NANOPOROUS PURE SILICA ZEOLITES

Abstract

This disclosure relates to nanoporous pure silica zeolite (PSZ) adsorbents and uses thereof.

Claims

1. A nanoporous pure silica zeolite (PSZ) adsorbent, comprising a chemical framework composition comprising Si.sub.64O.sub.128, wherein the nanoporous PSZ adsorbent comprises a DON phase.

2. The nanoporous PSZ adsorbent of claim 1 further comprising a surface area in the range of 250 m.sup.2 g.sup.1 to 600 m.sup.2 g.sup.1.

3. The nanoporous PSZ adsorbent of claim 1 further comprising an average pore size of about 12 .

4. The nanoporous PSZ adsorbent of claim 1 further comprising thermal stability up to about 600 C.

5. The nanoporous PSZ adsorbent of claim 1, wherein the PSZ adsorbent was prepared using bis(pentamethyl-cyclopentadienyl), cobalt (III) hydroxide (((Cp*).sub.2Co)OH) as a structure directing agent.

6. A filter, comprising: a) a substrate; and b) a nanoporous PSZ adsorbent associated with the substrate, wherein the nanoporous PSZ adsorbent comprises a chemical framework composition comprising Si.sub.64O.sub.128 and wherein the PSZ adsorbent comprises a DON phase.

7. The filter of claim 6, wherein the substrate comprises a housing and the nanoporous PSZ adsorbent is contained within the housing.

8. A method of removing a siloxane contaminant from a substance, comprising: a) providing a nanoporous PSZ adsorbent; b) contacting the substance to the nanoporous PSZ adsorbent, wherein the substance comprises a siloxane contaminant; and c) removing the siloxane contaminant from the substance by adsorption to the nanoporous PSZ adsorbent.

9. The method of claim 8, wherein the nanoporous PSZ adsorbent comprises a chemical framework composition comprising Si.sub.64O.sub.128.

10. The method of claim 9, wherein the nanoporous PSZ adsorbent comprises a DON phase.

11. The method of claim 8, wherein the nanoporous PSZ adsorbent has a surface area of about 400 m.sup.2 g.sup.1.

12. The method of claim 8, wherein the nanoporous PSZ adsorbent has an average pore size of about 12 .

13. The method of claim 8, wherein the nanoporous PSZ adsorbent has thermal stability up to about 600 C.

14. The method of claim 8, wherein the substance is an aqueous substance.

15. The method of claim 8, wherein the siloxane contaminant comprises one or more of TMS, MMST, DMSD, and/or DMSO.sub.2.

16. The method of claim 15, wherein up to about 3 wt. % TMS is adsorbed from the substance.

17. A method of removing a siloxane contaminant from a substance, comprising: a) providing a nanoporous PSZ adsorbent; b) contacting the substance to the nanoporous PSZ absorbent, wherein the substance comprises a siloxane contaminant; c) removing the siloxane contaminant from the substance by adsorption to the nanoporous PSZ adsorbent; and d) regenerating the nanoporous PSZ adsorbent.

18. The method of claim 17, wherein the nanoporous PSZ adsorbent is regenerated by treating the nanoporous PSZ adsorbent using a pH swing to change the adsorbent surface charge and produce desorption.

19. The method of claim 17, wherein the nanoporous PSZ adsorbent is regenerated by heating the nanoporous PSZ adsorbent to a temperature above the melting point of the adsorbed siloxanes but below the thermal stability point of the adsorbent structure.

20. The method of claim 19, wherein regeneration of the nanoporous PSZ adsorbent occurs within a period ranging from minutes to hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0017] FIG. 1. The average adsorption energy and loading values of PSZs towards four siloxanes or siloxane derivatives. The points at which the dotted lines cross represent average adsorption energy and loading for each data set. Markers shown in gray represent zeolites that exhibited adsorption energies and loadings above average. MMSTmonomethylsilanetriol, DMSDdimethylsilanediol, TMStrimethylsilanol, DMSO.sub.2dimethylsulfone.

[0018] FIG. 2. Illustration of synthesized absorbent with DON framework and pore channels.

