Reaction vanadium porphyrins

The problem of the origin of the metal-porphyrins is closely related to that of the origin of petroleum and is oie of the most basic and interesting questions of petroleum geochemistry. The most probable conclusion seems to be that the nickel and vanadium porphyrin complexes are formed by metal exchange reactions from animal and/or plant metabolic pigments such as hemoglobin and chlorophyll. 

Several different sequences of reactions may be postulated for the conversion of the magnesium complexes of pheophytlns (chlorophylls) and Iron complexes of protoporphyrin IX and related porphyrins (hemes and hemlns) Into the nickel and vanadium porphyrins found In petroleum. One possible reason for the Isolation of only the nickel and oxovanadlum metalloporphyrlns Is that only they were resistant to degradation. While studies of Hodgson do Indicate that complexatlon of vanadium and nickel do Impart added thermal stability to porphyrins (12). Berezin has found that complexatlon of other metal Ions such as cobalt and copper also Imparts added thermal stability (13. 14). In addition, Hodgson s study Indicates that relatively little thermal degradation of the metalloporphyrlns has taken place In most crude oils (which would lead to unbound vanadium and nickel), One would expect that if little degradation of these metalloporphyrlns has occurred, complete disappearance of other metalloporphyrlns by thermal degradation Is an unreasonable assumption. 

The most studied of the Group 5 porphyrins have been compounds with vanadyl and niobium metal ions no electrochemical data have yet been reported for tantalum porphyrins. Vanadium porphyrins have been synthesized as both V(IV) and V(II) complexes. The vanadyl derivatives, represented as (P)VO, generally undergo well-defined reduction and oxidation reactions involving the porphyrin, macrocyle the lower oxidation state V(II) complexes have been prepared as (P)V (L) and (P)V (L)2 derivatives, where P = T(p-Me)PP or OEP and L = THE or PPhMe2, but these species have not been examined as to their electrochemical properties [7]. 

The most important undesired metallic impurities are nickel and vanadium, present in porphyrinic structures that originate from plants and are predominantly found in the heavy residues. In addition, iron may be present due to corrosion in storage tanks. These metals deposit on catalysts and give rise to enhanced carbon deposition (nickel in particular). Vanadium has a deleterious effect on the lattice structure of zeolites used in fluid catalytic cracking. A host of other elements may also be present. Hydrodemetallization is strictly speaking not a catalytic process, because the metallic elements remain in the form of sulfides on the catalyst. Decomposition of the porphyrinic structures is a relatively rapid reaction and as a result it occurs mainly in the front end of the catalyst bed, and at the outside of the catalyst particles. 

The reaction of vanadium salts (VC14, V202(S04)2, V(OCOMe)4, VO(acac)2) and porphyrin gives a complex which, after work-up, is isolated as a very stable oxovanadium(IV) species, VO(Por) (for VO(OEP), V—O = 1.620(2)A, V—= 2.102A, A(N4) = 0.543 A).17 -21 In the presence of a large excess of nitrogenous ligand such as pyridine and piperidine, it forms a six-coordinate complex with a small equilibrium constant (K = 10 I-10 21 M-1).18 The effect of / substituents on the association constant (Kx) is expressed by the Hammett equation (equation 4). 

Valinomycin metal complexes, 969 Vanadium complexes acetylacetone exchange reactions, 380 1,4-diaza-l,3-butadiene, 209 dioxygen mononuclear, 321 hydrazido(2-), 148 hydroxamic adds, 506 phthalocyanines, 865 polypyrazolylborates, 248 porphyrins, 824 dioxygen adducts, 325... 

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... 

Intrinsic reactivity patterns of the different porphyrins are reflected in their metal deposition profiles, which serve as fingerprints marking the reaction sequence. Vanadium profiles (Fig. 25) from pure VO-etiopor-phyrin in oil demetallation experiments are steeper with less deposit in the pellets center than the nickel profiles (Fig. 26) from the analogous experiment with pure nickel porphyrin. Pure compound intrinsic reactivity data revealed that vanadium was more reactive than nickel at most temperatures of interest. However, a reduction in VO-porphyrin diffusion by stronger adsorption interactions would also contribute to a steepening of the metal deposition profiles. Metal profiles have not been examined from demetallating model oils containing both Ni- and VO-porphyrins. 

