Asphaltenes, vanadium

Another current development in the use of F-T chemistry in a three-phase slurry reactor is Exxon s Advanced Gas Conversion or AGC-21 technology (Eidt et al., 1994 Everett et al., 1995). The slurry reactor is the second stage of a three-step process to convert natural gas into a highly paraffinic water-clear hydrocarbon liquid. The AGC-21 technology, as in the Sasol process, is being developed to utilize the large reserves of natural gas that are too remote for economical transportation via pipelines. The converted liquid from the three-step process, which is free of sulfur, nitrogen, nickel, vanadium, asphaltenes, polycyclic aromatics, and salt, can be shipped in conventional oil tankers and utilized by most refineries or petrochemical facilities. 

In the heaviest fractions such as resins and asphaltenes (see article 1.2), metal atoms such as nickel and vanadium are found. They belong in part to molecules in the porphyrine family where the basic pattern is represented by four pyrrolic rings, the metal being at the center of this complex in the form Wi - or V0+ (< 3)... 

Asphaltenes have high concentrations of heteroelements sulfur, nitrogen, nickel and vanadium. Their content varies widely in petroleum oils (Table 1.5). They cause a number of problems throughout the petroleum industry. 

Physical methods of fractionation of tar sand bitumen usually indicate high proportions of nonvolatile asphaltenes and resins, even in amounts up to 50% wt/wt (or higher) of the bitumen. In addition, the presence of ash-forming metallic constituents, including such organometaUic compounds as those of vanadium and nickel, is also a distinguishing feature of bitumen. 

The presence of asphaltenes, originating in the fuel, acts as a trap for vanadium, nickel, and sodium (which promote slagging and sulfur corrosion)-, these asphalthenes often contain sulfur compounds, which simply add to the contaminant load. Additionally, asphaltenes act as precursors to spherical stack solids (cenospheres), which are exhausted with the flue gases as stack emissions. 

An additional mechanism affects the deposits formation from the H-Oil reactor, rejection of vanadium and nickel sulfides from the catalyst. In the vacuum tower, asphaltene precipitation was found to be the prevalent fouling mechanism. In asphaltene... 

Mogollon, L. Rodriguez, R. Larrota, W., et al., Biocatalytic removal of nickel and vanadium from petroporphyrins and asphaltenes. Appl Biochem Biotechnol, 1998. 70-72 pp. 765-777. 

Brunnock et al. [67] have also determined beach pollutants. They showed that weathered crude oil, crude oil sludge, and fuel oil can be differentiated by the n-paraffin profile as shown by gas chromatography, wax content, wax melting point, and asphaltene content. The effects of weathering at sea on crude oil were studied parameters unaffected by evaporation and exposure are the contents of vanadium, nickel, and n-paraffins. The scheme developed for the identification of certain weathered crude oils includes the determination of these constituents, together with the sulfur content of the sample. 

Vanadium Complexes and Porphyrins in Asphaltenes, J. Inst. Petrol. 

In Section II, the nature of the metal compounds in petroleum oils is discussed to establish a basic understanding of the targeted reactants. The chemical composition of the host petroleum and residuum is described, including a discussion of the two classes of metal compounds (1) metal-loporphyrins and (2) nonporphyrin metals. The troublesome asphaltenes will also be described. Comparison is made between the characteristics of vanadium and nickel complexes and their distribution in residua. 

Nickel and vanadium in petroleum exist as soluble organometallic complexes that fall into two categories metal porphyrins and nonporphyrin metal complexes. Both the porphyrins and the nonporphyrins may be distributed over a wide boiling range (350-650°C+), reflecting significant variations in molecular weight, structure, and polarity. Metal porphyrins and nonporphyrin metal complexes also tend to precipitate as part of the asphaltene materia] to an extent that varies with the source of the crude oil. 

Crude oil origin Asphaltenes (wt. %)d Nickel Vanadium Iron... 

Additional insight can be obtained with the successive use of various light paraffin and polar solvents as a separation strategy. Dean and Whitehead (1963) obtained C7 asphaltenes, a C5-insoluble-C7-soluble fraction (part of the resin), an acetone-immiscible fraction from the C5-soluble fraction and an acetone-miscible fraction for both Boscan and Gach Saran (Iranian Heavy) crude oils. They found that the vanadium was more concentrated in the C7 asphaltene and C5-insoluble-C7-soluable fractions, especially in the C7 asphaltene fraction. However, the metal-lopetroporphyrins were mostly concentrated in the C5-insoluble-C7-soluble and the acetone-miscible fractions. According to their data, only 5% of the metals in the asphaltenes are identified as metallopetroporphy-rins. This is consistent with the expectation that metal porphyrins are less polar than the metal nonporphyrins. 