[0019] FIG. 3. Single component equilibrium adsorption isotherms for different siloxanes onto a DON PSZ adsorbent. Conditions: ambient temperature and pH7. Basis: mass (mg) of siloxane adsorbed vs. solution.

[0020] FIG. 4. Illustration of synthesized absorbent with PSI framework and pore channels.

[0021] FIG. 5. Single component equilibrium adsorption isotherms for different siloxanes onto a PSI aluminophosphate adsorbent. Conditions: ambient temperature and pH7. Basis: mass (mg) of siloxane adsorbed vs. solution.

[0022] FIG. 6. Comparison of single component equilibrium adsorption isotherms for different siloxanes onto DON PSZ or PSI aluminophosphate adsorbents. (right panel) Ordinate axis in units of mass of siloxane adsorbed per adsorbent surface area. Conditions: ambient temperature and pH7. Basis: mass (mg) of siloxane adsorbed vs. solution.

[0023] FIGS. 7A and 7B. Single point (A) binary and (B) quaternary mixtures equilibrium uptakes for different siloxanes onto DON PSZ or FAU aluminosilicate adsorbents. Conditions: the initial concentration of each contaminant was 1 mg C L1, ambient temperature and pH7.

[0024] FIG. 8. Schematic of a contemplated filter according to one embodiment.

[0025] FIG. 9. Zeta potential profiles for UTD-1 (DON) and PST-6 (PSI).

DETAILED DESCRIPTION

[0026] It is to be understood that the particular aspects of the specification are described herein are not limited to specific embodiments presented, and can vary. It also will be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting. Moreover, particular embodiments disclosed herein can be combined with other embodiments disclosed herein, as would be recognized by a skilled person, without limitation.

[0027] Throughout this specification, unless the context specifically indicates otherwise, the terms comprise and include and variations thereof (e.g., comprises, comprising, includes, and including) will be understood to indicate the inclusion of a stated component, feature, element, or step or group of components, features, elements or steps but not the exclusion of any other component, feature, element, or step or group of components, features, elements, or steps. Any of the terms comprising, consisting essentially of, and consisting of may be replaced with either of the other two terms, while retaining their ordinary meanings.

[0028] As used herein, the singular forms a, an, and the include plural referents unless the context clearly indicates otherwise.

[0029] Percentages disclosed herein can vary in amount by 10, 20, or 30% from values disclosed and remain within the scope of the contemplated disclosure.

[0030] Unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the an, values herein that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the disclosure, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0031] As used herein, ranges and amounts can be expressed as about a particular value or range. About also includes the exact amount. For example, about 5% means about 5% and also 5%. The term about can also refer to 10% of a given value or range of values. Therefore, about 5% also means 4.5%-5.5%, for example.

[0032] As used herein, the terms or and and/or are utilized to describe multiple components in combination or exclusive of one another. For example, x, y, and/or z can refer to x alone, y alone, Z alone, x, y, and z, (x and y) or z, x or (y and z), or x or y or z.

[0033] Overview

[0034] Zeolites possess outstanding structural advantages as adsorbent materials due their surface chemistry. For zeolites that contain merely silicon and oxygen atoms, also known as pure silica zeolites (PSZs), their frameworks are highly hydrophobic and without acid sites. Thus, the competitive adsorption of water, which contains high concentrations of cations, would be significantly reduced (Pham et al., 2014). Moreover, zeolites are thermally stable and can be easily regenerated when their pores are saturated with adsorbates (Olson et al., 2004; Palomino et al., 2007; Zhu et al., 2000). It should be noted that there are numerous possible zeolites and screening these one by one as promising candidates for siloxane removal is not practical, if not impossible. However, Grand canonical Monte Carlo (GCMC) simulation methods can be used to simplify and expedite the screening.

