Kinetic modeling of deep hydrodesulfurization of dibenzothiophenes on NiMo/alumina catalysts modified by phosphorus

Mello, Matheus Dorneles de; Braggio, Flávia de Almeida; Magalhães, Bruno da Costa; Zotin, José Luiz; Silva, Mônica Antunes Pereira da

doi:10.1016/j.fuproc.2018.04.010

Cited by 33 publications

(7 citation statements)

References 48 publications

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“…For example, in the 90s, one unit that was designed to produce a targeted diesel with 1500-350 ppm S; now, the same unit has to produce <10 ppm S ULSD without sacrificing production and achieving API (American petroleum institute) uplift in the diesel product. On the other hand, the so-called ultra-deep hydrodesulfurization is needed to reach the sulfur content limits (present and future) [11][12][13]. Therefore, highly active catalysts seem to be the critical factor to deal with the bulk sulfur compounds and remove them selectively from refractory alkyl-substituted dibenzothiophene (DBT) molecules such as 4,6 dimethyl DBT (4,6-DM-DBT), 4-methyl 6-ethyl DBT (4M,6E-DBT), 4,6 dibutyl DBT (4,6-DB-DBT), or 4,6 dipropyl DBT (4,6-DP-DBT) [5,14].…”

Section: Introductionmentioning

confidence: 99%

Recent Insights in Transition Metal Sulfide Hydrodesulfurization Catalysts for the Production of Ultra Low Sulfur Diesel: A Short Review

et al. 2019

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The literature from the past few years dealing with hydrodesulfurization catalysts to deeply remove the sulfur-containing compounds in fuels is reviewed in this communication. We focus on the typical transition metal sulfides (TMS) Ni/Co-promoted Mo, W-based bi- and tri-metallic catalysts for selective removal of sulfur from typical refractory compounds. This review is separated into three very specific topics of the catalysts to produce ultra-low sulfur diesel. The first issue is the supported catalysts; the second, the self-supported or unsupported catalysts and finally, a brief discussion about the theoretical studies. We also inspect some details about the effect of support, the use of organic and inorganic additives and aspects related to the preparation of unsupported catalysts. We discuss some hot topics and details of the unsupported catalyst preparation that could influence the sulfur removal capacity of specific systems. Parameters such as surface acidity, dispersion, morphological changes of the active phases, and the promotion effect are the common factors discussed in the vast majority of present-day research. We conclude from this review that hydrodesulfurization performance of TMS catalysts supported or unsupported may be improved by using new methodologies, both experimental and theoretical, to fulfill the societal needs of ultra-low sulfur fuels, which more stringent future regulations will require.

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Section: Introductionmentioning

confidence: 99%

Recent Insights in Transition Metal Sulfide Hydrodesulfurization Catalysts for the Production of Ultra Low Sulfur Diesel: A Short Review

et al. 2019

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“…Arrhenius equation parameters, such as the activation energy (E HDS ) and pre-exponential factor (A) are determined. (6) where R is the universal gas constant, and T is the reaction temperature.…”

Section: Kinetic Studiesmentioning

confidence: 99%

“…Alumina has been widely applied commercially as an excellent support for such sulfides [3]. Hydrodesulfurization (HDS), the catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, occur through two main pathways: direct desulfurization (DDS), with the cleavage of C-S bond, or hydrogenation (HYD), which involves the formation of partially hydrogenated intermediates which further react to cyclohexylbenzene and bicyclohexyl [4][5][6]. The model compounds most frequently used, in order to develop kinetic expressions and reaction pathways that describe the HDS process, are heteroatomic aromatics (thiophenes): thiophene, benzothiophene and dibenzothiophene.…”

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confidence: 99%

“…Although, as a class, these are the least reactive, they are also the most prevalent organosulfur compounds found in the heavier feedstocks currently being introduced and are therefore viewed as better analogs for the actual industrial HDS process [7]. Thiophene and DBT reacts preferentially through DDS route, whereas DMDBT hydrodesulfurization occurs predominantly via HYD route [6,[8][9]. A lot of kinetic studies have been carried out for compounds such as thiophenes, benzothiophene, dibenzothiophene and alkyl-dibenzothiophenes.…”

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confidence: 99%

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Comparative Study Between two Reaction Kinetic Mechanisms of Thiophene Hydrodesulphurization over CoMo /gama - Al2O3 Supported Catalyst

Doukeh¹,

Bombos²,

Bolocan³

2019

Rev. Chim.

