Asphaltenes solvents

Dautzenberg and de Deken [11] have suggested that such processes could be important in hydroprocessing. They viewed the overall process as a competition between thermal and catalytic reactions. Over ca 430°C, thermal reactions were suggested to predominate and the removal/inter-conversion of oils, resins and asphaltenes proceeded at about the same rate. At somewhat lower temperatures, preferential removal of oils and resins was suggested via a catalytic reaction. The consequent removal of asphaltene solvent then led to precipitation of the asphaltenes and to coking. Similar arguments can be used to explain the results of Mochida et al [12] and of Nakata et al [13]. 

Rahimi, P.M. Dettman, H.D. Dawson, W.H. Nowlan, V. Del Bianco, A. Chomet, E. Coke fonnation from asphaltenes - solvent and concentration effects, CONRAD workshop on bitumen upgrading chemistry, June 7-8,1995, Calgary, Alberta. 

According to the nature of the solvent employed, the yields and constitutions of the asphaltenes are different. In the United States, asphaltenes are obtained by precipitation from normal pentane. 

Propane deasphalting uses propane as an anti-solvent for asphaltenes. 

Solvent deasphalting. This is an extraction of the heaviest fractions of a vacuum residue or heavy distillate. The extract is used to produce the bitumen. The separation is based on the precipitation of asphaltenes and the dissolution of the oil in an alkane solvent. The solvents employed are butane or propane or a butane-propane mixture. By selecting the proper feedstock and by controlling the deasphalting parameters, notably temperature and pressure, it is possible to obtain different grades of bitumen by this process. 

Fractionation. Kett-McGee developed the ROSE process for separating the heavy components of cmde oil, eg, asphaltenes, resins, and oils, in the 1950s. This process was commercialized in the late 1970s, when cmde oil and utility costs were no longer inexpensive. In the ROSE process (Fig. 11), residuum and pentane ate mixed and the soluble resins and oils recovered in the supetctitical phase. By stepwise isobatic temperature increases, which decrease solvent density, the resin and oil fractions ate precipitated sequentially. 

However, for the past 30 years fractional separation has been the basis for most asphalt composition analysis (Fig. 10). The separation methods that have been used divide asphalt into operationally defined fractions. Four types of asphalt separation procedures are now in use ( /) chemical precipitation in which / -pentane separation of asphaltenes is foUowed by chemical precipitation of other fractions with sulfuric acid of increasing concentration (ASTM D2006) (2) solvent fractionation separation of an "asphaltene" fraction by the use of 1-butanol foUowed by dissolution of the 1-butanol solubles in... 

The fractions obtained in these schemes are defined operationally or proceduraHy. The amount and type of asphaltenes in an asphalt are, for instance, defined by the solvent used for precipitating them. Fractional separation of asphalt does not provide well-defined chemical components. The materials separated should only be defined in terms of the particular test procedure. 

Many attempts have been made to characterize the stabiUty of the colloidal state of asphalt at ordinary temperature on the basis of chemical analysis in generic groups. For example, a colloidal instabiUty index has been defined as the ratio of the sum of the amounts in asphaltenes and flocculants (saturated oils) to the sum of the amounts in peptizers (resins) and solvents (aromatic oils) (66) ... 

Bitumen Insoluble in Paraffin Maphtha (AASHPO T46). This test designated by the American Association of State Highway and Transportation Officials (AASHTO) is used to indicate the content of naphtha-insoluble asphaltenes in an asphalt. Other solvents such as / -heptane (ASTM D3279), / -hexane, and / -pentane have been substituted for the naphtha solvent. 

Black, viscous residuum direc tly from the still at 410 K (390°F) or higher serves as fuel in nearby furnaces or may be cooled and blended to make commercial fuels. Diluted with 5 to 20 percent distillate, the blend is No. 6 fuel oil. With 20 to 50 percent distillate, it becomes No. 4 and No. 5 fuel oils for commercial use, as in schools and apartment houses. Distillate-residual blends also serve as diesel fuel in large stationaiy and marine engines. However, distillates with inadequate solvent power will precipitate asphaltenes and other high-molecular-... 

Solvent Deasphalting This is the solvent extraction of virgin residuum to remove asphaltenes or other tarry constituents. The deasphalted oil may be further processed into lubricating oils and greases, or used as cat cracking feed. 

Residues containing high levels of heavy metals are not suitable for catalytic cracking units. These feedstocks may be subjected to a demetallization process to reduce their metal contents. For example, the metal content of vacuum residues could be substantially reduced by using a selective organic solvent such as pentane or hexane, which separates the residue into an oil (with a low metal and asphaltene content) and asphalt (with high metal content). Demetallized oils could be processed by direct hydrocatalysis. 

