Metallic constituents

Petroleum, as recovered from the reservoir, contains metallic constituents but also picks up metallic constituents during recovery, transportation, and storage. Even trace amounts of these metals can be deleterious to refining processes, especially processes in which catalysts are used. Trace components, such as metallic constituents, can also produce adverse effects in refining either (1) by causing corrosion or (2) by affecting the quality of refined products. 

it is important to have test methods that can determine metals, both at trace levels and at major concentrations. Thus test methods have evolved that are used for the determination of specific metals as well as the multielement methods of determination using techniques such as atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, and X-ray fluorescence spectroscopy. 

Nickel and vanadium along with iron and sodium (from the brine) are the major metallic constituents of crude oil. These metals can be determined by atomic absorption spectrophotometric methods (ASTM D-5863, IP 285, IP 288, IP 465), wavelength-dispersive X-ray fluorescence spectrometry (IP 433), and inductively coupled plasma emission spectrometry (ICPES). Several other analytical methods are available for the routine determination of trace elements in crude oU, some of which allow direct aspiration of the samples (diluted in a solvent) instead of time-consuming sample preparation procedures such as wet ashing (acid decomposition) or flame or dry ashing (removal of volatile/combustible constituents) (ASTM D-5863). Among the techniques used for trace element determinations are conductivity (IP 265), flameless and flame atomic absorption (AA) spectropho- 

Inductively coupled argon plasma emission spectrophotometry (ASTM D-5708) has an advantage over atomic absorption spectrophotometry (ASTM D-4628, ASTM D-5863) because it can provide more complete elemental composition data than the atomic absorption method. Flame emission spectroscopy is often used successfully in conjunction with atomic absorption spectrophotometry (ASTM D-3605). X-ray fluorescence spectrophotometry (ASTM D-4927, ASTM D-6443) is also sometimes used, but matrix effects can be a problem. 

The method to be used for the determination of metallic constituents in petroleum is often a matter of individual preference. 

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Perchloric acid is used in analytical chemistry for the determination of trace metal constituents in oxidizable substances as well as in the production of high... 

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. 

This test indicates the amount of metallic constituents in a crude oil. The ash left after completely burning an oil sample usually consists of stable metallic salts, metal oxides, and silicon oxide. The ash could be further analyzed for individual elements using spectroscopic techniques. 

Graphitic Corrosion corrosion of grey cast iron in which the metallic constituents are removed as corrosion products, leaving the graphite. 

Procedures have also been devised for the determination of metallic constituents. Thus, mercury is absorbed in nitric acid and titrated with sodium diethyldithiocarbamate, whilst zinc is absorbed in hydrochloric acid and determined by an EDTA titration (see Section 10.65). 

Description of the cell composition is based - as far as possible - on the Stockholm convention (1953), i.e. the left-hand electrode constitutes the negative terminal of the cell. Cells are listed according to the metallic constituent of the electrode mentioned first which is involved in the electrode reaction establishing the respective electrode potential. Contact materials and conductive additives may be mentioned first before the actual element of interest only for the sake of correct materials sequence. The sequence of electrode components is stated as reported in the original publications. When an oxygen electrode is used as reference electrode an oxygen partial pressure of 0.21 atm is assumed. 

The wear and subsequent failure of a cutting tool is a complex mechanism that usually involves a number of physical and chemical phenomena. Temperatures at the tool/workpiece interface (cutting edge) may reach up to 1200°C in a very short period of time. This creates a pronounced thermal shock and promotes oxidation of the tool surface and the diffusion of metallic constituents of the tool into the chip with a resulting loss of tool strength. 

Figure 1 presents a scheme for the formation of B—B bonds in binary metal borides, i.e., the occurrence of one-, two- and three-dimensional B aggregates as a function of the periodic group of the metal constituent. 

