Catalytic hydrodenitrogenation of basic and non-basic nitrogen compounds in Athabasca bitumen distillates

Furimsky, Edward; Ranganathan, Ramaswami; Parsons, B I

doi:10.1016/0016-2361(78)90059-5

Cited by 22 publications

(13 citation statements)

References 5 publications

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“…The former catalyst was much more selective for HDN than was the NiMo/Al 2 O 3 catalyst. However, at 13.7 MPa and 673 K this, trend was reversed (498). However, at 13.7 MPa and 673 K this, trend was reversed (498).…”

Section: Hydrodenitrogenation Of Petroleummentioning

confidence: 86%

Hydrodenitrogenation of Petroleum

Furimsky¹,

2005

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A high level of hydrodenitrogenation (HDN) is required to achieve a desirable conversion of other hydroprocessing reactions. This results from a strong adsorption of nitrogen-containing compounds on catalytic sites that slows down the hydrogen activation process and hinders the adsorption of other reactants. Studies on model compounds and real feeds indicate that less than 50 ppm of nitrogen in the feed can poison catalytic sites. Kinetic studies determined adsorption constants of various nitrogen-containing compounds and concluded that at least four different catalytic sites are required to interpret experimental observations in contrast with a dual site site ffi concept, which only considered two sites. The advancements in experimental techniques allowed identification of products formed during very early stages of hydrodenitrogenation. These results confirmed that the removal of the amino group from saturated amines, as the last step in hydrodenitrogenation, is governed by the type of carbon to which the amino group is attached rather than the number of hydrogen atoms attached to carbon in a and b position to nitrogen Performance of conventional Co(Ni)Mo(W)/Al 2 O 3 catalysts during hydrodenitrogenation was enhanced by combination with various additives and by replacing the traditionally used g-Al 2 O 3 support with novel supports. Catalytic functionalities could be modified by using different precursors of active metals and varying conditions during preparation. Progress has been made in the development of catalysts possessing a high selectivity for hydrodenitrogenation. In this case, the nonconventional catalysts based on the carbides and nitrides of transition metals exhibited high activity and selectivity. Noble metal sulfides alone or supported on different supports were active for HDN as well. Feedstocks used for catalyst evaluation included model compounds and mixtures of model compounds as well as real feeds. The challenges in the development of catalysts for hydrodenitrogenation of heavy feeds containing asphaltenes and metals have been identified.In general, compared to Q, conversions were little affected by a methyl (Me) on the aromatic ring, while being lower for Me on the N-ring, except for 2-MeQ. It is evident that Me substitution in the 2-position had little effect on HDN over the NiMoP/Al 2 O 3 catalyst, whereas it actually enhanced the HDN rate over the CoMo/Al 2 O 3 catalyst. For both catalysts the HDN rate was suppressed in 6-MeQ and particularly in 3-MeQ and 4-MeQ. The distribution of N-containing intermediates was influenced by the ring substitution and the type of catalyst. This suggests that several factors influence the overall HDN mechanism of Qs. This should be kept in mind while analyzing differences in the networks proposed by different authors.The preceding discussion on the HDN of Q mostly referred to conventional catalysts. A number of studies on the HDN of Q were conducted over unconventional catalysts. For example, 3-and 4-MeQs were more reactive than Q over the unsupported Zr,...

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Section: Hydrodenitrogenation Of Petroleummentioning

confidence: 86%

Hydrodenitrogenation of Petroleum

Furimsky¹,

2005

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“…For example, 36% of the nitrogen was removed from coker kerosene when the unpromoted catalyst was used, while 50% of the nitrogen was removed over the promoted catalyst. Furthermore, nonbasic nitrogen compounds had higher removal rates than basic nitrogen compounds, and nitrogen removal was increased by increasing the ratio of hydrogenation promoter to Mo up to a maximum of 0.6 …”

Section: Hydrotreatingmentioning

confidence: 99%

Nitrogen Removal from Oil: A Review

2016

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The selective removal of nitrogen-containing compounds from oil and oil fractions is of interest because of the potential deleterious impact of such compounds on products and processes. Problems caused by nitrogen-containing compounds include gum formation, acid catalyst inhibition and deactivation, acid−base pair-related corrosion, and metal complexation. A brief overview of the classes of nitrogen compounds found in oil is provided. The review of processes to remove nitrogen from oil emphasizes studies that investigated denitrogenation of industrial feedstocks, such as refinery fractions, heavy oils, and bitumens. The main topics covered are hydrotreating, liquid−liquid phase partitioning, solvent deasphalting, adsorption, chemical conversion followed by separation, and microbial conversion. Chemical conversion processes include oxidative denitrogenation, N-alkylation, complexation with metal salts, and conversion in high-temperature water. There are many processes for denitrogenation by separation of the nitrogen-rich products from oil without removing the nitrogen group from the nitrogencontaining compounds. As a consequence, most of these processes are viable mainly for removal of nitrogen from low-nitrogencontent oils, typically with <0.1 wt % N. At present, hydrodenitrogenation appears to be the only industrially viable process for nitrogen removal from oils with high nitrogen content.

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“…Additionally, nitrogen compounds were barely affected, most likely because they are part of the polyaromatic structures rather than of the alkyl chains; for instance, to be able to convert them, high severity conditions should be employed . Despite the fact that NiW catalysts have powerful hydrogenating capabilities, it is well-known that to be able to perform HDN the aromaticity of the molecule has to be broken first …”

Section: Analysis Of Asphaltenes Using X-ray Photoelectron Spectroscopymentioning

confidence: 99%

“…41 Despite the fact that NiW catalysts have powerful hydrogenating capabilities, it is well-known that to be able to perform HDN the aromaticity of the molecule has to be broken first. 42 The usual metals found in asphaltenes, Fe, V, etc., were not detected with this set of samples; only the resin fraction showed the presence of Si (0.3%; Figure 5).…”

Section: Energy and Fuelsmentioning

confidence: 99%

X-ray Photoelectron Spectroscopy Analysis of Hydrotreated Athabasca Asphaltenes

et al. 2017

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C7 asphaltenes from Athabasca crude oil were hydrotreated using a commercial NiW/Al2O3 catalyst and analyzed using X-ray photoelectron spectroscopy. Results showed that the catalyst performed better in the removal of sulfur rather than nitrogen and that sulfur concentration is higher at the surface in comparison to the bulk structure. Moreover, the sample after reaction had a higher oxygen content in comparison to the untreated asphaltene, indicating poor hydrodeoxygenation performance of the catalyst in addition to a higher reactivity toward atmospheric oxygen at the surface of the asphaltene. The latter is proposed to arise once the layer of resin covering the asphaltene is partially converted during the hydrotreating process.

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Catalytic hydrodenitrogenation of basic and non-basic nitrogen compounds in Athabasca bitumen distillates

Cited by 22 publications

References 5 publications

Hydrodenitrogenation of Petroleum

Hydrodenitrogenation of Petroleum

Nitrogen Removal from Oil: A Review

X-ray Photoelectron Spectroscopy Analysis of Hydrotreated Athabasca Asphaltenes

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