Solvent extraction may also be used to reduce asphaltenes and metals from heavy fractions and residues before using them in catalytic cracking. The organic solvent separates the resids into demetallized oil with lower metal and asphaltene content than the feed, and asphalt with high metal content. Figure 3-2 shows the IFP deasphalting process and Table 3-2 shows the analysis of feed before and after solvent treatment. Solvent extraction is used extensively in the petroleum refining industry. Each process uses its selective solvent, but, the basic principle is the same as above. 

The heptane insoluble (ASTM D-3279) method is commonly used to measure the asphaltene content of the feed. Asphaltenes are clusters of polynuclear aromatic sheets, but no one has a clear understanding of their molecular structure. They are insoluble in C3 to paraffins. The amount of asphaltenes that precipitate varies from one solvent to another, so it is important that the reported asphaltene values be identified with the appropriate solvent. Both normal heptane and... 

Furthermore, the injection of organic aromatic solvents and soaking is a feasible method to remove the precipitates [924]. The precipitation of asphalt from crude oil can be reduced by adding an N,N-dialkylamide of a fatty acid [1525,1527]. When asphaltenes are precipitated out, they can be removed from the walls of a well, pipeline, and so forth by washing with a hydrocarbon solvent. However, it has been shown that isopropyl benzoate is exceptionally useful as a solvent for asphaltene removal [1583]. 

Temperature-Controlled Residuiun Oil Supercritical Extraction (ROSE) The Kerr-McCee ROSE process has been used worldwide for over two decades to remove asphaltenes from oil. The extraction step uses a hquid solvent that is recovered at supercritical conditions to save energy as shown in Fig. 20-21. The residuum is contacted with butane or pentane to precipitate the heavy asphaltene fraction. The extract is then passed through a series of heaters, where it goes from the liquid state to a lower-density SCF state. Because the entire process is carried out at conditions near the critical point, a relatively small temperature change is required to produce a fairly large density change. After the light oils have been removed, the solvent is cooled back to the liquid state and recycled. 

The classic definition of asphaltenes is based on the solution properties of petroleum residua in various solvents. The word asphaltene was coined in France by J.B. Boussingault in 1837. Boussingault described the constituents of some bitumens (asphalts) found at that time in eastern France and in Peru. He named the alcohol insoluble, essence of turpentine soluble solid obtained from the distillation residue "asphaltene", since it resembled the original asphalt. 

In modern terms, asphaltene is conceptually defined as the normal-pentane-insoluble and benzene-soluble fraction whether it is derived from coal or from petroleum. The generalized concept has been extended to fractions derived from other carbonaceous sources, such as coal and oil shale (8,9). With this extension there has been much effort to define asphaltenes in terms of chemical structure and elemental analysis as well as by the carbonaceous source. It was demonstrated that the elemental compositions of asphaltene fractions precipitated by different solvents from various sources of petroleum vary considerably (see Table I). Figure 1 presents hypothetical structures for asphaltenes derived from oils produced in different regions of the world. Other investigators (10,11) based on a number of analytical methods, such as NMR, GPC, etc., have suggested the hypothetical structure shown in Figure 2. 

David, A., Asphaltenes Flocculation During Solvent Simulation of Heavy Oils. American Institute of Chemical Engineers. Symposium Series 1973, 2 (no. 127), 56-8. 

The crude oil produced from the Main Zone of the Torrance Field has an API gravity of 18° and contains 5.3 weight percent asphaltenes. The solubility of the asphaltene molecules in Main Zone oil was measured by the Oliensis Test(35). In this test, the solubility parameter Qf ie oil was lowered by adding to the oil successively larger volumes of hexadecane, a poor solvent for asphaltene molecules. The minimum volume (in milliliters) of hexadecane, which when added to 5 g of crude oil, will cause the chromatographic separation of the asphaltene fraction is termed the Oliensis Number. The Oliensis Number for the Main Zone crude oil is 3, indicating that the asphaltene molecules are not well-solubilized in the oil. Small changes in the solubility parameter of the Main Zone oil can cause the asphaltenes to precipitate. 

The present authors studied the solvolytic liquefaction process ( ,7) from chemical viewpoints on the solvents and the coals in previous paper ( 5). The basic idea of this process is that coals can be liquefied under atmospheric pressure when a suitable solvent of high boiling point assures the ability of coal extraction or solvolytic reactivity. The solvent may be hopefully derived from the petroleum asphaltene because of its effective utilization. Fig. 1 of a previous paper (8) may indicate an essential nature of this process. The liquefaction activity of a solvent was revealed to depend not only on its dissolving ability but also on its reactivity for the liquefying reaction according to the nature of the coal. Fusible coals were liquefied at high yield by the aid of aromatic solvents. However, coals which are non-fusible at liquefaction temperature are scarcely... 

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