[0035] As used herein, the pure silica zeolites are understood to be substantially formed only from silicon and oxygen in an approximately 2:1 atomic ratio. Accordingly, in certain embodiments as otherwise described herein, no more than 10 at % of the PSZ is comprised of elements besides silicon and oxygen. For example, in particular embodiments, no more than 5 at % (e.g., no more than 3 at %, or 1 at %, or 0.1 at %) of the PSZ is comprised of elements besides silicon and oxygen. In certain embodiments, surface hydroxyl groups will result in small amount of hydrogen content in the PSZ. Accordingly, in those embodiments, no more than 10 at % (e.g., no more than 5 at %, or 3 at %, or 1 at %, or 0.1 at %) of the PSZ is comprised of elements besides silicon, oxygen and hydrogen. It will be understood that the atomic purity of the PSZ refers to covalently bonded species, and does not include adsorbed species such as H.sub.2O. In particular embodiments, the PSZ contains substantially no (e.g., less than 5 at %, or less than 1 at %, or an undetectable amount) of Zr, Al, Zn, Mg, Ca, P, or Na.

[0036] The present inventors have determined that the DON zeolite phase is ideal for siloxane adsorption desorption. Accordingly, in certain embodiments as otherwise described herein, the nanoporous PSZ adsorbent comprises a DON phase. For example, in particular embodiments, the PSZ adsorbent comprises no more than 10% other crystalline phases, e.g., no more than 5%, or 3%, or 1% other crystalline phases. In some embodiments, no other crystalline phase is detectable through methods conventional in the art, such as powder x-ray diffraction.

[0037] Provided herein are zeolites for the adsorption of siloxanes and siloxane derivatives from the environment. In some embodiments, zeolites of the present disclosure can adsorb siloxanes and derivatives thereof from fluid phases, such as water and air. Adsorption can occur at various temperatures, including, for example at ambient temperature (e.g., about 25 C.) or at temperatures near or below the boiling point of the liquid solvent where the siloxanes reside.

[0038] Exemplary zeolites contemplated herein include pure silica zeolites (PSZs), though other zeolites are also contemplated herein. In some embodiments, PSZs can have pore sizes anywhere within the micropore and mesopore range (from about 20 to about 500 ) and could be prepared or modified to include silanol groups (i.e., OH sites) to enhance their potential for capturing siloxanes from fluid media. PSZs with structural faulting that leads to the formation of silanols display considerable adsorption capacity toward certain linear siloxanes.

[0039] Accordingly, in certain embodiments as otherwise described herein, the nanoporous PSZ adsorbent comprises an average pore size in the range of 5 to 20 . For example, in particular embodiments, the nanoporous PSZ adsorbent comprises an average pore size in the range of 6 to 18 , e.g., 8 to 16 , or 10 to 14 , or about 12 .

[0040] Advantageously, the PSZ adsorbent as described herein has a high surface area. Accordingly, in certain embodiments, the nanoporous PSZ adsorbent may comprise a surface area of about 400 m.sup.2 g.sup.1. Accordingly, in particular embodiments, the nanoporous PSZ adsorbent comprises a surface area of 250 m.sup.2 g.sup.1 to 600 m.sup.2 g.sup.1. For example, in some embodiments, the PSZ adsorbent comprises a surface area of 250 m.sup.2 g.sup.1 to 550 m.sup.2 g.sup.1, e.g., 250 m.sup.2 g.sup.1 to 500 m.sup.2 g.sup.1, or 250 m.sup.2 g.sup.1 to 450 m.sup.2 g.sup.1, or 300 m.sup.2 g.sup.1 to 600 m.sup.2 g.sup.1, or 350 m.sup.2 g.sup.1 to 600 m.sup.2 g.sup.1, or 300 m.sup.2 g.sup.1 to 500 m.sup.2 g.sup.1, or 350 m.sup.2 g.sup.1 to 450 m.sup.2g.sup.1.

[0041] Filters

[0042] Zeolites that exhibit selectivity toward siloxanes and derivatives thereof can be used as the main, active component of fixed bed type filters for deployment in scenarios such as continuous flow water treatment systems, including those capable of handling large scale purification of water (i.e., water treatment plants) and consumer level scale systems (i.e., in line water purification systems for home applications). These zeolites can also be prepared in membrane form for removal of siloxanes based on nanofiltration, ultrafiltration, and/or osmosis. Furthermore, the siloxane selective zeolites can be employed for the development of sensing applications, with systems based on or combined with zeolitic thin films and other appropriate forms or shapes. In some embodiments, a zeolite can form the active component in the sensing element, which can produce a signal upon adsorbing a siloxane from water based on chemical changes on its surface (e.g., a change in zeolitic structure upon adsorbing a siloxane can be translated into a detectable signal). Detection of changes in zeolitic structure can be accomplished by various means as are appreciated by a person of skill in the art. For example, siloxane adsorption by a contemplated zeolite can be measured, for example, by sensing a change in adsorption energy leading to a measurable temperature change. In some embodiments, devices are contemplated herein that incorporate such zeolite sensing elements and can be used to detect the presence of siloxanes in fluids, such as drinking water. In some embodiments, such devices can combine zeolite filters and zeolite sensors.

