Asphaltenes products

A feasible procedure for the recovery of oil from the residual solids in the first stage of coal hydrogenation consists in treating the heavy oil slurry from the hot catchpot with superheated steam (25). At short contact times of a spray of heavy oil slurry with superheated steam, a high recovery of oil, with little or no coking or secondary asphaltene production, was achieved. 

To test these hypotheses, a tar sand bitumen containing 20 wt % pentane asphaltenes was characterized and processed by hydropyrolysis before and after removal of asphaltenes. Product yields and structure were determined and the influence of asphaltenes on results was determined by inferrence. Feedstocks and products were characterized according to elemental analysis, physical properties, simulated distillation, and carbon-type analysis. Inferences made in this study are discussed in the context of the reported literature. 

In oil bearing formations, the presence of polar chemical functions of asphaltenes probably makes the rock wettable to hydrocarbons and limits their production. It also happens that during production, asphaltenes precipitate, blocking the tubing. The asphaltenes are partly responsible for the high viscosity and specific gravity of heavy crudes, leading to transport problems. 

The complexity of petroleum products raises the question of sample validity is the sample representative of the total flow The problem becomes that much more difficult when dealing with samples of heavy materials or samples coming from separations. The diverse chemical families in a petroleum cut can have very different physical characteristics and the homogeneous nature of the cut is often due to the delicate equilibrium between its components. The equilibrium can be upset by extraction or by addition of certain materials as in the case of the precipitation of asphaltenes by light paraffins. 

The conversion to lighter products is limited by the asphaltenes content (C insolubles). At high conversions, the residual asphaltenes —no longer being soluble in their environment— tend to precipitate, resulting in the production of unstable residues that are unmarketable. 

An important industrial example of W/O emulsions arises in water-in-crude-oil emulsions that form during production. These emulsions must be broken to aid transportation and refining [43]. These suspensions have been extensively studied by Sjoblom and co-workers [10, 13, 14] and Wasan and co-workers [44]. Stabilization arises from combinations of surface-active components, asphaltenes, polymers, and particles the composition depends on the source of the crude oil. Certain copolymers can mimic the emulsion stabilizing fractions of crude oil and have been studied in terms of their pressure-area behavior [45]. 

Tars can be hydrogenated to produce Hquid fuels. High hydrogen and low asphaltene, ie, benzene-soluble and pentane-iasoluble, contents are desirable. The central German brown coals are attractive for this reason. The tars from the eastern part of Germany require much lower pressures and less hydrogen per unit of product than do brown coals near Cologne, which can require pressures up to 71 MPa (700 atm) (see Petroleum). 

Aromaticity is the most important property of a carbon black feedstock. It is generally measured by the Bureau of Mines Correlation Index (BMCI) and is an indication of the carbon-to-hydrogen ratio. The sulfur content is limited to reduce corrosion, loss of yield, and sulfur in the product. It may be limited in certain locations for environmental reasons. The boiling range must be low enough so that it will be completely volatilized under furnace time—temperature conditions. Alkane insolubles or asphaltenes must be kept below critical levels in order to maintain product quaUty. Excessive asphaltene content results in a loss of reinforcement and poor treadwear in tire appHcations. 

Sandstone rock surfaces are normally highly water-wet. These surfaces can be altered by treatment with solutions of chemical surfactants or by asphaltenes. Increasing the pH of the chemical treating solution decreases the water wettability of the sandstone surface and, in some cases, makes the surface medium oil-wet [1644]. Thus the chemical treatment of sandstone cores can increase the oil production when flooded with carbon dioxide. 

S. D. Dzhanakhmedova, E. I. Pryanikov, S. A. Sulejmanova, K. K. Mamedov, E. G. Dubrovina, N. M. Indyukov, and A. B. Sulejmanov. Composition for preventing asphaltene-resin-paraffin deposits—contains waste from production of synthetic glycerine, in mixture with polyacrylamide. Patent SU 1761772-A, 1992. 

