Precision petroleum industry

A number of other words that have traditionally been used in the petroleum industry are difficult to define precisely. These refer pardy to specific hoiling ranges, but also to certain intended uses. Thus, gasoline boils lower than naphtha, and kerosenes generally higher, but these terms are applied to products that ate intended as fuels, rather than as solvents. 

Further indication of how much more chemical the analytical requirements of the petroleum industry have become is evident from the nature of the problems on which the Committee on Analytical Research of the American Petroleum Institute is engaged. These problems include precise determinations of oxygen, nitrogen, and trace metals in crude oils, charge stocks, and cracking catalysts. 

Miscellaneous physical chemical measurements, some quite empirical, are of great importance to the petroleum industry because they are used for control in manufacture and are included in customer s specifications. Macro methods are of course available, but occasionally the sample is too small and this is frequently the case when the problem is particularly important. Micro modifications of these macro methods have often proved extremely helpful. Microchemistry is not a fad but it is not a panacea either. It should be employed where it is necessary, as where the sample is very small or where it offers a definite and substantial advantage in accuracy, precision, or economy of time or materials. If in a particular case it offers none of these advantages there is no good reason to employ it. 

Zeolites are combinations of A1203 and Si02 that are crystalline structures with precisely defined pore structures in the molecular size range (0.4—1.5 nm or 4-15 A). A related group of materials known as mesoporous silica-alumina has extended the range of pore sizes attainable in ordered Si02-Al203 supports to 4 nm (40 A). They are commonly used in the chemical and petroleum industry due to their surface acidity and ability to exclude molecules... 

Although modem electroanalytical techniques are characterized by high sensitivity (sub-nanogram levels are measurable), a degree of selectivity, a capability for multi-element analysis, and excellent accuracy and precision, these techniques have not been widely applied for trace elemental analysis in the petroleum industry, primarily for two reasons ... 

The first of the separation techniques to be used in process measurement was gas chromatography (GC) in 1954. The GC has always been a robust instrument and this aided its transfer to the process environment. The differences between laboratory GC and process GC instruments are important. With process GC, the sample is transferred directly from the process stream to the instrument. Instead of an inlet septum, process GC has a valve, which is critical for repetitively and reproducibly transferring a precise volume of sample into the volatiliser and thence into the carrier gas. This valve is also used to intermittently introduce a reference sample for calibration purposes. Instead of one column and a temperature ramp, the set up involves many columns under isothermal conditions. The more usual column types are open tubular, as these are efficient and analysis is more rapid than with packed columns. A pre-column is often used to trap unwanted contaminants, e.g. water, and it is backflushed while the rest of the sample is sent on to the analysis column. The universal detector - thermal conductivity detector (TCD)-is most often used in process GC but also popular are the FID, PID, ECD, FPD and of course MS. Process GC is used extensively in the petroleum industry, in environmental analysis of air and water samples" and in the chemical industry with the incorporation of sample extraction or preparation on-line. It is also applied for on-line monitoring of volatile products during fermentation processes" ... 

To satisfy the requirements of catalytic facilities in our refineries, catalyst production and sales have been thriving. Precise statistics for the catalyst industry are not available. But, in our evaluation, current sales of the main catalysts for cracking, reforming, and hydrogen pretreatment, are probably at an annual rate of 165 million dollars. Considering the future development of the apphcation of catalysis to the petroleum industry, sales may attain, by 1965, a level of 325 million dollars (see Table IV) (8). 

In 2000, the U.S. EPA published requirements for tier 2 fuels and also mandated the test methods that can be used for sulfur determination in these fuels. ASTM D 6428 was chosen as the mandatory method for diesel fuels with ASTM D 2622, D 3120, and D 5453 methods allowed as alternates if their accuracy and precision were shown to be equivalent to those of D 6428 method. The petroleum industry widely uses the latter three test methods for sulfur but had virtually no experience with the mandated D 6428 method, which is under the jurisdiction of ASTM D 16 Committee on Aromatic Hydrocarbons and Related Chemicals. The method was written for the sulfur determination of liquid aromatic hydrocarbons, their derivatives, and related chemicals. The precision quoted in this method was for aromatic hydrocarbons and not for petroleum products. Moreover, it was inadequate (10 analyses by one operator on two samples) and did not conform to the statistical protocols used in the D02 Committee test methods for calculating the precision and bias estimates. 