Wilson, Abel Lewis (1974), in a detailed chemical study of erosion in aqueous solution, found that in the first 24 hours of the cement s life the ions eluted were Zn, Mg, HPO " and H2PO4. Far more Mg ions were eluted than Zn ions, despite zinc being the major metal constituent of the zinc phosphate cement. These workers deduced that magnesium is far less firmly bound to phosphate than is zinc and that, consequently, its presence in the oxide is a source of weakness. These results were later confirmed by Anzai et al. (1977). 

Stable isotopes Organo-metallic constituents Agrochemical contaminants Aliphatic and aromatic hydrocarbons Chlorinated hydrocarbons... 

STABL Stabilization Stabilization (also referred to as solidification) involves the addition of stabilizing agents (e.g., Portland cement) to a waste to reduce the teachability of metal constituents... 

Lambert, A.L., et al., Enhanced allergic sensitization by residual oil fly ash particles is mediated by soluble metal constituents, Toxicol. Appl. Pharmacol. 165, 1, 84, 2000. 

For metallic constituents, some attempts have been made using electrochemical techniques but without real success, because of the existing interferences in wastewater and the high detection limit required with respect to... 

For non-metallic constituents, several systems exist especially for nutrients monitoring, considering their importance in the eutrophication phenomenon. The on-line measurement of some nitrogen compounds (nitrate and ammo-... 

Except for the development of on-line systems for nutrients monitoring, the measurement of other inorganic non-metallic constituents is rather rare. Some commercial systems based on electrochemical sensing are proposed for the measurement of cyanide. A simple and rapid procedure for sulphide measurement in crude oil refinery wastewater has been developed [ 32 ]. Based on the de-convolution of the UV spectrum of a sample, this method has a detection limit of 0.5 mg L 1 and has been validated for crude oil refinery wastewater. 

Parallel studies were performed by Liu and Davison (1988), who investigated the process of chemisorption on inverse-supported catalysts, where the surface him is a semiconductor and the underlying support is a metal. Again a key parameter was found to be him thickness, and the substrate was observed to behave as either an acceptor or a donor, depending upon that thickness. The lack of charge self-consistency in this work was addressed by Sun et al (1994a), who also studied the effects of thickness and different metal constituents. 

In very general terms, petroleum is a mixture of (1) hydrocarbon types, (2) nitrogen compounds, (3) oxygen compounds, (4) sulfur compounds, and (5) metallic constituents. Petrolenm prodncts are less well defined in terms of heteroatom compounds and are better defined in terms of the hydrocarbon types present. However, this general definition is not adequate to describe the true composition as it relates to the behavior of the petroleum, and its products, in the environment. For example, the occnrrence of amphoteric species (i.e., compounds having a mixed acid-base natnre) is not always addressed, nor is the phenomenon of molecnlar size or the occnrrence of specific functional types that can play a major role in petrolenm behavior. 

Carbon and hydrogen in coke can be determined by the standard analytical procedures for coal and coke (ASTM D3178, D3179). However, in addition to carbon, hydrogen, and metallic constituents, coke contains considerable amounts of nitrogen and sulfur that must be determined prior to sale or use. These elements will appear as their oxides (NO, SO ), respectively, when the coke is combusted, thereby causing serious environmental issues. 

In addition to modification of surfaces by non-metals, the catalytic properties of metals can also be altered greatly by the addition of a second transition metaP ". Interest in bimetallic catalysts has arisen steadily over the years because of the commercial success of these systems. This success results from an enhanced ability to control the catalytic activity and selectivity by tailoring the catalyst composition . A long-standing question regarding such bimetallic systems is the nature of the properties of the mixed-metal system which give rise to its enhanced catalytic performance relative to either of its individual metal components. These enhanced properties (improved stability, selectivity and/or activity) can be accounted for by one or more of several possibilities. First, the addition of one metal to a second may lead to an electronic modification of either or both of the metal constituents. This... 

Zinc is the metal constituent of a number of very important enzymes including carbonic anhydrase, carboxypeptidase, thermolysin and alcohol dehydrogenase, number of... 

In ash and soot residues from Orimulsion-lired power stations, the dominating metal constituents are vanadium, nickel, and iron, together with... 

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