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Description
Pervaporation is a membrane separation technology that has had industrial application and which is the subject of ongoing research. Two major factors are important in judging the quality of a membrane: selectivity and permeation flux. Although many types of materials can be used for the separation layer, zeolites will be

Pervaporation is a membrane separation technology that has had industrial application and which is the subject of ongoing research. Two major factors are important in judging the quality of a membrane: selectivity and permeation flux. Although many types of materials can be used for the separation layer, zeolites will be the material considered in this thesis. A simple mathematical model has been developed to demonstrate the inter-relationships between relative permeation flux, reduced selectivity, and the relative resistance to mass transfer of the support to the zeolite layer. The model was applied to several membranes from our laboratory and to two examples from the literature. The model offers a useful way of conceptualizing membrane performance and facilitates the comparison of different membrane performances. The model predicts the effect of different supports on zeolite supported membrane performance.
ContributorsMann, Stewart (Author) / Lin, Jerry (Thesis advisor) / Lind, Mary Laura (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Membranes are a key part of pervaporation processes, which is generally a more

efficient process for selective removal of alcohol from water than distillation. It is

necessary that the membranes have high alcohol permeabilities and selectivities.

Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have

demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71)

demonstrated promising alcohol

Membranes are a key part of pervaporation processes, which is generally a more

efficient process for selective removal of alcohol from water than distillation. It is

necessary that the membranes have high alcohol permeabilities and selectivities.

Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have

demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71)

demonstrated promising alcohol separation abilities. In this dissertation, we present

fundamental studies on the synthesis of ZIF-71/PDMS MMMs.

Free-standing ZIF-71/ PDMS membranes with 0, 5, 25 and 40 wt % ZIF-71

loadings were prepared and the pervaporation separation for ethanol and 1-butanol from

water was measured. ZIF-71/PDMS MMMs were formed through addition cure and

condensation cure methods. Addition cure method was not compatible with ZIF-71

resulting in membranes with poor mechanical properties, while the condensation cure

method resulted in membranes with good mechanical properties. The 40 wt % ZIF-71

loading PDMS nanocomposite membranes achieved a maximum ethanol/water selectivity

of 0.81 ± 0.04 selectivity and maximum 1-butnaol/water selectivity of 5.64 ± 0.15.

The effects of synthesis time, temperature, and reactant ratio on ZIF-71 particle

size and the effect of particle size on membrane performance were studied. Temperature

had the greatest effect on ZIF-71 particle size as the synthesis temperature varied from -

20 to 35 ºC. The ZIF-71 synthesized had particle diameters ranging from 150 nm to 1

μm. ZIF-71 particle size is critical in ZIF-71/PDMS composite membrane performance

for alcohol removal from water through pervaporation. The membranes made with

micron sized ZIF-71 particles showed higher alcohol/water selectivity than those with

smaller particles. Both alcohol and water permeability increased when larger sized ZIF-

71 particles were incorporated.

ZIF-71 particles were modified with four ligands through solvent assisted linker

exchange (SALE) method: benzimidazole (BIM), 5-methylbenzimidazole (MBIM), 5,6-

dimethylbenzimidazole (DMBIM) and 4-Phenylimidazole (PI). The morphology of ZIF-

71 were maintained after the modification. ZIF-71/PDMS composite membranes with 25

wt% loading modified ZIF-71 particles were made for alcohol/water separation. Better

particle dispersion in PDMS polymer matrix was observed with the ligand modified ZIFs.

For both ethanol/water and 1-butanol/water separations, the alcohol permeability and

alcohol/water selectivity were lowered after the ZIF-71 ligand exchange reaction.
ContributorsYin, Huidan (Author) / Lind, Mary Laura (Thesis advisor) / Mu, Bin (Committee member) / Nielsen, David (Committee member) / Seo, Don (Committee member) / Lin, Jerry (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Depletion of fossil fuel resources has led to the investigation of alternate feedstocks for and methods of chemical synthesis, in particular the use of E. coli biocatalysts to produce fine commodity chemicals from renewable glucose sources. Production of phenol, 2-phenylethanol, and styrene was investigated, in particular the limitation in yield

