Processing of Oil Sludges by Hydrocracking
The task of synthesizing the acidic component of carrier for the hydrocracking catalyst is rather difficult. This is due to the fact that the carrier must exhibit certain textural properties, in particular, a high specific surface area and an optimal acidity spectrum: to crack large molecules of heavy feedstock, the carrier must have a large number of acid sites active within a temperature range of 300 to 400 °C.
It was expected that the use of structured micro/mesoporous aluminosilicates with different acidic characteristics, acting as active components of the carriers, would allow optimizing the hydrocracking catalyst composition and hydrogenating sulphur compounds most effectively. The choice of the above materials among other mesoporous aluminosilicates was based on the fact that these materials have a pore size more than 40 Å; their synthesis is conducted in mild conditions, and the acidic properties can be regulated at the stage of synthesis. For the purpose, four different types of micro/mesoporous aluminosilicates have been obtained, all having high specific surface areas and rather strong acidic properties. The physicochemical characteristics of the obtained materials are described in publications [
20,
27]. Based on the synthesized alumino-silicates, sulphide Ni-W catalysts have been obtained and their activity in the oil sludge hydrocracking process has been studied.
To compare the effectivity of the synthesized catalysts of oil sludge hydrocracking, a series of experiments has been carried out using the SGK-5 industrial catalyst.
The results of the catalytic experiments are shown in
Table 2. The experiments have shown that in the studied temperature range, the main products of oil sludge hydrocracking were hydrocarbons of diesel fraction. The maximum yield of light products was observed in experiments at a process temperature of 400 °C and an initial hydrogen pressure of 110 atm (H
2-to feed stock = 1700 ncm
3/cm
3).
The results obtained show dependence of the yield of liquid products on the process temperature. At an initial hydrogen pressure of 50 atm observed is the determinate decrease in the yields of liquid reaction products with the simultaneous increase in the gas yield and an in-crease in the process temperature. An increase in pressure is also accompanied by a decrease in the yield of liquid products and an increase in gas formation.
The sulphide Ni-W catalysts obtained on the basis of micro/mesoporous materials were tested during the oil sludge hydrocracking. The results are given in
Table 3. For comparison, we present the results of the experiment conducted under the same conditions with the use of the SGK-5 industrial catalyst.
Catalysts NiS-WS2/SBA-15-MFI and NiS-WS2/MCM-41-ZSM-5 displayed maximum activity during oil sludge hydrocracking process because the yield of light fractions reached the largest values. For example, on the SBA-15-MFI-based catalyst, the ultimate yield of gasoline and diesel fractions was 51%, the conversion of heavy fraction distillated at a boiling point of more than 500 °C was 40%. On the NiS-WS2/MCM-41-ZSM-5 catalyst, the ultimate yield was 48% and the conversion of heavy fraction—38%. Whereas in contrast, on the SGK-5 catalyst, the same indicators were 17% for the light fraction, and 10% for the conversion. Moreover, in the case of synthesized catalysts, the maximum yield of gas products was observed, which is an evidence of the presence of strong acidic sites. Thus, the yields increase in the series of carriers SBA-15-MFI > MCM-41-ZSM-5 > TUD-zeolite-BEA > SBA-15-ZSM-5 > SBA 15-zeolite-BEA, which correlates to the data on acidity and textural characteristics that decrease in this series.
The products of oil sludge hydrocracking on micro/mesoporous catalysts were defined by the simulated distillation method; the curves of true boiling points were plotted based on the data obtained (
Figure 3). This graphic representation more clearly demonstrates the hydrocarbon fractions contained in hydrocracking products. So, for example, the products of oil sludge hydrocracking over catalyst NiS-WS
2/MCM-41 ZSM-5 contain more light hydrocarbons (T boil<150 °C) than the products obtained with the use of the catalyst NiS-WS
2/SBA-15 MFI, though the use of the latter catalyst resulted in the presence of more middle distillates in the hydrocracking products. Such results can be explained by the fact that the material of type MCM-41 ZSM-5, according to the data of the phase analysis by X-ray diffraction (PXRD) and NH
3 temperature programmed desorption (TPD), has high crystallinity and acidity that allows obtaining lighter products. In its turn, the material of type SBA-15 MFI contains a less prominent crystalline phase but more structured mesopores, which is an important point for obtaining diesel fractions, because in this case diffusion limitations are almost completely removed and large molecules of feedstock quickly penetrate and exit from the pores of the catalyst, practically without cracking to gaseous products.
