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HEAVY OIL HYDROCRACKING ON A LIQUID CATALYST Felipe de Jesus Ortega García, and Elizabeth Mar Juárez Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b01132 • Publication Date (Web): 06 Jul 2017 Downloaded from http://pubs.acs.org on July 8, 2017
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HEAVY OIL HYDROCRACKING ON A LIQUID CATALYST F. J. Ortega García*, E. Mar Juárez Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas No 152, México D.F. 07730, México * Corresponding author. E-mail:
[email protected] Abstract. Heavy crude oil was upgraded into a lighter oil by means of hydrocracking on an acid MoNi liquid catalyst. Upgrading was measured in terms of specific gravity, viscosity and distillates yield. Experimental results show that heavy crude oil was upgraded at an extent which depends on the severity of the reaction conditions, in all cases hydrocracked oil was lighter, less viscous and richer in valuable distillates (up to 60 wt % more), as well as with less contaminants (sulfur and nitrogen) than the heavy crude oil. Hydrocracking experiments were carried out in a batch reactor which was operated at typical hydrocracking conditions, conversion was varied modifying reaction time over a range from 30 to 90 minutes or reaction temperature from 350 to 450 °C. Sediments and toluene insoluble hydrocarbons formation increased as reaction severity and conversion were higher, however, values obtained were small and lower than those obtained with a commercial heterogeneous catalyst, and in both cases no precipitation was observed. Comparison versus an industrial heterogeneous catalyst at the same reaction conditions indicates that performance of the liquid catalyst was better in terms of heavy molecules cracking but not as good in terms of contaminants removal. Key Words: Heavy crude oil, Upgrading, liquid catalyst, hydrocracking.
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Introduction U. S. Energy Information Administration forecast indicates that total world energy consumption will expand from 549 quadrillion Btu in 2012 to 815 quadrillion Btu in 2040, a 48% increase from 2012 to 2040. Fossil fuels shall continue to provide most of the world’s energy in 2040; liquid fuels, natural gas, and coal shall account for 78% of total world energy consumption. Although their share of total world energy consumption will decline from 33% in 2012 to 30% in 2040, petroleum and other liquid fuels shall remain the largest sources of energy.1 Heavy oil and bitumen are viewed as a large potential sources of liquid fuels since their total reserve of about 9–13 trillion barrels outweighs conventional light crude oil reserves of about 1.02 trillion barrels. However, transforming heavy crude oils into valuable fuels is not an easy task since they contain huge amounts of residual hydrocarbons boiling above 540 °C, these hydrocarbons include resins and asphaltenes which give them the characteristics of high viscosity, high density/low API gravity and high metals and contaminants content, making them difficult and expensive to process in conventional refineries.2-3 Currently there are several commercial refining thermal processes such as viscosity reduction, solvent extraction, gasification and coking, designed to process heavy oils; these processes, however, have many drawbacks: consume large amounts of energy, emit pollutants to the atmosphere, produce large amounts of coke, low yield and quality of valuable products (which need further processing to meet commercial specifications), have short operating cycles, etc.; even so, they share around 80 % of the worldwide installed capacity of heavy oil processing plants, the other 20 % is shared by catalytic hydrocracking. 4-10
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Hydrocracking processes are designed to transform heavy hydrocarbons into valuable distillates (naphtha, diesel and gasoil), to achieve this goal, heavy oil is subjected to high pressures and temperatures in the presence of hydrogen and a solid catalyst. Hydrocracking offer better yield and quality of liquid fuels than thermal processes, even so they are not the preferred option of refiners; this is mainly due to the higher investment and operating costs derived from the high hydrogen partial pressure required to promote catalytic reactions and to slow down catalyst deactivation.11-13 Heterogeneous catalysts are widely and effectively used for hydroprocessing light petroleum fractions such as naphtha, jet fuel or kerosene, however, when processing heavy fractions, such as heavy gas oils or residues, catalysts effectiveness is importantly affected because of the presence of large hydrocarbons found in those fractions; diffusion through the catalyst pores is slower as larger are the hydrocarbons processed, for instance, complex hydrocarbons such as asphaltenes cannot easily flow through the catalyst pores, some of them agglomerate and plug the pores reducing the catalyst efficiency. Fast catalyst deactivation is one of the greatest drawbacks of heavy oil hydrocracking processes, since it shortens operating cycle of fixed bed reactors or increases catalyst consumption in moving bed, ebullated bed or slurry bed reactors. Moreover, hydrocracking conversion is limited by sediments formation; sediments deposit on catalyst surface and cause deactivation; likewise, sediments also gradually deposit on process equipment causing fouling problems that can lead to plant shut down.14-16 Sediments formation is induced by high reaction temperature and also by high residence time, large hydrocarbons diffuse more slowly in catalyst pores, this increases exposure time in the catalyst and this can be an important factor for sediments formation.
