Copper Removal from Fuel by Solid-Supported Polyamine Chelating Agents

Puranik, Dhanajay B.; Guo, Yan; Singh, Alok; Morris, Robert E.; Huang, Angus; Salvucci, L.; Kamin, R.; David, Vikram A.; Chang, Eddie L.

doi:10.1021/ef980006y

Cited by 6 publications

(7 citation statements)

References 20 publications

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“…Most studies involving silica-based materials covalently functionalized with cyclam derivatives have been performed by the groups of Guilard, ,,− Corriu, − and some others. ,− Materials were either silica gel bound cyclam (obtained by grafting or sol−gel synthesis) − ,− ,− or cyclam-functionalized mesoporous solids (grafted or co-condensed with cyclam groups attached to the surface of mesochannels, or as periodic mesoporous organosilicas containing cyclam moieties in the mesopore walls). ,− ,, They have found applications mainly in catalysis, , chromatography, ,, or gas adsorption. ,, Metal-loaded hybrid materials incorporating metal cations such as Cu(II), Co(II), or Eu(III) have also been prepared and characterized. It was suggested that their coordination chemistry in the solid differs from that in solution. ,,, Metalation can be performed before synthesis of the hybrid (i.e., on the cyclam-functionalized alkoxysilane precursor) or afterward by allowing the materials to react with solutions containing the metal ions.…”

Section: Introductionmentioning

confidence: 99%

“…Most studies involving silica-based materials covalently functionalized with cyclam derivatives have been performed by the groups of Guilard, 38,39,[43][44][45][46][47][48] Corriu, [46][47][48][49][50][51][52][53] and some others. 37,[54][55][56][57][58] Materials were either silica gel bound cyclam (obtained by grafting or sol-gel synthesis) [37][38][39][45][46][47][48][49][54][55][56][57] or cyclam-functionalized mesoporous solids (grafted or co-condensed with cyclam groups attached to the surface of mesochannels, or as periodic mesoporous organosilicas containing cyclam moieties in the mesopore walls). 43,[50][51][52][53]58,59 They have found applications mainly in catalysis, 58,59 chromatography, 54,55,57 or gas adsorption.…”

Section: Introductionmentioning

confidence: 99%

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Factors Affecting Copper(II) Binding to Multiarmed Cyclam-Grafted Mesoporous Silica in Aqueous Solution

et al. 2009

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Single- as well as multi-anchored cyclam-functionalized silica samples have been prepared by grafting amorphous silica gel (K60) and mesostructured silica (SBA-15) with silylated cyclam precursors bearing one, two, or four triethoxysilyl groups, respectively ascribed to cyclam-mono, cyclam-di, and cyclam-tetra. Their reactivity toward copper(II) has been thoroughly investigated in aqueous solution and discussed with respect to the number of arms tethering the ligand to the silica surface and the structural ordering of the adsorbent in terms of capacity, long-term stability, and speed of access to the binding sites. Less-than-complete metal ion uptake was always observed, even in excess of cyclam groups with respect to solution-phase Cu(II), suggesting lower stability of immobilized complexes relative to those in solution. Therefore, the number of arms attaching cyclam moieties to the silica walls (one, two, or four) was found to dramatically affect the binding properties of these hybrids toward copper(II), revealing significantly larger capacities when reducing the number of arms (less rigidity constraints in the macrocycle). In parallel, multiarm tethering resulted in better chemical resistance toward degradation as evidenced by UV-visible monitoring of Cu-cyclam complexes in solution (i.e., more ligand leaching from the adsorbent for singly tethered cyclam). On the other hand, electron spin resonance (ESR) experiments did not evidence significant differences between complexes bearing one, two, or four alkyl arms, since all Cu(II)-cyclam surface complexes were found to be hexacoordinated with a strong equatorial ligand field. Comparison of amorphous gels and mesostructured materials indicates that the binding properties of the adsorbents were hardly influenced by their level of ordering, suggesting that accessibility to the binding sites was not the limiting factor. Some advantage belonging to mesostructured adsorbents was however observed with respect to the rate of access to the active centers at pH values close to neutrality (due to faster mass transport), but this was no more the case when operating at lower pH values where the formation of the Cu-cyclam complex became the rate-determining step, as pointed out by electrochemistry.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Factors Affecting Copper(II) Binding to Multiarmed Cyclam-Grafted Mesoporous Silica in Aqueous Solution

et al. 2009

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“…The first method is usually costly and not always effective. The second method has been the subject of recent investigations, , but overall economic viability in full-scale commercial and military applications has yet to be clearly demonstrated. The last method is the one usually chosen, and is accomplished by using additives known as copper (or metal) deactivators that form complexes with the copper, rendering it catalytically inactive.…”

