Filtering by
- All Subjects: Adsorption
- Creators: Chemical Engineering Program
- Creators: Lind, Marylaura
- Resource Type: Text
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
Much of Nepal lacks access to clean drinking water, and many water sources are contaminated with arsenic at concentrations above both World Health Organization and local Nepalese guidelines. While many water treatment technologies exist, it is necessary to identify those that are easily implementable in developing areas. One simple treatment that has gained popularity is biochar—a porous, carbon-based substance produced through pyrolysis of biomass in an oxygen-free environment. Arizona State University’s Engineering Projects in Community Service (EPICS) has partnered with communities in Nepal in an attempt to increase biochar production in the area, as it has several valuable applications including water treatment. Biochar’s arsenic adsorption capability will be investigated in this project with the goal of using the biochar that Nepalese communities produce to remove water contaminants. It has been found in scientific literature that biochar is effective in removing heavy metal contaminants from water with the addition of iron through surface activation. Thus, the specific goal of this research was to compare the arsenic adsorption disparity between raw biochar and iron-impregnated biochar. It was hypothesized that after numerous bed volumes pass through a water treatment column, iron from the source water will accumulate on the surface of raw biochar, mimicking the intentionally iron-impregnated biochar and further increasing contaminant uptake. It is thus an additional goal of this project to compare biochar loaded with iron through an iron-spiked water column and biochar impregnated with iron through surface oxidation. For this investigation, the biochar was crushed and sieved to a size between 90 and 100 micrometers. Two samples were prepared: raw biochar and oxidized biochar. The oxidized biochar was impregnated with iron through surface oxidation with potassium permanganate and iron loading. Then, X-ray fluorescence was used to compare the composition of the oxidized biochar with its raw counterpart, indicating approximately 0.5% iron in the raw and 1% iron in the oxidized biochar. The biochar samples were then added to batches of arsenic-spiked water at iron to arsenic concentration ratios of 20 mg/L:1 mg/L and 50 mg/L:1 mg/L to determine adsorption efficiency. Inductively coupled plasma mass spectrometry (ICP-MS) analysis indicated an 86% removal of arsenic using a 50:1 ratio of iron to arsenic (1.25 g biochar required in 40 mL solution), and 75% removal with a 20:1 ratio (0.5 g biochar required in 40 mL solution). Additional samples were then inserted into a column process apparatus for further adsorption analysis. Again, ICP-MS analysis was performed and the results showed that while both raw and treated biochars were capable of adsorbing arsenic, they were exhausted after less than 70 bed volumes (234 mL), with raw biochar lasting 60 bed volumes (201 mL) and oxidized about 70 bed volumes (234 mL). Further research should be conducted to investigate more affordable and less laboratory-intensive processes to prepare biochar for water treatment.
Using DFT calculations and GAMESS computational software, porphine and its derivatives were analyzed for unique sites to accept the adsorbates As(III), As(V) and P(V) in order to compare resulting adsorption energies and determine if any of these molecules prefer arsenic oxyanions over phosphate. Pure porphine preferred As(III) over P(V) with a resulting adsorption energy of -0.7974 eV. Of the functionalized porphyrins tested, carboxyl porphyrin preferred As(V) over P(V) with a total adsorption energy of -0.7345 eV. Ethyl, methyl, chlorine and amino porphyrin all preferred As(III), with energies of -0.7934, -0.8239, -0.7602, and -0.8508 eV, respectively. Of the metalated porphyrins tested, copper and vanadium porphyrin preferred As(V) over P(V) with adsorption energies of -0.7645 and -2.0915 eV. Chromium, iron and magnesium porphyrin all preferred As(III) over P(V) with energies of -0.5993, -1.4539, and - 1.0790 eV, respectively.
A perovskite oxide material, La0.1Sr0.9Co0.9Fe0.1O3-δ (LSCF1991), was investigated first for high-temperature air separation. The oxygen sorption/desorption behavior of LSCF1991 was studied by thermogravimetric analysis (TGA) and fixed-bed breakthrough experiments. A parametric study was performed to design and optimize the operating parameters of the high-temperature air separation process by pressure swing adsorption (PSA). The results have shown great potential for applying LSCF1991 to the high-temperature air separation due to its excellent separation performance and low energy requirement.
Research on using nanostructured zeolite NaX (NZ) as adsorbents for CO2 capture was subsequently conducted. The CO2/N2 adsorption characterizations indicated that the NZ samples lead to enhanced adsorption properties compared with the commercial zeolites (MZ). From the two-bed six-step PSA simulation, NZ saved around 30% energy over MZ for CO2 capture and recovery while achieving a higher CO2 purity and productivity.
A unique screening method was developed for efficient evaluation of adsorbents for PSA processes. In the case study, 47 novel adsorbents have been screened for coal bed methane (CBM) recovery. The adsorbents went through scoring-based prescreening, PSA simulation, and optimization. The process performance indicators were correlated with the adsorption selectivity and capacities, which provides new insights for predicting the PSA performance.
A new medium-temperature oxygen sorbent, YBaCo4O7+δ (YBC114), was investigated as an oxygen pumping material to facilitate solar thermochemical fuel production. The oxygen uptake and release attributes of YBC114 were studied by both TGA and a small-scale evacuation test. The study proved that the particle size has a significant effect on the oxygen pumping behavior of YBC114, especially for the uptake kinetics.
This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs.
Utilizing DFT calculations, various substitutions on the AlPO-5 zeolite were screened for adsorption of common air molecules. Furthermore, free energy analyses using the Helmholtz free energy equation were performed to determine candidates for selective adsorption of one specific air molecule, and their operating temperature range. Through this study, it was found that Cerium- (92-542 K), Germanium- (69-370 K), Chromium- (35-293 K), and Praseodymium- (0-420 K) substituted AlPO-5 selectively adsorbs to O2 molecules for the given temperature ranges. In addition, Palladium-substituted AlPO-5 selectively adsorbs to CO within 430-755 K.