hence it is possible to take the short-chain branching of the polymer directly into account. Th e LCT will be utilized to model phase equilibria of polymer containing mixtures. Polymers involved in this research are polyolefi ns and hyperbranched polymers. In the case of polyolefi ns, which are semi-crystalline polymers, the chemical composition, the molecular weight distribution, stereoregularity and short-chain branching distributions (SCBD) play the dominant role for the material properties. All these properties show an impact of the related phase equilibria (solid-liquid equilibria, liquid-liquid demixing at high pressure).                                                                                     

This contribution demonstrated the possibilities as well as the limitation of the LCT and their modifi cations for phase equilibria predictions. Hyperbranched polymers carry a large number of polar terminal groups and therefore they are widely applied for increasing the solubility in water and consequently the bioavailability of hydrophobic API. In this contribution the increase of the solubility of the model API quercetin, which has very poor water solubility, by adding a hyperbranched polymer will be discussed. Alcohols are excellent solvents for quercetin, however, quercetin degraded in this solvent. Additionally, the prediction of the relevant liquid-liquid equilibria using the LCT is discussed in detail. One example is the ternary system composed of hyperbranched polymer+water+butanol (Figure-1).

                                                                               

Kirsten Grubel has studied Chemistry at Ruhr-University Bochum in Germany. For her interdisciplinary Master thesis, she changed from the research field of

Inorganic Chemistry to the Departments of Technical Chemistry and Mechanical Engineering. In her Master thesis, she investigated and developed methods to analyze the solubility properties of light gases in volatile solvents and joined PhD project in 2015, dealing with investigation of thermophysical properties of fluids under high pressure.

For commercial production of basic and fine chemicals, like aldehydes, ketones and dioles, alcohol oxidations are commonly used. Th ese processes suff er from the use of toxic oxidizing agents and the production of a vast amount of toxic by-products. In this regard, an important fi eld in chemical research is catalyst development in order to substitute commercial toxic substrates and to reduce environmental pollution. The heterogeneously catalyzed aerobic ethanol oxidation features the utilization of oxygen from air as oxidizing agent. This approach is not only cost and atom effi cient, it also bears the benefit of a greener industrial process since oxygen is non-toxic, readily available and water is the only by-product. Unfortunately, little is known about the solubility properties of the air components N₂ and O₂ in aqueous ethanol solutions at process conditions. This lack of data impedes to find optimal reaction conditions and to develop optimal catalyst with desired requirements. Within this project, solubility properties of the air components in dependence of temperature, pressure and liquid phase compositions are measured.

                                         

The setup for the gas solubility measurements mainly consists of a high pressure autoclave connected to a gas chromatograph. To investigate the solubility properties of a gas, the autoclave is filled with thoroughly degassed ethanol/water mixtures, heated to the desired temperature, pressurized with the gas to be analyzed and the mixture is stirred to accelerate equilibration times. At equilibrium conditions, samples from the liquid phase are withdrawn via the capillary of the sampling valve and preceded to the gas chromatograph via the superheated, helium purged transfer line, in order to evaporate the liquid sample content. By means of the at-line chromatograph, the molar amount of dissolved gases in the solvent (ethanol water mixtures) can be quantitatively determined. These data will help to optimize reaction conditions and to evaluate catalyst requirements for optimal efficiency and selectivity.