Effect of H2S on the stability of CoMo/Al2O3 catalysts during hydrodeoxygenation

Viljava, Tuula-Riitta; Komulainen, R.S.; Krause, A.O.I.

doi:10.1016/s0920-5861(00)00320-5

Cited by 175 publications

(102 citation statements)

References 13 publications

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“…Previous work has also shown that oxygen atoms from the HDO reaction can replace framework S-atoms in the MoS2 with insufficient sulfur in the feed [47,[55][56][57][58]. The natural content of sulfur in bio-oil does not appear sufficient for sustaining the catalyst in the active form during operation and addition of DMDS/H2S is consequently recommended during HDO of a real bio-oil feed.…”

Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

“…It has previously been described that co-feeding H2S during HDO on MoS2 type catalysts results in a competitive adsorption of H2S and the oxy-compound [24,46,55,59]. Based on DFT calculations, Badawi et al [23] found that the adsorption of H2S and H2O was stronger on CoMoS sites compared to phenol and these species therefore have an inhibiting effect on the catalyst.…”

Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

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Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Mortensen

Gardini

Damsgaard

et al. 2016

Applied Catalysis A: General

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Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol, Applied Catalysis A, General http://dx.doi.org/10. 1016/j.apcata.2016.06.002 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Graphical abstractHighlights  Impurities as Cl, S, and K found in bio-oil will deactivate or inhibit MoS2-type catalyst by competing for the active sites  MoS2-based catalysts will produce sulfur containing hydrocarbons during HDO, but these can be removed again if a sufficiently high residence time is used enabling desulfurization of the product  Chlorine binds more strongly to the active sites of MoS2 based catalysts compared to H2O and H2S, while K irreversibly deactivates the catalyst 3 AbstractThe stability of Ni-MoS2/ZrO2 toward water, potassium, and chlorine containing compounds during hydrodeoxygenation (HDO) of a mixture of phenol and 1-octanol was investigated in a high pressure gas and liquid continuous flow fixed bed setup at 280°C and 100 bar. To maintain the stability of the catalyst, sufficient co-feeding of a sulfur source was necessary to avoid oxidation of the sulfide phase by oxygen replacement of the edge sulfur atoms in the MoS2 structure. However, the addition of sulfur to the feed gas resulted in the formation of sulfur containing compounds, mainly thiols, in the oil product if the residence time was too low. At a weight hourly space velocity (WHSV) of 4.9 h -1 the sulfur content in the liquid product was 980 ppm by weight, but this could be decreased to 5 ppm at a WHSV of 1.4 h -1 . A high co-feed of sulfur was needed when water was present in the feed and the H2O/H2S molar ratio should be below ca. 10 to maintain a decent stability of the catalyst. Chlorine containing compounds caused a reversible deactivation of the catalyst when co-fed to the reactor, where the catalytic activity could be completely regained when removing it from the feed. Commonly, chlorine, H2O, and H2S all inhibited the activity of the catalyst by competing for the active sites, with chlorine being by far the strongest inhibitor and H2S and H2O of roughly the same strength. Dissimilar, potassium was a severe poison and irreversibly deactivated the catalyst to <5% degree of deoxygenation when impregnated on the catalyst in a stoichiometric ratio relative to the active metal. This deactivation was a result of adsorption of potassium on the edge vacancy sites of the MoS2 slabs.

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Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Mortensen

Gardini

Damsgaard

et al. 2016

Applied Catalysis A: General

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“…[7][8][9][10][11][12][13][14] While the high price of the noble metals can be avoided by using the sulfided catalysts, slow desulfurization reduces their activity and contaminates the fuel. [7,9,15] Furthermore, these catalysts have shown poor selectivity, favoring cracking and decarbonylation over hydrodeoxygenation to produce broad hydrocarbon distributions. [16] In an effort to establish a more economical sulfur-free catalyst to upgrade renewable oils, Lercher has demonstrated the hydrodeoxygenation of microalgae oil to alkanes by cascade reactions on bifunctional catalysts based on Ni and an acidic zeolite.…”

Section: Introductionmentioning

confidence: 99%

Supported iron nanoparticles for the hydrodeoxygenation of microalgal oil to green diesel