Section: Introductionmentioning

confidence: 99%

The Development and Use of Metal Deactivators in the Petroleum Industry: A Review

Waynick

2001

Energy Fuels

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The development of metal deactivator additives for the petroleum industry is reviewed from the first additive used in gasoline to the present. The chemistry of how these additives are thought to work is detailed and related to chemical structure. Discussions of the three classes of action attributed to metal deactivators: chelation, surface passivation, and bulk phase reactivity, are provided. In this regard, special emphasis is given to the metal deactivator N,N′-disalicylidine-1,2-propane diamine (MDA) in aviation turbine fuels. Previously reported work, especially work from 1991 to the present, investigating the impact of MDA on jet fuel thermal stability is reviewed. A discussion of the six classes of metal deactivators most commonly found in the literature is also provided.

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“…The majority of studies involving silica functionalised with macrocycles, such as cyclen and cyclam (Figure 4.2), were conducted by Guilard 123,[235][236][237][238][239][240][241] and Corriu 235,237,239,240,[242][243][244][245] , but a number of others [246][247][248][249][250][251] have contributed to the literature as well. These materials are mainly used for gas adsorption, catalysis, or chromatography.…”

Section: Incorporation Of Cu(ii)-ligand Complexesmentioning

confidence: 99%

“…At times, assumptions are made about the product without satisfactory final characterisation, and, in multiple cases, characterisation data of the modified silica are incomplete or absent. For instance, Puranik et al 248 and Bagnoud et al 255 infer the generation of the desired product from its ability to retain Cu(II), rather than from direct measurements and characterisation of the modified silica. For those studies in which data are reported, common characterisation techniques of the silica include FT-IR spectroscopy, CHN elemental analysis, microscopy, solid-state cross-polarisation magic angle spinning nuclear magnetic resonance spectroscopy (CP-MAS NMR), and Brunauer, Emmett, and Teller (BET) surface area measurements.…”

Section: Incorporation Of Cu(ii)-ligand Complexesmentioning

confidence: 99%

Selective Metal Coordination in Antifouling Coatings

Robinson¹

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<p>Marine biofouling is the accumulation of biological material (e.g. microorganisms, soft- and hard-fouling organisms) on the surface of an object submerged in seawater, and it remains a worldwide problem for shipping industries. The fouling of ship hulls results in a reduction of speed and manoeuvrability due to frictional drag, as well as increased fuel consumption and accelerated corrosion, and the exorbitant expenses and losses of efficiency attributed to biofouling have prompted the development of antifouling coatings. Current antifouling paints use copper as a biocidal agent, but copper-based paints are increasingly being banned due to environmental concerns about the non-target effects of leached copper. This project aims to circumvent these concerns and tightening regulations via a revolutionary concept: the development of marine antifouling paints that incorporate Cu(II)-selective ligands to draw the biocidal ingredient (i.e. Cu(II)) from seawater. A multistage strategy emerged for the development of this technology. First, criteria were established for the project’s ideal ligand, and ligands were synthesised or selected based on these criteria. Second, the ligands were incorporated in coatings through covalent modification of the paint binder or additives. Third, methodology was developed and implemented to test each coating’s ability to coordinate and retain Cu(II), as well as its subsequent ability to prevent microfouling by marine bacteria. The suitability of two ligand classes was assessed: acylhydrazones and tetraaza macrocycles, specifically cyclen. Unlike the acylhydrazones, cyclen met the established criteria and was initially evaluated as a curing agent and/or surface-modifier in a two-pack epoxy system with resin Epikote™ 235. However, the Cu(II)-loading by these coatings was relatively low, being at most ~0.05% w/w, and the modification of silica, a common paint additive, with cyclen was explored as an alternative formulation route. The method for the functionalisation of silica with cyclen was optimised, and the maximum Cu(II)-loading achieved by the product was 2.60% w/w. The cyclen-functionalised silica was incorporated on the surface of an epoxy coating, and a bacterial adherence assay was developed to assess the cellular attachment of marine bacterium Vibrio harveyi to this coating, which was found to be undeterred. Yet, the development of the strategy and testing methodology by which the project’s goals may be achieved provides a solid foundation for future work.</p>

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Copper Removal from Fuel by Solid-Supported Polyamine Chelating Agents

Cited by 6 publications

References 20 publications

Factors Affecting Copper(II) Binding to Multiarmed Cyclam-Grafted Mesoporous Silica in Aqueous Solution

Factors Affecting Copper(II) Binding to Multiarmed Cyclam-Grafted Mesoporous Silica in Aqueous Solution

The Development and Use of Metal Deactivators in the Petroleum Industry: A Review

Selective Metal Coordination in Antifouling Coatings

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