The focus of this paper is on the technique of Combustion CVAAS and its applicability to some of the samples encountered in the petroleum industry. It describes the equipment and test procedure adopted by our laboratory for the determination of total mercury in crude oil, condensate, and other process stream samples. Validation of this technique using standard reference materials (SRM), certified standards, and spiked samples is addressed. Instrument response to various organic mercury species and precision data derived from actual crude oil samples is presented. 

For many years double focusing sector instruments were the instruments of choice for highly accurate and precise (within lppm) measurements of molecular mass, used to determine molecular compositions of unknown compounds or at least limit the possibilities to a small number. This role is now usually fiUed by upper-end TOF analyzers (less expensive, superior ease of use, but lower accuracy and precision) and by FTICR and Orbitrap instruments (more expensive but higher RP possible). Magnetic sector instruments are still used by the petroleum industry in type analysis (see Preface), and also for GC/HRMS quantitation as mentioned above, since TOF, FTICR and Orbitrap instruments do not posses the necessary combination of figures of merit for such trace quantitative analyses. 

The Norwegian petroleum industry is efficient and professional, with highly skilled professionals involved safety authorities, the industry themselves, researchers and consultants. But, it is precisely this efficient and professional work mode that creates a danger in that various concepts (like culture ) are eagerly taken aboard and efficiently installed as part of the prevailing, often tacit world views. 

A significant advance in metal soap technology occurred in the 1920s with the preparation of the metal naphthenates. Naphthenic acids (qv) are not of precise composition, but rather are mixtures of acids isolated from petroleum. Because the mixture varies, so does acid number, or the combining equivalent of the acid, so that the metal content of the drier would not always be the same from lot to lot. The preparation of solvent solutions of these metal naphthenates gave materials that were easy to handle and allowed the metal content to be standardized. Naphthenates soon became the standard for the industry. 

Erickson believes that industrial biotechnology is attractive to business because it can decrease production costs and increase profits, increase the sustainability profile, allow for broader use of renewable agricultural feedstocks instead of using petroleum, and provide precision catalysis. However, he thinks industrial biotechnology can also be disruptive as it converges with other scientific disciplines because of its shorter research and development cycles. Erickson then discussed the importance of partnership among companies, which is detailed in Chapter 5. 

The application of atomic spectroscopy methods to the analysis of petroleum products is important to the oil industry. All oil samples must be prepared in solution form and be at a concentration so as to be detected to quantify all metals of interest with accuracy and precision. Solutions containing petroleum products in organic solvents may be measured directly or with the use of internal standards to correct for viscosity effects. It is important that the selected solvent dissolves the oil and products and does not cause erratic flickering of the plasma, or quenches it. It is also important that the same solvent can be used to prepare calibration standards. The following methods are common sample preparation methods for metal analysis of crude and lubricating oils. 

D4294 Energy Dispersive XRF All liquid petroleum products and oils Widely used in industry because of low cost instrumentation poor precision at low sulfur levels... 

There are about 20 laboratory based ASTM standard test methods available for the determination of sulfur in various petroleum products and lubricant samples [6]. These utilize diverse analytical techniques and have applicability range sparming from m% to low mg/kg levels. However, at the very low end of sulfur analysis there are only three or four test methods which can adequately determine sulfur in such fuels. These lab-based standard test methods include ASTM D 2622 - wavelength dispersive X-ray fluorescence, D 3120 - oxidative microcoulometry, D 5453 - combustion UV-fluorescence, and D 6920 - oxidative combustion electrochemical detection methods. Without a doubt, the most widely used two methods out of these in oil industry laboratories are D 2622 and D 5453. Studies have shown that at truly ultra-low levels of sulfur only D 5453 can deliver accurate and precise results. This conclusion has... 

Stoddard solvent is a multipurpose petroleum solvent (McDermott 1975). Industrial uses include paint vehicles thinning agent for paints, coatings, and waxes printing inks adhesives and as a solvent in liquid photocopier toners (Air Force 1989b McDermott 1975). Stoddard solvent is commonly used at air fields as a degreaser for precision engine parts in machine shops and in automotive repair applications. 

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