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The kinetic study of the thiophene hydrodesulphurisation process was carried out for CoMo/gama-Al2O3 catalyst, at temperatures between 175 and 275 �C, pressure ranged from 30bar to 60 bar and the liquid hourly space velocity from 1h-1 to 4 h-1. For the reaction mechanism, the Langmuir-Hinshelwood-Hougen-Watson model (LHHW) was used and two kinetic models were proposed: the first model, that considered that H2 is adsorbed on a different type of active center than thiophene and the second model, that considered that the two reactants are adsorbed on the same type of active sites. The values obtained for the average relative error (ARE) and the correlation coefficient between the experimental and the calculated data (R2) indicate that the Langmuir-Hinshelwood model, describing the adsorption on two active sites, best describes the kinetics of the thiophene hydrodesulfurization reaction over CoMo/gama-Al2O3 tested catalyst.

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“…On the other hand, environmental regulations necessitate limiting the amount of the sulfur component present in the fuel [8][9][10][11][12][13]. As a result, a decrease in sulfur content of re nery feedstock and fuel products is of environmental and industrial importance in the petroleum re ning industry [14][15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Comparison of γ and δ-Al2O3 supported CoMo catalysts in the hydrodesulfurization of straight-run gas oil

2019

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The e ect of two di erent crystal species of alumina on the hydrodesulfurization activity of the corresponding CoMo catalysts was studied. Cylindrical extruded alumina with two di erent crystal structures, i.e., -Al2O3 and -Al2O3, was prepared using boehmite and nitric acid as a peptizing agent by calcination at 550 C and 900 C, respectively. Al2O3 supports were impregnated with 9 wt.% of Mo and 2 wt.% Co by an incipient wetness impregnation method. CoMo/Al 2 O 3 catalysts were used for hydrodesulfurization (HDS) and hydrodenitri cation (HDN) of Iranian Straight-Run Gas Oil (ISRGO). The supports and catalysts were characterized by nitrogen adsorptiondesorption isotherm, XRD, UV-vis-DRS, TPD, TPR, CO chemisorption, and ICP-OES. The HDS activity of CoMo/ -Al2O3 catalyst was higher than that of CoMo/ -Al2O3 and was found to be 95.74%. This result was obtained from the formation of larger CoMoO 4 and MoO 3 crystals in CoMo/ -Al 2 O 3 catalyst, thus reducing the active metal phase dispersion and the performance of the catalyst. The HDS activity of CoMo/ -Al2O3 catalyst was remarkable as the metal content of the catalyst was low. The HDN activity of CoMo/ -Al2O3 was also about 66%.

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Kinetic modeling of deep hydrodesulfurization of dibenzothiophenes on NiMo/alumina catalysts modified by phosphorus

Cited by 33 publications

References 48 publications

Recent Insights in Transition Metal Sulfide Hydrodesulfurization Catalysts for the Production of Ultra Low Sulfur Diesel: A Short Review

Recent Insights in Transition Metal Sulfide Hydrodesulfurization Catalysts for the Production of Ultra Low Sulfur Diesel: A Short Review

Comparative Study Between two Reaction Kinetic Mechanisms of Thiophene Hydrodesulphurization over CoMo /gama - Al2O3 Supported Catalyst

Comparison of γ and δ-Al2O3 supported CoMo catalysts in the hydrodesulfurization of straight-run gas oil

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