[0043] In some embodiments, one or more filters containing a PSZ adsorbent are contemplated. For example, a contemplated filter 10 is shown in FIG. 8. The filter 10 includes a substrate 12, which can be a two-dimensional solid or flexible structure or a three-dimensional structure or housing. The filter 10 further includes a PSZ adsorbent 14 that is permanently or removably affixed to the substrate 12. The filter 10 can further include area 16 that can serve as an opening into a housing to allow entry of a substance to be filtered and an area 18 that can serve as an exit for the filtered substance.

[0044] Reclamation Systems

[0045] Reclamation systems (e.g., water reclamation systems) are contemplated herein that incorporate one or more zeolite filters, such as those that can be employed in closed or limited environment systems, for example, those used in water-poor environments or in space applications. In some embodiments, siloxanes adsorbents can be incorporated into reclamations systems in filter form, as described herein elsewhere. In some embodiments, contemplated zeolite filters containing PSZ adsorbents form part of a train chain of water treatment steps. In some embodiments, such siloxane adsorption filters are located strategically within the chain. For instance, as a polishing stage at the very end of the train, or at a place following the contaminant point source (e.g., in the case of space applications).

[0046] Methods

[0047] In some embodiments, methods of removing siloxanes and derivatives thereof from water include contacting a zeolitic adsorbent with a volume of water either in batch or flow fashion. When used in batch processing, a method of removing siloxanes and derivatives thereof can include mixing of the adsorbent particles (in pellet or any other appropriate form) with a particular amount of water containing one or more siloxane and/or siloxane derivatives at a given concentration. This batch process can include contacting both the solid and liquid phases for a given amount of time (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 24, 36, 48, 72, or 96 hours or more), followed by a solid phase separation step (i.e., precipitation, centrifugation, etc.) to recover the purified water. For flow systems, a fixed bed approach could be used. In such systems, the adsorbent solid particles can be packed into a given volume (i.e., a cylindrical column or any other desired volume). This bed can then be contacted by a water flow that contains a given concentration of one or more siloxanes and/or siloxane derivatives. The bed can be used for filtration purposes until determined to be exhausted, which occurs when the effluent siloxanes or siloxane derivatives concentration(s) matches that of the bed inlet. Once a bed is determined to be exhausted, the bed can be replaced with a fresh bed, and the exhausted bed can be regenerated.

[0048] Methods of Regenerating PSZs

[0049] Most zeolite materials are thermally stable and this can be advantageous for potential thermally based regeneration after the materials are determined to be exhausted (i.e., once the materials have reached their maximal potential for adsorption of siloxanes and/or derivatives thereof). PSZ UTD-1 (DON), for instance, is stable to at least 1000 C. Therefore, this material can be regenerated via thermal cycling under a flow of air or any other suitable gas after being exhausted with the uptake of siloxanes. In some embodiments, a temperature of about 250 C. can be used to desorb DMSO.sub.2, while a much lower temperature range (about 200 C.) can be used to eliminate linear siloxanes like MMST, DMSD, and TMS.

[0050] Another contemplated regeneration strategy includes removal of siloxanes and/or derivatives thereof from contemplated adsorbents by exposing the adsorbents to changes in pH. Based on Zeta potential measurements (see FIG. 9), acidic conditions change the adsorbent surface charge to positive; furthermore, the added protons would interact with the OH groups of the structure of materials like UTD-1, favoring the regeneration of the material. Also, it is important to state that the material structure and performance would not be affected by acidic conditions, since UTD-1 is already subjected to acidic conditions during its synthesis.