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On the other hand, the logistics of fresh catalyst supply and disposal of wasted catalyst also may become very complicated because of the large amounts required and the stringent environmental regulations.17 Moreover, the price of the catalysts, which are made of molybdenum, nickel, cobalt and tungsten supported on alumina, has dramatically risen in the last 10 years, reducing the profit margins of these processes. In order to overcome this problem it has been proposed the use of more active and poison resistant catalysts,18-19 the use of disposable and dispersed catalysts such as the iron-containing ‘red mud’, a waste product created during the processing of bauxite for aluminum production in the Bayer process, which can significantly reduce catalyst cost.20 In most industrial plants hydrocracking is promoted by elevated temperatures which also promote coke and sediment formation. Carbon-carbon bond breakage can be catalyzed by acidic materials achieving the same conversion as thermal cracking but at lower reaction temperature, reducing coke and sediments formation; Silica-alumina, zeolites and other acidic materials have been used as hydrocracking supported catalysts,
21-23
however, even
using mesoporous supports, internal diffusion problems remain. Following these ideas, we propose a liquid catalyst which has a strong cracking activity and a moderated hydrogenation function. This catalyst properly mixed with the heavy oil can avoid the diffusional problems of the heterogeneous catalyst and promote hydrocracking reactions more easily. This catalyst may also help to solve problems of catalyst handling and improve profitability margins since it reports higher distillates yield and is cheaper than current heterogeneous catalysts.
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Experimental Catalyst preparation. 50 ml of demineralized water at 40 ° C were placed in a continuously stirred Erlenmeyer flask, then 1 g of sulfuric acid (H2SO4, from Fermont) was added, after that 5 g of ammonium molybdate tetrahydrate (NH4)6Mo7O24 4H2O from J T Baker) was incorporated until it was completely dissolved, finally 10 g of nickel sulfate (NiSO4 6H2O, from SigmaAldrich) were added and dissolved until a clear emerald green solution was observed. The solution was allowed to stand for 24 hours at 25 °C, no precipitation of solids was observed. The acidity of the solution was measured with a pH meter and molybdenum and nickel content were determined by atomic absorption (table 1).
Hydrocracking Hydrocracking experiments were carried out in a Parr batch reactor as follows: 200g of heavy oil were mixed with 2 g of liquid catalyst. Before each experimental test, the reactor was purged with N2 and stabilized at the required reaction pressure, temperature and stirring rate. Reactor was pressurized to 100 kg/cm2 with hydrogen and stirred at 500 RPM; then, reactor was heated to the selected reaction temperature at a rate of 50 °C/h. Hydrogen was fed or gases released to keep reactor pressure constant. In a series of experiments hydrocracking extent was varied modifying reaction time (30, 60 and 90 minutes) keeping reaction temperature constant (400 °C); in another series hydrocracking was varied modifying reaction temperature (350, 375, 400 and 450 °C) keeping reaction time constant
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(60 min); In order to compare the performance of the liquid catalyst against an heterogeneous industrial supported catalyst, an additional experiment were conducted at 400 °C reaction temperature and 60 minutes reaction time. Properties of the industrial catalyst are shown in table 2. To confirm results experiments were done twice. Physical and chemical properties of the feed and hydrocracked products were determined according to the ASTM methods. API gravity was measured according ASTM-D287 method. The kinematic viscosity was determined using a rotary viscometer. SARA (saturates, aromatics, resins and asphaltenes) analysis were determined by ASTM-D4124 method. Sulfur content was measured by ASTM-D4294 method and distillation curves were obtained by ASTM-D2887 method. Sediments and toluene insoluble on feedstock and hydrocracked products were determined by ASTM D4870 and ASTM D4072 methods respectively. After experiments catalyst was decanted from the hydrocracked product, its properties were different from the fresh catalyst (Specific gravity @ 15.6 °C/15.6°C 1.13, Viscosity @ 25 °C 1.56 cSt, pH < 4, Nickel, wt % 4.4, Molybdenum, wt % 3.4, indicating that some of the acid and some of the metals remained in the reaction product.