Oil sludge processing using a sorbing electrochemical matrix.
As an alternative to the classical high-temperature oil sludge hydrocracking, we have proposed a method of low-temperature hydrogenation in sorbing electrochemical matrices.
For the purpose, we prepared three samples of water–oil emulsions with the following sludge/polycompexone ratios—4:1 (I) 3:2 (II) and 4.5:5.5 (III). Hydrogenation of water–oil emulsions was carried out in a sorbing electrochemical matrix (
Figure 1). Emulsions were placed in a reaction container. The study was performed with specified current J = 100 A, hydrogen production rate was 0.051 mmol/sec. During the process, we measured circuit voltage; using UV irradiation, monitored the appearance of S
2− or SO
32− in emulsion and in anolyte, and also derivatives of polymucosaccharides and triglycerides. It was found that voltage increased from
38–37 V to 42–34 V during 25–27 min, after which it achieved plateau. The appearance of S
2− in emulsion and SO
32− in anolyte is indicative of the transformation of sulphur-containing compounds, at which sulphur is released, of S
2− transfer from the reaction mass to anolyte and their oxidation at the anode to SO
32−. The appearance of green luminescence in catolyte testifies to the presence of water-soluble porphyrin complexes of vanadium and zink, while the appearance of violet luminescence in anolyte—to the presence of porphyrin complexes of iron [
15]. The simultaneous transition to catolyte and anolyte of polymucosaccharide derivatives during hydrogenation means the occurrence of the destruction of oil components with metal-porphyrin groups and the generation of polynuclear mixed-ligand metal complexes with ligand groups that are derivatives of polymucosaccharides and porphyrins. Depending on the total charge, they are transferred to catolyte or anolyte. Throughout the process, the yellowish-green luminescence of the emulsion disappears and a shade of blue appears. Oil luminescence depends on its group composition and the specified change in luminescence corresponds to a decrease in the content of resins and heavy aromatic compounds. Similar processes take place during high-temperature hydrogenation of oil.
Separation of emulsions into oil and water phases was performed with the use of nitrilotriacetic acid. It was found that during emulsion separation, derivatives of triglycerides of fatty acids passed into the oil phase while polymucosaccharide derivatives—into the water phase.
Table 4 presents the data on the content of sulphur and metals in oil phases.
We can observe from the table that the content of sulphur and metals decreases when the share of polycomplexones in emulsion increases. It is worth noting that the sulphur content in the oil phase after low-temperature hydrogenation in sorbing electrochemical matrices is by an order of magnitude less than after high-temperature hydrocracking.
After the hydrogenation of water–oil emulsions is completed, the oil phase was dehydrated by water stripping at 85 to 90 °C. The density and viscosity of obtained synthetic crude oils are given in the table (
Table 5).
The group composition was established for oil obtained from oil phase III (
Table 6).
Before hydrogenation, the water–oil emulsion contained about 40 g of iminodiacetate derivatives of triglycerides per 100 g of sludge. In the group composition, they are determined together with paraffins and naphthenes. If the amount of other components remained unchanged, then the content of paraffins and naphthenes should have increased to 55.8%, while the content of other components should have decreased by 1.4 times. In fact, the share of paraffins and naphthenes increased to 58.9%, i.e., by 3.1% above the expected one. The share of light aromatic hydrocarbons decreased by 1.85%, and of medium aromatic hydrocarbons—by 1.2% as compared with the expected one. The content of oxidized resins and asphaltenes decreased by 1.7% and 1%, and of heavy aromatic hydrocarbons and resins increased by 0.3% and 1.5%, as compared with the expected content. Metal complexes and sulphur-containing compounds are concentrated in resins and asphaltenes. During hydrogenation, a partial destruction of resins and asphaltenes occurs, owing to which the transformation of sulphur-containing compounds and the release of metal porphyrins become possible.