[0051] The nanoporous PSZ adsorbents as described herein advantageously possess excellent thermal stability. This is important as it allows facile siloxane desorption without degradation of the underlying PSZ adsorbent. Accordingly, in certain embodiments as otherwise described herein, the nanoporous PSZ adsorbent comprises thermal stability up to a temperature of at least 450 C., e.g., of at least 500 C., or 550 C., or 600 C.

EXAMPLES

[0052] The Examples that follow are illustrative of specific embodiments of the disclosure, and various uses thereof. They are set forth for explanatory purposes only and should not be construed as limiting the scope of the disclosure in any way.

Example 1: Formation and Characterization of PSZs

Introduction

[0053] The present invention identified candidate PSZs for removal of siloxane contaminants for the environment.

[0054] Methods

[0055] Grand Canonical Monte Carlo (GCMC) simulations in the sorption module of Materials Studio 8.0 were conducted to evaluate the absorption performance of 232 randomly selected zeolites towards the linear methyl-siloxanes of monomethylsilanetriol (MMST), trimethylsilanol (TMS), and dimethylsilanediol (DMSD) and the siloxane derivative species dimethylsulfone (DMSO.sub.2) (see Lin e/al., Machine-learning-assisted screening of pure-silica zeolites for effective removal of linear siloxanes, J. Mater. Chem. A, 2020, 8, 3228). GCMC is a statistical-mechanical approach, in which the adsorption process is investigated relying on random sampling and probabilistic interpretation in the sorbent framework.

[0056] Average adsorption loading (molecules nm.sup.3) and adsorption energy (kcal mol.sup.1) were calculated, and the 10 lowest-energy adsorption geometries of each adsorption system (where more substantial adsorption loading and higher adsorption energy indicate better adsorption performances) were identified. GCMC simulations were carried out in a zeolite cell containing a section of the model pore, and each cell had a length of around 4.0 nm, which was sufficiently large to make the effect of finite system size negligible. The systems were equilibrated for 100,000 GCMC steps, and data were collected for another 1,000,000 production steps to get the average amount adsorbed. All the GCMC simulations were carried out at a temperature of 298 K and a fixed pressure of 101.33 kPa with the Metropolis Monte Carlo method and COMPASS forcefield.

[0057] Production of PSZs

[0058] PSZs were prepared via templated hydrothermal crystallization, starting with saturated gels containing the silicon and oxygen sources and a structure directing agent (SDA, many types can be used). The gels and the SDA mixtures were then placed inside Teflon lined autoclaves, sealed, and heated to a particular temperature, usually above the boiling point of the solvent medium (i.e., water). It should be noted that the heat source maybe a traditional oven or it could be based on microwave assisted heating. The preparation could last from several hours to several days. Upon full crystallization, the solids are recovered via centrifugation and/or filtration. The solids were cleaned with pure, deionized, distilled water to assist in the removal of unreacted species and impurities. The recovered solids can be dried overnight using heat sources, such as a forced convection oven.

[0059] The SDA is subsequently removed to expose the micro and/or mesoporosity of the PSZs. Its removal may be accomplished via thermal calcination and pyrolysis of the as-prepared PSZ solids. Depending on the nature of the SDA, acid or solvent treatments may be required to remove inorganic portions or residues generated during the decomposition of the SDA.

[0060] Equilibrium adsorption tests were conducted by mixing the adsorbent (i.e., PSZ) with aqueous siloxane solutions (i.e., 10-200 L.sup.1) inside borosilicates tubes. The tubes were shaken for a certain amount of time at neutral pH. The liquid and solid phases were separated via centrifugation, and aliquots were transferred afterward to glass vials and sealed with an open-top polypropylene closure (with PTFE/silicone lined). Tests were conducted in triplicate and the equilibrium concentration of siloxane in the liquid phase was estimated using a Total Organic Carbon (TOC) analyzer following standard procedures. The amounts of adsorbed siloxanes were calculated based on a mass balance:

[00001]$q_e=\frac{V_i\left(C_i-C_e\right)}{m_{\mathrm{ads}}}$

where q.sub.e is the siloxane adsorbed amount (mg g.sup.1), C.sub.i is the initial siloxane concentration in solution (mg L.sup.1), and C.sub.e is the concentration of siloxane at equilibrium (mg L.sup.1), V.sub.i is the liquid volume of the siloxane solution (L), and m.sub.adx is the mass of the adsorbent (g).