Results Hydrocracking experiments Experimental results are shown in table 3. As expected, in all cases heavy oil was effectively transformed into a lighter oil as evidenced by the higher API gravity and the lower viscosity of the cracked products which were lighter as reaction time or reaction temperature increased; for instance, at 400 °C reaction temperature and after 30 minutes
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reaction time API gravity increased by 5.5 units whereas at 90 minutes the increment was 8.7 units; likewise, viscosity was significantly reduced, heavy oil which hardly can flow at room temperature was converted into a light oil which flows more easily, at 400 °C reaction temperature and after 30 minutes reaction time, viscosity fell from 13490 cSt to 486 cSt and after 90 minutes viscosity was 106 cSt. At the less severe reaction conditions (350 °C and 60 minutes) upgrading was marginal, specific gravity only increased by 1.6 API and
hydrocracked oil was still too viscous (8600 cSt) indicating an incipient
conversion. In contrast, at the more severe reaction conditions (450 °C and 60 minutes), specific gravity increased by 14.2 API and viscosity was only 23 cSt, almost like water. Total Conversion, defined as the amount of hydrocarbons boiling above 540 °C that were transformed into hydrocarbons boiling below 540 °C, also increased as reaction conditions were more severe (figs 1 and 2). At the less severe reaction conditions, total conversion was only 6 wt %, and at the more severe reaction conditions it was considerably high, 81 wt %. It is noticeable that even though asphaltenes are the more complex species, they were the more converted, over 80 % of total conversion was due to asphaltenes conversion. This can be explained by the fact that asphaltenes can be transformed into resins, aromatic and saturated hydrocarbons, but these hydrocarbons cannot be transformed into asphaltenes. As conversion increased, sediments and toluene insoluble hydrocarbons also increased, however, the increment was discrete, the highest values observed, were 0.57 and 0.17 wt % respectively. These values are relatively low, however, considering an industrial plant procesing 20000 barrels per day, the amounts of sediments and toluene insoluble would be 17 and 5 tons per, enough to shut the plant down in one day. Fortunately they are kept dispersed in the oil helped by resins and aromatic hydrocarbons in which asphaltenes are at least partially soluble, precipitation rate must be slow; if this were not the case industrial
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hydrocracking plants could not operate. At least, no precipitation was observed in the experimental hydrocracked products even after several weeks. Distillation curves (figures 3 and 4) show that valuable distillates (naphtha, diesel and gasoil) in hydrocracked oil increased while residual hydrocarbons decreased as reaction time or reaction temperature increased, indicating that heavy hydrocarbons in crude oil were transformed into lighter hydrocarbons. Assuming 221 °C as the final boiling point for naphtha, 343 °C for diesel and 540 °C for gasoil, the correspondent yields for each cut were estimated from distillation data. At 400°C reaction temperature and 30 minutes reaction time, hydrocracked oil contain 52 wt % valuable distillates, which is 28 wt % more than the distillates content on the heavy crude oil; at 90 minutes reaction time, valuable distillates increment was about 55 wt %. At the less severe reaction conditions (350 °C and 60 minutes), valuable distillates only increased by 3 wt %, confirming that at this temperature, conversion is very low; in contrast, at 450 °C reaction temperature valuable distillates increased about 60 wt %. In all cases gasoil yield is the highest, followed by diesel, and naphtha, this suggests that hydrocarbons boiling above 540 °C (residue) are converted into gasoil, gasoil is converted into diesel and diesel is converted into naphtha. It is important to mention that even at a high reaction temperature, there was no coke production as it happens in thermal cracking processes. Hydrocarbon families evolution is illustrated in figures 5 and 6, in all cases asphaltenic hydrocarbons content in the hydrocracked oil is lower than in the heavy crude oil; resins increase at low conversion and decrease as conversion increases; aromatics and saturated hydrocarbons increase in all cases; this indicates that crude oil upgrading is mainly due to asphalthenes and resins conversion. For instance, at 400 °C reaction temperature and 90