Asphaltenes may contain both porphyrin and nonporphyrin metals, depending upon the origin of the crude oil. Yen et al. (1969) characterized the vanadium complexes in a petroleum asphaltene by mass spectroscopy, optical spectroscopy, and ESR. Porphyrins (Etio and DPEP), acid-resistant porphyrin macrocycles of increased aromaticity (Rhodo), and nonporphyrins with mixed donor complexes were identified. Baker (1966) and Baker et al. (1967) extracted porphyrins from Boscan crude oil asphaltenes and also found Etio and DPEP as the two major porphyrin series. These homologous series range in molecular weight by 7 to 18 methylene groups. Gallegos (1967) observed by mass spectroscopy that asphaltenes and maltenes from a Boscan crude oil had nearly identical porphyrins in terms of mass distribution. 

Percent Vanadium in Each Molecular Weight Category of Vanadyl Compounds in the Four Heavy Crude Petroleums and Their Asphaltenes, Maltenes, Asphaltene Polar Extracts, and Extracted Asphaltenes by 50/100/1000 A SEC-HPLC-GFAA Analysis"- ... 

The effect of temperature on the association of vanadium compounds in asphaltenes was investigated by Tynan and Yen (1969). Using electron spin resonance (ESR), they observed both anisotropic and isotropic hyperfine structures of vanadium, interpreted as bound or associated and free vanadium, from asphaltenes precipitated for a Venezuelan petroleum and reintroduced to various solvents. Higher temperatures and more polar solvents resulted in a transition from bound to free vanadium, as shown in Fig. 12. At 282°C, only 1% of the anisotropic spectrum was observed. An activation energy of 14.3 kcal/mole was observed for the transition. 

Fig. 12. Temperature dependence of the ratio of isotropic vanadium to anisotropic vanadium in asphaltenes in solutions of diphenylmethane (DPM), benzyl n-butyl ether (BBE), and tetrahydrofuran (THF) (Tynan and Yen, 1969).

Vanadyl salen is readily converted at 100°C with H2S in the absence of a catalyst to a vanadium sulfide and a free organic ligand (or decomposition products). Vanadyl phthalocyanine is more stable with respect to ring attack and demetallation. Rates relative to catalytic reactions have not been measured. If VO-salen is an appropriate model of vanadium binding in asphaltenes, asphaltenic metals are more readily converted to sulfides under hydrotreating conditions than the porphyrinic metals. This suggests... 

A spectrum of metal compound reactivities in petroleum could arise for several reasons. Nickel and vanadium exist in a diversity of chemical environments. These can be categorized into porphyrinic and non-porphyrinic species vanadyl and nonvanadyl or associated with large asphaltenic groups and small, isolated metal-containing molecules. Each can be characterized by unique intrinsic reactivity. Reaction inhibition which occurs between the asphaltenes and the nonasphaltenes, as well as between Ni and V species, can also contribute to reactivity distributions. The parallel reaction interpretation of the observed reaction order discrepancy is therefore compatible with the multicomponent nature of petroleum. Data obtained at low conversion could appear as first order and only at higher conversions would higher-order effects become obvious. The... 

Vanadyl and nickel reactivity differences resulting from the chemistry of the oxygen ligand on vanadium were discussed in Section IV,A,l,c. Enhanced V reactivity could also arise from molecular size constraints. Beuther and co-workers (Beuther and Schmid, 1963 Larson and Beuther, 1966) speculate that nickel concentrates in the interior of asphaltene micelles while vanadium concentrates on the exterior. Thus a combination of stronger adsorption due to the oxygen ligand and inhibition of Ni reaction, coupled with the exposed position at the periphery of the asphaltene, may all contribute to the enhanced vanadium reactivity relative to nickel. 

A linear relationship is often observed between vanadium removal and sulfur removal, whereas the relationship between nickel and sulfur removal is linear but of smaller slope (Massagutov et al., 1967). For asphaltene-containing stocks, this phenomenon is interpreted on the basis of heteroatom distribution within the asphaltene micelles (Beuther and Schmid, 1963). Sulfur and vanadium are concentrated on the exterior, whereas nickel is concentrated in the interior. Conversion of the asphaltene generally leads to simultaneous removal of sulfur and vanadium, whereas nickel removal is more difficult. 

Takeuchi et al. (1985) tested the catalytic activity of deposited Ni and V by use of a catalytic metal-free alumina base. These interesting results are shown in Fig. 42. After accumulation of 10wt.% vanadium on the catalyst, the alumina base, with little initial activity, has essentially the same activity for HDM and asphaltene cracking as the catalytic metal-... 

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