[0061] Results

[0062] FIG. 1 shows adsorption energy versus adsorption loading profiles for various PSZs as calculated from Grand Canonical Monte Carlo (GC-MC) simulations. A total of 232 zeolitic materials were tested and Table No. 1 lists them by the crystal topology three-letter code assigned by the International Zeolite Association. Table No. 2 lists the framework topologies of zeolites that exhibited above average adsorption energies and loadings for at least two of the siloxane contaminants evaluated (i.e., MMST, DMSD, TMS, and DMSO.sub.2).

TABLE-US-00001 TABLE NO. 1 Topology codes of tested PSZs. ABW ACO AEI AEL AEN AET AFG AFI AFN AFO AFR AFS AFT AFV AFX AFY AHT ANA APC APD AST ASV ATN ATO ATS ATT ATV AVL AWO AWW BCT BEA BEC BIK BOF BOG BOZ BPH BRE BSV CAN CAS CDO CFI CGF CGS CHA CHI CLO CON CSV CZP DAC DDR DFO DFT DOH DON EAB EDI BEI EMT EON EPI ERI ESV ETL ETR EUO EWT EZT FAR FAU FER FRA GIS GIU GME GON GOO HEU IFO IFR IFU IFW IFY IHW IMF IRN IRR IRY ISV ITE ITG ITH ITN ITR ITT ITV ITW IWR IWS IWV IWW JBW JNT JOZ JRY JSN JSR JST JSW KFI LAU LEV LIO LIT LOS LOV LTA LTF LTJ LTL LTN MAR MAZ MEI MEL MEP MER MFI MFS MON MOR MOZ MRE MSE MSO MTF MTN MTT MTW MVY MWF MWW NAB NAT NES NON NPO NPT NSI OBW OFF OKO OSI OSO OWE PAR PAU PCR PHI PON POS PSI PUN RHO RON RRO RSN RTE RTH RUT RWR RWY SAF SAO SAS SAT SAV SBE SBN SBS SBT SEW SFE SFF SFG SFH SFN SFO SFS SFV SFW SGT SIV SOD SOF SOS SSF SSO SSY STF STI STO STT STW SVR SVV SZR TER THO TOL TON TSC TUN UEI UFI UOS UOV UOZ USI UTL UWY VET VFI VNI VSV WEI WEN YUG ZON

TABLE-US-00002 TABLE NO. 2 Topology codes of tested PSZs that exhibited above average adsorption energies. AEL AFG AFI AFN AFO AFT AFV AFX AST ASV ATO AVL AWW BEA BEC BOF BOG BPH BRE CDO CGS CHA CON CSV DDR DFO DOH DON EAB EEI ERI ESV ETL ETR EUO EZT FAR FER GIU GME GON HEU IFR IFY IHW ISV ITG ITH ITN ITR IWR JST JSW KFI LAU LOS MAZ MEI MEL MER MFI MOZ MRE MSE MSO MTF MTN MTT MTW MWW NES NON NPT OFF OKO OSI OWE PCR PHI PON POS PSI PUN RTE RUT SAO SAT SBS SEW SFG SFS SGT SIV SSO STI STT SVR SVV TSC TUN UFI UOS UOV UOZ USI UWY VET ZON

[0063] Guided by computational driven screening, a nanoporous PSZ adsorbent was chosen for synthesis to test its ability to remove siloxanes from water. The PSZ adsorbent was a material with a DON phase (PSZ-DON, see FIG. 2). The PSZ-DON was prepared using bis (pentamethyl-cyclopentadienyl), cobalt (III) hydroxide ([(Cp*).sub.2Co]OH) as a structure directing agent (SDA) (Freyhardt et al., 1996). The final PSZ-DON product was a crystalline powder with a chemical framework Composition [Si.sub.64O.sub.128] besides the SDA. Upon removal of the SDA, the PSZ-DON had a surface area of 400 m g.sup.1 and an average pore size of about 12 . The PSZ-DON demonstrated thermal stability up to about 600 C.