Depletion of fossil fuel resources has led to the investigation of alternate feedstocks for and methods of chemical synthesis, in particular the use of E. coli biocatalysts to produce fine commodity chemicals from renewable glucose sources. Production of phenol, 2-phenylethanol, and styrene was investigated, in particular the limitation in yield and accumulation that results from high product toxicity. This paper examines two methods of product toxicity mitigation: the use of efflux pumps and the separation of pathways which produce less toxic intermediates. A library of 43 efflux pumps from various organisms were screened for their potential to confer resistance to phenol, 2-phenylethanol, and styrene on an E. coli host. A pump sourced from P. putida was found to allow for increased host growth in the presence of styrene as compared to a cell with no efflux pump. The separation of styrene producing pathway was also investigated. Cells capable of performing the first and latter halves of the synthesis were allowed to grow separately and later combined in order to capitalize on the relatively lower toxicity of the intermediate, trans-cinnamate. The styrene production and yield from this separated set of cultures was compared to that resulting from the growth of cells containing the full set of styrene synthesis genes. Results from this experiment were inconclusive.
ContributorsLallmamode, Noor Atiya Jabeen (Author) / Nielsen, David (Thesis director) / Cadillo-Quiroz, Hinsby (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / School of Life Sciences (Contributor)
Created2015-05
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Description
In our modern world the source of for many chemicals is to acquire and refine oil. This process is becoming an expensive to the environment and to human health. Alternative processes for acquiring the final product have been developed but still need work. One product that is valuable is butanol.

In our modern world the source of for many chemicals is to acquire and refine oil. This process is becoming an expensive to the environment and to human health. Alternative processes for acquiring the final product have been developed but still need work. One product that is valuable is butanol. The normal process for butanol production is very intensive but there is a method to produce butanol from bacteria. This process is better because it is more environmentally safe than using oil. One problem however is that when the bacteria produce too much butanol it reaches the toxicity limit and stops the production of butanol. In order to keep butanol from reaching the toxicity limit an adsorbent is used to remove the butanol without harming the bacteria. The adsorbent is a mesoporous carbon powder that allows the butanol to be adsorbed on it. This thesis explores different designs for a magnetic separation process to extract the carbon powder from the culture.
ContributorsChabra, Rohin (Author) / Nielsen, David (Thesis director) / Torres, Cesar (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
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Description
The goals of the styrene oxide adsorption experiments were to develop reliable isotherms of styrene oxide onto Dowex Optipore L-493 resin and onto mesoporous carbon adsorbents, in addition to determining the ideal conditions for styrene oxide production from E. coli. Adsorption is an effective means of separation used in industry

The goals of the styrene oxide adsorption experiments were to develop reliable isotherms of styrene oxide onto Dowex Optipore L-493 resin and onto mesoporous carbon adsorbents, in addition to determining the ideal conditions for styrene oxide production from E. coli. Adsorption is an effective means of separation used in industry to separate compounds, often organics from air and water. Styrene oxide adsorption runs without E. coli were conducted at concentrations ranging from 0.15 to 3.00 g/L with resin masses ranging from 0.1 to 0.5 g of Dowex Optipore L-493 and 0.5 to 0.75 g of mesoporous carbon adsorbent. Runs were conducted on a shake plate operating at 80 rpm for 24 hours at ambient temperature. Isotherms were developed from the results and then adsorption experiments with E. coli and L-493 were performed. Runs were conducted at glucose concentrations ranging from 20-40 g/L and resin masses of 0.100 g to 0.800 g. Samples were incubated for 72 hours and styrene oxide production was measured using an HPLC device. Specific loading values reached up to 0.356 g/g for runs without E. coli and nearly 0.003 g of styrene oxide was adsorbed by L-493 during runs with E. coli. Styrene oxide production was most effective at low resin masses and medium glucose concentrations when produced by E. coli.
ContributorsHsu, Joshua (Co-author) / Oremland, Zachary (Co-author) / Nielsen, David (Thesis director) / Staggs, Kyle (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / School of Sustainability (Contributor)
Created2014-05
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Description
The inability of a single strain of bacteria to simultaneously and completely consume multiple sugars, such as glucose and xylose, hinder industrial microbial processes for ethanol and lactate production. To overcome this limitation, I am engineering an E. coli co-culture system consisting of two ‘specialists'. One has the ability to

The inability of a single strain of bacteria to simultaneously and completely consume multiple sugars, such as glucose and xylose, hinder industrial microbial processes for ethanol and lactate production. To overcome this limitation, I am engineering an E. coli co-culture system consisting of two ‘specialists'. One has the ability to only consume xylose and the other only glucose. This allows for co-utilization of lignocellulose-derived sugars so both sugars are completely consumed, residence time is reduced and lactate and ethanol titers are maximized.
ContributorsAyla, Zeynep Ece (Author) / Nielsen, David (Thesis director) / Flores, Andrew (Committee member) / Chemical Engineering Program (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
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Description
Escherichia coli is a bacterium that is used widely in metabolic engineering due to its ability to grow at a fast rate and to be cultured easily. E. coli can be engineered to produce many valuable chemicals, including biofuels and L-Phenylalanine—a precursor to many pharmaceuticals. Significant cell growth occurs in