Kandel

Anderegg

Nelson

et al. 2014

Journal of Catalysis

140

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Iron nanoparticles supported on mesoporous silica nanoparticles (Fe-MSN) catalyze the hydrotreatment of fatty acids with high selectivity for hydrodeoxygenation over decarbonylation and hydrocracking. The catalysis is likely to involve a reverse Mars-Van Krevelen mechanism, in which the surface of iron is partially oxidized by the carboxylic groups of the substrate during the reaction. The strength of the metal-oxygen bonds that are formed affects the residence time of the reactants facilitating the successive conversion of carboxyl first into carbonyl and then into alcohol intermediates, thus dictating the selectivity of the process. The selectivity is also affected by the pretreatment of Fe-MSN, the more reduced the catalyst the higher the yield of hydrodeoxygenation product. Fe-MSN catalyzes the conversion of crude microalgal oil into dieselrange hydrocarbons. Disciplines Materials Chemistry | Other Chemistry | Physical ChemistryComments NOTICE: this is the author's version of a work that was accepted for publication in Journal of Catalysis. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Catalysis, [314, (2014)

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“…Peneliti Viljava et al (2000) telah melakukan reaksi deoksigenasi anisol menggunakan katalis CoMo/Al 2 O 3 , dihasilkan rendemen produk total yaitu 96,8 %. Sementara Li et al (2011) Mora et al (2014) tersebut, berhasil diperoleh produk bebas oksigen yaitu benzena, dan sikloheksana.…”

Section: Pendahuluanunclassified

CATALYTIC ACTIVITY CoMo/USY ON DEOXYGENATION REACTION OF 4-METHOXYPHENOL IN BATCH REACTOR

2017

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ABSTRAKPenelitian ini bertujuan untuk mengetahui pengaruh jenis katalis CoMo/USY dan waktu terhadap produk pada reaksi deoksigenasi 4-metoksi fenol. Jenis katalis yang digunakan adalah CoMo/USY, Co-Mo/USY, dan Mo-Co/USY. Produk yang terbentuk dianalisis menggunakan kromatografi gas (GC) dan kromatografi gas-spektrometer massa (GC-MS). Aktivitas katalis Co-Mo/USY lebih tinggi daripada CoMo/USY, dan MoCo/USY, dilihat dari nilai rendemen total dan selektivitasnya. Katalis Co-Mo/USY mengalami peningkatan rendemen total yang signifikan (dari 3,71 % menjadi 9,41 %) seiring berjalannya waktu. Katalis Co-Mo/USY memiliki selektivitas tertinggi terhadap produk 1,4-dimetoksi benzena saat waktu reaksi 1 jam (0,92 %) dan selektivitas terhadap produk 1,4-dihidroksi benzena saat 2 jam (0,43 %).Kata kunci: aktivitas katalitik, deoksigenasi, katalis CoMo/USY, 4-metoksi fenol. ABSTRACTThis research was conducted to study the effect of catalyst type of CoMo/USY and the reaction time on the deoxygenation reaction of 4-methoxyphenol. The catalyst type used were CoMo/USY, Co-Mo/USY, and Mo-Co/USY. The product was analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The activity of the Co-Mo/USY catalyst is higher than CoMo/USY and Mo-Co/USY, it can be seen from the value of total yield and the selectivity. The Co-Mo/USY catalysts shows a significant increasing on the total yield percentage (from 3.71 % to 9.41 %) during catalytic testing. The Co-Mo/USY catalyst has a highest selectivity toward 1,4-dimethoxybenzene product when the reaction time was one hour (0.92 %) and selectivity toward 1,4-dihidroxybenzene when reaction time two hours (0.43 %).

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Effect of H2S on the stability of CoMo/Al2O3 catalysts during hydrodeoxygenation

Cited by 175 publications

References 13 publications

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Supported iron nanoparticles for the hydrodeoxygenation of microalgal oil to green diesel

CATALYTIC ACTIVITY CoMo/USY ON DEOXYGENATION REACTION OF 4-METHOXYPHENOL IN BATCH REACTOR

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