[0064] The PSZ-DON provided advantages over other zeolites based on framework compositional contrast (i.e., an aluminophosphate or aluminosilicates vs. a PSZ). In addition, it could be successfully produced in a pure phase and in amounts required to perform uptake tests. Other materials presented in the results (i.e., FAU and PSI) highlighted the need for a specific type of composition (surface, etc.) in order to achieve the best adsorption amounts. While not wishing to be bound by theory, it appears that structural faulting in DON advantageously leads to the formation of surface silanol sites that also interact selectively with TMS siloxanes.

[0065] FIG. 3 shows single component equilibrium adsorption isotherms for DMSD, MMST, or DMSD onto the PSZ-DON at pH7 and ambient temperature. The PSZ-DON was capable of removing up to 3 wt. % TMS at saturation, a capacity that is an order of magnitude higher compared to the other tested siloxanes.

[0066] Another adsorbent synthesized and tested was one with a PSI phase (PSI, see FIG. 4). PSI was prepared in a two step synthesis, the first involving a hydrothermal aging process using diethylamine as a SDA and a second step of thermal treatment crystal transformation at 550 C. (Lee et al., 2014). The resulting material, however, had a framework composition [Al.sub.72P.sub.72O.sub.228] and a surface of 91 m.sup.2 g.sup.1. FIG. 5 shows single component adsorption isotherms gathered at ambient temperature for PSI. The adsorption capacities are considerable, but not as large as those of PSZ-DON (FIG. 2). The lesser adsorption capacity of PSI is probably due to its aluminum/phosphorus content, which results in a lesser degree of hydrophobicity compared to the silica rich framework of PSZs. Nevertheless, the PSI material has selectivity toward TMS over DMSD.

[0067] A direct comparison of single component adsorption performance of PSZ-DON versus PSI is presented in the adsorption isotherms shown in FIG. 6. Furthermore, the adsorption loadings (ordinate axis) are presented as siloxane mass per adsorbent surface area. These data show that PSI, despite any hydrophobicity limitation due to framework composition, possesses a surface capable of undergoing significant interactions with siloxanes, such as TMS.

[0068] Evaluation of multi-component adsorption (i.e., simultaneous adsorption of contaminants) was evaluated via single point batch equilibration tests, for aqueous phase solutions containing initially about 1 mg carbon (C) L.sup.1(1 ppm) of each contaminant. DMSO.sub.2 was included in these tests, and the data also include a Faujasite zeolite (FAU) for comparison purposes. FAU has an average pore size of about 7 , and its framework includes not only silicon but also aluminum tetrahedra and, therefore, metal cations that balance its structural charge. FIGS. 7A-7B show evidence of co-adsorption, with TMS being the main driving force perhaps because of strong adsorbate-adsorbate interactions. In the case of binary mixtures (FIG. 7A), it is difficult to elucidate how much of the adsorbed amount corresponds to TMS versus the other contaminant (i.e., initial concentration of each adsorbate is 1 mg CL.sup.1). However, it is apparent from data gathered for a quaternary mixture of contaminants (FIG. 7B) and that of the binary systems that TMS is perhaps the main contributor to the substantial uptakes via co-adsorption. This is possibly attributable to the strong adsorbate-adsorbate interactions between TMS and other siloxanes.

[0069] In general, it appears that a silica-rich surface zeolite is appropriate for the removal of these contaminants and that water containing a mixture of said contaminants could be advantageously treated with a DON adsorbent when TMS is already present in the matrix (i.e., co-adsorption).

[0070] The embodiments illustratively described herein suitably can be practiced in the absence of any element or elements, limitation or limitations that are not specifically disclosed herein. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments claimed. Thus, it should be understood that although the present description has been specifically disclosed by embodiments, optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of these embodiments as defined by the description and the appended claims. Although some aspects of the present disclosure can be identified herein as particularly advantageous, it is contemplated that the present disclosure is not limited to these particular aspects of the disclosure.

[0071] Claims or descriptions that include or between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The disclosure includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[0072] Furthermore, the disclosure encompasses all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim. Where elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group.

[0073] It should it be understood that, in general, where the disclosure, or aspects of the disclosure, is/are referred to as comprising particular elements and/or features, certain embodiments of the disclosure or aspects of the disclosure consist, or consist essentially of, such elements and/or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein.

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