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- Creators: Chemical Engineering Program
- Creators: Civil, Environmental and Sustainable Eng Program
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
Enzyme-induced carbonate precipitation (EICP) is a biocementation technique that produces comparatively fewer carbon dioxide emissions than traditional cementation. However, the use of synthetic reagents for EICP is costly, and the process produces an ammonium byproduct which is a harmful pollutant. This study utilizes fresh urine as a source of urea and calcium-rich zeolites as an ammonium adsorbent and a source of calcium ions for the EICP cementation technique. Batch hydrolysis and adsorption experiments were conducted to determine the effects of zeolite type, zeolite form, and solution composition on ammonium adsorption and calcium release. Cementation experiments were then conducted to determine the effects of different hydrolysis and adsorption times on ammonium adsorption and calcium carbonate precipitation. The results showed that calcium-rich chabazite could be used as a source of calcium ions and as an effective adsorbent of ammonium for EICP. Additionally, synthetic, fresh urine and real, fresh urine had comparable ammonium adsorption and calcium release trends. Finally, inclusion of a pre-hydrolysis step reduced the ammonium adsorption and calcium release, but longer adsorption times lead to calcium carbonate precipitation outside of the sand column, which is an undesirable outcome for soil biocementation; even with this limitation, the calcium carbonate content of sand columns ranged from 0.48% to 0.92%, which signifies the potential of the proposed process for cementation, given a higher initial concentration of urea.
Carbon capture has been a highly sought-after technology for decades because of its<br/>capabilities to restore atmospheric damage done by greenhouse gasses. Thanks to evolving<br/>separation techniques, carbon capture is becoming more efficient with every new discovery in<br/>the field. Currently the biggest problems that carbon capture are facing is the cost of<br/>manufacturing material to aid the process and obtaining ideal conditions for removal of carbon<br/>from air and devising solutions for removal of CO2 in ambient and flue gas conditions.<br/>This Honors Thesis is a continuation of Dr. Shuguang Deng and Dr. Mai Xu’s research<br/>initiative to manufacture and test various zeolitic CO2 removal efficiencies. The goals of this<br/>Honors Thesis are to investigate the adsorption/desorption kinetics and isothermal equilibrium<br/>CO2 capacity of a NaX nanozeolite under ambient air conditions.<br/>What was determined from the following testing was that the zeolite of interest had a<br/>higher adsorption capacity of CO2 at lower temperatures, had a maximum equilibrium quantity<br/>adsorbed of 0.203 mmol/g for CO2 and 0.367 mmol/g of N2, had a maximum breakthrough CO2<br/>capacity of 0.101 mmol of CO2 per gram of zeolite at dry conditions and 298.15K and this<br/>linearly decreased to 0.040 mmol/g at 25% relative humidity.