In this zone, the quantity of extracted oil is generally sufficient to obtain the distribution of the different structural groups (SARA analysis) except for oil A (Fig. 6 to 9) For oil B (Fig. 6), for the first two samples, the amount of extracted products is too low and the analysis is uncertain. It can only be noticed that the asphaltene content is null. On the contrary, just beyond the coke zone (samples III-IV), the asphaltene content respectively reaches 12.9 and 5 4 whereas the asphaltene content of the initial oil is only 0.3. This effect is also observed for oil C (10 versus 6.3%) (Fig. 7), D 24% versus 13.8 ) (Fig. 8), E (24 4 versus 8.1 ) (Fig. 9) For all the oils, the amount of resins+asphaltenes generally remains constant and the amount of saturates increases... 

Asphaltene deposition during oil production and processing is a very serious problem in many areas throughout the world. In certain oil fields (12,13,14) there have been wells that, especially at the start of production, would completely cease flowing in a matter of a few days after an initial production rate of up to 3,000 BPD. The economic implications of this problem are tremendous considering the fact that a problem well workover cost could get as high as a quarter of a million... 

Even for reservoirs in which asphaltene deposition was not reported previously during the primary and secondary recovery, it was reported that asphaltene deposits were found in the production tubing during carbon dioxide injection enhanced oil recovery projects (18). 

Asphaltene precipitation, in many instances, carries from the well tubing to the flow lines, production separators, and other downstream equipment. It has also been reported (19) that asphaltic bitumen granules occured in the oil and gas separator with oil being produced from certain oil fields. 

The postulated and sufficiently proven notion that asphaltenes are oxidation products of resins and that resins are oxidation products of oil (11) sort of makes the probability of finding oils whose actual resin concentration is less than their critical resin concentration small. In other... 

Figure 12 clearly shows the effect of iron sulfide content of the coal on total conversion and liquid product yield during hydrogenation. The conversion increased from about 52 per cent to 70 per cent using the hot-rod reactor with no added catalyst. The yield of toluene soluble product (oil plus asphaltene) increased from about 30 to 44 per cent with total sulfur increase from 1 to 6.5 per cent. Thus it would appear that iron sulfide can act catalytically in the dry hydrogenation reaction as well as in slurried reactions (15). 

A question then arises as to whether the CSD recovery is being limited by the preasphaltene content produced from direct products of coal liquefaction or whether by low liquefaction severity a more thermally sensitive product is produced resulting in retrogressive reactions of liquefaction products to "post-asphaltenes." There is some indication that "virgin" preasphaltenes, primary products of coal dissolution, are more easily recovered via CSD as shown in Table VII however, "postasphaltenes" made from thermal regressive reactions are not. 

A most striking result from the work described above is that the composition of the bottoms product and residues from the dissolution reaction did not depend on the chemical structure of the original coal material only their relative quantities differed. This supports the view of a mechanism involving the stabilisation of reactive fragments rather than an asphaltene-intermediate mechanism. The formation of a carbon-rich condensed material as a residue of the reaction and the fact that hydrogen transfer occurred largely to specific parts of the coal further supports this view. 

In this paper we have looked firstly at the effect that the catalyst concentration, secondly at the effect that the reactor temperature and finally at the effect that the residence time at temperature have on the chemical structure of the oils (hexane soluble product) produced on hydropyrolysis (dry hydrogenation) of a high volatile bituminous coal. Generally, the hydropyrolysis conditions used in this study resulted in oil yields that were considerably higher than the asphaltene yields and this study has been limited to the effects that the three reaction conditions have on the chemical nature of the oils produced. 

The product was removed from the cooled reactor and from the condenser with the aid of toluene. The solid residue was extracted with boiling toluene (250 ml) in a soxhlet extractor for 12 hours. The toluene solutions were combined and the toluene removed under reduced pressure. Hexane (250 ml) was added to the extract and it was allowed to stand for 24 hours with occasional shaking. The solution was filtered to leave a residue (asphaltene) and the hexane was removed from the filtrate under reduced pressure to give the oil. 

Product distribution For many years high pressure hydrogenation reaction has been dealt with as a consecutive reaction with asphaltene as the intermediate (4,5,6). Further it has been pointed out that Py-1, O2 likewise shows the behavior of intermediates. (See Figure 1) (3). 

---