Desulfurization of Commercial Liquid Fuels by Selective Adsorption via π-Complexation with Cu(I)−Y Zeolite

Hernández‐Maldonado, Arturo J.; Yang, Ralph T.

doi:10.1021/ie0301132

Cited by 218 publications

(205 citation statements)

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“…N-hexane (AR, Sinopharm Chemical Reagent Lo., Ltd.) was used as model liquid fuel, and thiophene (AR, Sinopharm Chemical Reagent Lo., Ltd.), a major sulfur-containing compound in fossil fuel (Dai et al, 2008), was added to n-hexane to vary the sulfur content in fuel as used in previous studies (Bladt et al, 2012;Dai et al, 2008;GÜLder and Glavin CEvski, 1991;Hernandez-Maldonado and Yang, 2003).…”

Section: Soot Productionmentioning

confidence: 99%

Influence of sulfur in fuel on the properties of diffusion flame soot

Zhao

2016

Atmospheric Environment

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h i g h l i g h t sLean flame soot was influenced more by sulfur in fuel than rich flame soot. Sulfate species were mainly formed on the surface of soot. The diameter of primary lean flame soot from high sulfur content fuel increased. The hygroscopicity of lean flame soot from high sulfur content fuel increased. a r t i c l e i n f o a b s t r a c tPrevious studies indicate that sulfur in fuel affects the hygroscopicity of soot. However, the issue of the effect of sulfur in fuel on soot properties is not fully understood. Here, the properties of soot prepared from fuel with a variable sulfur content were investigated under lean and rich flame conditions. Lean flame soot was influenced more by sulfur in fuel than rich flame soot. The majority of sulfur in fuel in lean flame was converted to gaseous SO 2 , while a small fraction appeared as sulfate and bisulfate (referred to as sulfate species) in soot. As the sulfur content in fuel increased, sulfate species in lean flame soot increased nonlinearly, while sulfate species on the surface of lean flame soot increased linearly. The hygroscopicity of lean flame soot from sulfur-containing fuel was enhanced mainly due to sulfate species. Meanwhile, more alkynes were formed in lean flame. The diameter of primary lean flame soot particles increased and accumulation mode particle number concentrations of lean flame soot from sulfurcontaining fuel increased as a result of more alkynes. Because the potential effects of soot particles on air pollution development greatly depend on the soot properties, which are related to both chemical aging and combustion conditions, this work will aid in understanding the impacts of soot on air quality and climate.

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Section: Soot Productionmentioning

confidence: 99%

Influence of sulfur in fuel on the properties of diffusion flame soot

Zhao

2016

Atmospheric Environment

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“…-complexation. 21 Figures 13 and 14 show the heats of adsorption for n-octane and thiophene on these two sorbents, which are also included in There was also additional heat released with the increased loading due to increased sorbate-sorbate van der Waals interactions.…”