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... 

Model compound studies have shown the importance of porphyrin macrocycle basicity, resulting from electron-withdrawing substituents and metal ligands, on the reducibility and susceptibility of the central metal to reaction. Similar insight into the differences in relative basicity of vanadium- and nickel-containing complexes found in petroleum may therefore be valuable in rationalizing the observed effects and predicting demetallation activity. 

Vanadium is present in crudes mainly in the +4 state (58). In fact, up to 50% of the total vanadium in crude oil can be found as V02+ in organometallic compounds such as porphyrins and naphthenates (59-63). During the cracking reaction in a FCCU, these compounds deposit V (probably in the form of VO+2 cations) on the catalyst surface. Then, after steam-stripping and catalyst regeneration, formation of V+5 surface phases occur. The effects of vanadium on FCC properties are more severe than any of the other metals present in petroleum feedstocks. In fact, vanadium causes an irreversible loss of cracking activity which is the result of a decrease in crystallinity, pore volume and surface area of the catalyst, Figure 5. 

Chlorophylls and Iron porphyrins are prevalent In plant and animal matter whereas only nickel (as Nl(II)) and vanadium (as oxovanadlum V(IV), V 0) metalloporphyrlns are found In petroleum. To determine a plausible reaction sequence for these conversions, we are studying hydrolysis and metallatlon reactions of metal complexes of pheophytlns (the demetallated ligands of chlorophylls) and of porphyrins. The pheophytlns and metal pheophytlnates, Including the chlorophylls and the most abundant natural porphyrins, are highly llpophyllc and have very low solubilities In aqueous... 

Further support for the concept of a sequential reaction leading to metals deposition comes from an analysis of the deposition profiles of vanadium [17]. A kinetic analysis of a two step process for V removal was developed, in which the first step was suggested to involve hydrogenation of the V containing porphyrin, while the second produces deposits of vanadium sulphide on the surface. Increased levels of HzS in the gas stream inhibited HDS of the material but increased HDV. For vanadium, the second reaction leading to metal deposits, with levels of H2S expected in an industrial reactor, was found to be some 85 x faster than the first hydrogenation reaction [17]. Under these conditions, it is not surprising that the bulk of the deposition of vanadium occurs near the pellet surface. 

With drastic variations in sediments, composition as well as types of vanadium complexes vary. Even within a series of samples there is a noticeable variation of the vanadium complexes. For example, as the age or the depth of the fossil remains increases, a transformation of the porphyrin types from philo to etio takes place. This is merely one example of the large variety of reactions and transformations occurring in petroleum as well as other bituminous substances. The study of such effects would reveal much knowledge concerning the migration, maturation, and transformation of a diversity of fossil remains. 

In order to interpret better the nature of the reactions involved in these reactions involving vanadium removal and metalloporphyrin destruction, extensive studies have been made on synthetic porphyrins... 

The greater lability toward vanadium removal and porphyrin destruction for the vanadyl petroporphyrins over the synthetic vanadyl porphyrins is a fortunate circumstance. This difference can be rationalized based upon structural differences of the porphyrins involved. Phyllo-type petroporphyrins all contain a cyclopentane ring, fused to one of the pyrrole rings with the methine carbon one of the units of the carbo-cyclic structure. Etio- and rhodo-type petroporphyrins appear to have alkyl substitution at one or more methine positions, as based upon nmr spectral data. Should all petroporphyrins have a carbon substituent on one or more methine carbons, the carbonium ion formed by the reaction would tend to have more charge localization on those methine carbons. These ions are a more stable species by an order of magnitude over those porphyrins without methine substitution. 

Other metal species, which are known to be active in aerobic radical reactions such as vanadium compounds [83], Co naphthenate [84], CoJacetateJj [85], Co oleate [86], and metal porphyrins [87], were also reported to give low yields of AA with molecular oxygen. When the aerobic scission of olive oil fatty acids in a ball mill in the presence of Ce02 stopped at the aldehyde stage, 9-oxononanoic acid and nonanal besides a range of other aldehydes were received [88]. 

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