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minutes reaction time, 68 % of the asphalthenes and 42 % of the resins of the crude oil were converted; at 450 °C reaction temperature and 60 minutes reaction time, asphalthenes were converted by 82 % and resins by 43 %. In contrast, at 400 °C reaction temperature and 90 minutes reaction time, saturated and aromatic hydrocarbons content in hydrocracked oil were 30.8 and 47.5 wt % respectively, which are 130 and 17 % higher than the respective content of those hydrocarbons in the heavy crude oil; at 450 °C and 60 minutes results are similar, saturated hydrocarbons increased by 156 % whereas aromatic hydrocarbons increased by 19 %. These results imply that asphalthenes were converted into resins, resins into aromatics and saturated hydrocarbons, aromatic hydrocarbons into saturated hydrocarbons and heavy saturated hydrocarbons into light saturated hydrocarbons. Even though the catalyst was not intended to achieve high levels of hydrodesulfurization (HDS) and hydrodenitrogenation (HDN), both contaminants, sulfur and nitrogen, were significantly removed as shown in figures 7 and 8. Contaminants removal was higher as reaction severity increased. At 400 °C reaction time and 30 minutes reaction time, HDS and HDN were 30 and 23 wt % respectively; At 400 °C reaction time and 90 minutes reaction time, HDS was 53 wt % and HDN 40 wt %. At 350 °C and 60 minutes, contaminants removal was marginal, only 14 wt % of sulfur and 7 wt % nitrogen were removed; in contrast at 450 °C and 60 minutes HDS and HDN were 61 and 47 wt % respectively. As shown in table 3 thermal cracking was incipient, less than 3 wt % gas was produced at 400 °C reaction time and 30 minutes reaction time and only 5.3 wt % at 90 minutes; at 350 °C and 60 minutes gas yield was 1.2 wt %, however, at 450 °C and 60 minutes gas yield was about 10 wt %, an important increment which indicates that optimum reaction temperature should be below 450 °C since high gas yield implies higher investment and
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operating costs. In all cases hydrogen sulfide resulting from hydrodesulfurization was the main gas component. All these results are consistent with our previous work.24 Comparison versus the industrial heterogeneous catalyst at the same reaction conditions is shown in table 4. Both catalyst upgrade crude oil converting asphalthenes and resins into aromatic and saturated hydrocarbons by means of hydrocracking, however, as indicated by the distillates yield, liquid catalyst cracking activity is higher than the heterogeneous catalyst, reporting 16 wt % more valuable distillates, as a consequence physical properties of hydrocracked product are better. Nevertheless, sulfur and nitrogen removal were higher with the heterogeneous catalyst, indicating that its hydrogenating function is better than in the liquid catalyst. This can be explained by the higher amount of nickel and molybdenum in the solid catalyst. Even though conversion was lower for the heterogeneous catalyst, sediments and toluene insoluble hydrocarbons were significantly higher, this may be due to diffusional effects that imply a higher residence time of some hydrocarbons in the catalyst which promotes dehydrogenation and condensation reactions. Liquid catalyst consumption is considerably higher than heterogeneous catalyst consumption (a typical value for H-Oil units was assumed), 1.4 vs 0.32 kg per processed barrel, however, since liquid catalyst is cheaper than heterogeneous catalyst (2.94 vs 20 USD/kg), liquid catalyst cost is lower than heterogeneous catalyst (4.12 vs 6.4 USD per processed barrel). All these results show the ideas supporting this work may be right.
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Heavy crude oil was effectively transformed into lighter oil by a liquid Ni – Mo catalyst. This catalyst avoids internal diffusional effects of large hydrocarbons which affect heterogeneous catalyst effectiveness. Liquid catalyst promotes asphaltenes conversion which are the most complex and undesirable hydrocarbons of crude oils, additionally it shows a moderate activity to remove contaminants such as sulfur and nitrogen, and reports low values of sediments and toluene insoluble hydrocarbons. Therefore it is an interesting alternative for upgrading the heavy oil due to its low processing cost.
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Tables caption Table 1. Liquid catalyst properties Table 2. Commercial heterogeneous catalyst properties Table 3. Hydrocracking experimental results Table 4. Hydrocracking comparison: heterogeneous vs liquid catalysts
Figures caption Fig 1. Conversion as a function of reaction time @ 400 °C reaction temperature. Fig 2. Conversion as a function of reaction temperature @ 60 min reaction time. Fig 3. Hydrocracked oil simulated distillation as a function of reaction time @ 400 °C reaction temperature. Fig 4. Hydrocracked oil simulated distillation as a function of reaction temperature @ 60 min reaction time. Fig 5. Hydrocarbon families evolution as a function of reaction time @ 400 °C reaction temperature. Fig 6. Hydrocarbon families evolution as a function of reaction temperature @ 60 min reaction time. Fig 7. Sulfur and nitrogen removal as a function of reaction time @ 400 °C reaction temperature. Fig 8. Sulfur and nitrogen removal as a function of reaction temperature @ 60 min reaction time. Table 1 Specific gravity @ 15.6 °C/15.6°C Viscosity @ 25 °C, cSt pH Nickel, wt %
1.198 1.88