Section: Heats Of Adsorption From Vapor Phasementioning

confidence: 99%

Adsorption and Ultrasound-Assisted Sorbent Regeneration

Wang¹,

Ma²,

Yang³

2006

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This work was conducted for the department of Energy. In this work, we developed a class of new sorbents that were highly sulfur sepective and had high sulfur capacities. The study consisted of two sections. Development of the new sorbents is described in Section 1, and Section was a fundamental study, conducted for a better understanding for desulfurization of jet fuels. More details of the results are given blow separately for the two sections. Section 1: Desulfurization of Model Jet Fuels by Adsorption on Carbon-based Sorbents and Ultrasound-Assisted Sorbent RegenerationSeveral high-sulfur-capacity carbon-based adsorbents, CuCl/AC, PdCl 2 /AC, and Pd/AC (where AC denotes activated carbon), were studied for desulfurization of a model jet fuel by selective adsorption of thiophenic molecules. The model jet fuel (150 ppmw-S BT and 250 ppmw-S MBT in 19.75 wt% benzene + 80 wt% n-octane containing 700 ppmw naphthalene) was formulated such that it represented all jet fuels well. In addition, a commercial jet fuel, JP-5 was included in the tests. Comparisons with γ-Al 2 O 3 support and desulfurization of a commercial jet fuel were also studied. The results showed that the selective sulfur adsorption capacity of PdCl 2 was higher than that of CuCl and Pd 0 , in agreement with molecular orbital results. It was also found that the activated carbon is the best support for π-complexation sorbents to remove sulfur-containing compounds, i.e. benzothiophene and methylbenzothiophene. Among all the adsorbents studied, PdCl 2 /AC had the highest capacity for desulfurization. A significant synergistic effect was 3 observed between the carbon substrate and the supported π-complexation sorbent, and this effect was explained by a geometric effect. The saturated sorbent was regenerated by desorption assisted by ultrasound with a solvent of 30 wt% benzene and 70 wt% noctane. The results showed that the amount of sulfur desorbed was higher with ultrasound, 65 wt% desorption vs. 45 wt% without ultrasound in a static system at 50 o C. Section 2: Selective Adsorption of Sulfur Compounds: Isotherms, Heats and Relationship between Adsorption from Vapor and Liquid SolutionThis was a basic study in order to understand and better design sorbents for desulfurization of jet fuels. Adsorption isotherms were measured for thiophenic sulfur compounds, thiophene (T), benzothiopnene (BT), 2-methyl benzothiophene (2-MBT) and dibenzothiophene (DBT), from their binary solutions in n-octane. Two sulfur-selective, π-complexation sorbents were studied: Cu(I)-Y zeolite and PdCl 2 impregnated on activated carbon (PdCl 2 /AC). Vapor-phase isotherms of n-octane and thiophene were also measured. The selectivity of adsorption from liquid solutions followed the order of: T < BT < 2-MBT < DBT for PdCl 2 /AC, and T < DBT < 2-MBT < BT for Cu(I)-Y zeolite. The adsorption bond energies, which approximate the heats of vapor-phase adsorption, followed the order: T < BT < 2-MBT < DBT. This order was not followed for adsorption from liquid solutions on Cu-Y zeolite...

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“…Therefore, to reduce the sulfur content in gasoline below 10 ppm, it is necessary to increase the severity of HDS process, which results in the excessive saturation of olefins, causing the loss in octane value of gasoline. Alternative technologies, such as adsorption desulfurization [7][8][9], oxidation desulfurization [10,11], extraction [12,13] and bio-catalytic treatment [14,15] have been developed. Among them, the reactive adsorption desulfurization (RADS) using a solid adsorbent is considered to be the most effective approach for the ultra-deep desulfurization of gasoline [16].…”

Section: Introductionmentioning

confidence: 99%

“…Following this pioneer work, a significant amount of efforts have been made for the development of Ni/ZnO based adsorbents [20][21][22]. By studying the desulfurization mechanism of thiophenic compounds [9,22,23], the RADS process using Ni/ZnO adsorbent was found to combine advantages of both HDS and adsorption desulfurization [24][25][26]. As revealed, organic sulfur compounds in the feed firstly decompose on the surface of Ni particles to form Ni 3 S 2 [27].…”

Section: Introductionmentioning

confidence: 99%

Remarkably high performance of clew-like ZnO superstructure in reactive adsorption desulfurization

Peng

Liu

et al. 2017

Sci. China Mater.

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In this study, a clew-like ZnO superstructure was synthesized by a copolymer-controlled self-assembly homogeneous precipitation method. Ni was impregnated to the clew-like ZnO superstructure to obtain Ni/ZnO adsorbents. The synthesized materials were characterized by scanning electron microscopy, transmission electron microscopy, N 2 sorption, X-ray diffraction, Fourier transform infrared spectrometry, and H 2 -temperature programmed reduction techniques. The reactive adsorption desulfurization (RADS) performance of the adsorbents was evaluated in a fixed bed reactor using thiophene in n-octane as a model fuel. Sample Ni/ZnO-4h exhibits a remarkably high performance with a sulfur capacity of 189.1 mg S g -1 , which is above 6 times that of the one prepared with commercial ZnO. Characterization results show that the morphology changes from micro-clews to large solid sticks with the increase of the crystallization time.The loose and open architecture of the clew-like ZnO superstructure facilitates the diffusion of reactants/products, and prevents the adsorbent particles from breakage by supplying space for the volume expansion during the RADS process. The small nanoparticles in ZnO nanostrips result in a high sulfur adsorption capacity and also favor the dispersion of Ni, leading to an excellent RADS performance.

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Desulfurization of Commercial Liquid Fuels by Selective Adsorption via π-Complexation with Cu(I)−Y Zeolite

Cited by 218 publications

References 35 publications

Influence of sulfur in fuel on the properties of diffusion flame soot

Influence of sulfur in fuel on the properties of diffusion flame soot

Adsorption and Ultrasound-Assisted Sorbent Regeneration

Remarkably high performance of clew-like ZnO superstructure in reactive adsorption desulfurization

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