Escherichia coli is a bacterium that is used widely in metabolic engineering due to its ability to grow at a fast rate and to be cultured easily. E. coli can be engineered to produce many valuable chemicals, including biofuels and L-Phenylalanine—a precursor to many pharmaceuticals. Significant cell growth occurs in parallel to the biosynthesis of the desired biofuel or biochemical product, and limits product concentrations and yields. Stopping cell growth can improve chemical production since more resources will go toward chemical production than toward biomass. The goal of the project is to test different methods of controlling microbial uptake of nutrients, specifically phosphate, to dynamically limit cell growth and improve biochemical production of E. coli, and the research has the potential to promote public health, sustainability, and environment. This can be achieved by targeting phosphate transporter genes using CRISPRi and CRISPR, and they will limit the uptake of phosphate by targeting the phosphate transporter genes in DNA, which will stop transcriptions of the genes. In the experiment, NST74∆crr∆pykAF, a L-Phe overproducer, was used as the base strain, and the pitA phosphate transporter gene was targeted in the CRISPRi and CRISPR systems with the strain with other phosphate transporters knocked out. The tested CRISPRi and CRISPR mechanisms did not stop cell growth or improved L-Phe production. Further research will be conducted to determine the problem of the system. In addition, the CRISPRi and CRISPR systems that target multiple phosphate transporter genes will be tested in the future as well as the other method of stopping transcriptions of the phosphate transporter genes, which is called a tunable toggle switch mechanism.
ContributorsPark, Min Su (Author) / Nielsen, David (Thesis director) / Machas, Michael (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
Styrene, a component of many rubber products, is currently synthesized from petroleum in a highly energy-intensive process. The Nielsen Laboratory at Arizona State has demonstrated a biochemical pathway by which E. coli can be engineered to produce styrene from the amino acid phenylalanine, which E. coli naturally synthesizes from glucose.

Styrene, a component of many rubber products, is currently synthesized from petroleum in a highly energy-intensive process. The Nielsen Laboratory at Arizona State has demonstrated a biochemical pathway by which E. coli can be engineered to produce styrene from the amino acid phenylalanine, which E. coli naturally synthesizes from glucose. However, styrene becomes toxic to E. coli above concentrations of 300 mg/L, severely limiting the large-scale applicability of the pathway. Thus, styrene must somehow be continuously removed from the system to facilitate higher yields and for the purposes of scale-up. The separation methods of pervaporation and solvent extraction were investigated to this end. Furthermore, the styrene pathway was extended by one step to produce styrene oxide, which is less volatile than styrene and theoretically simpler to recover. Adsorption of styrene oxide using the hydrophobic resin L-493 was attempted in order to improve the yield of styrene oxide and to provide additional proof of concept that the flux through the styrene pathway can be increased. The maximum styrene titer achieved was 1.2 g/L using the method of solvent extraction, but this yield was only possible when additional phenylalanine was supplemented to the system.
ContributorsMcDaniel, Matthew Cary (Author) / Nielsen, David (Thesis director) / Lind, Mary Laura (Committee member) / McKenna, Rebekah (Committee member) / Barrett, The Honors College (Contributor) / Department of Chemistry and Biochemistry (Contributor) / Chemical Engineering Program (Contributor)
Created2013-05
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Description
Four enzymes, ATF1, ATF2, ATF, and CAT, were screened to determine which would be most effective at catalyzing the formation of aromatic esters. The CAT enzyme successfully catalyzed the reaction to produce 2-phenethyl acetate using 20x more lysate to improve the probability of enzyme presence in the lysate. The CAT

Four enzymes, ATF1, ATF2, ATF, and CAT, were screened to determine which would be most effective at catalyzing the formation of aromatic esters. The CAT enzyme successfully catalyzed the reaction to produce 2-phenethyl acetate using 20x more lysate to improve the probability of enzyme presence in the lysate. The CAT enzyme was able to catalyze the reaction producing concentrations that increased by 62% every 12 hours. Enzymatic activity resulted in the production of 2.15 mg/L of 2-phenethyl acetate at 12 hours, 5.62 mg/L of 2-phenethyl acetate at 24 hours, and 15.12 mg/L of 2-phenethyl acetate at 48 hours.
ContributorsBrown, Kristen Ashley (Author) / Nielsen, David (Thesis director) / Thompson, Brian (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05