JPH0237390B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for lightening heavy hydrocarbon oil for converting heavy hydrocarbon oil into light hydrocarbon oil. The heavy hydrocarbon oils targeted by the present invention include crude oil, crude oil, atmospheric distillation residue or vacuum distillation residue oil of crude oil, tar sand crude oil extracted from tar sands, coal liquefied oil, and mixtures thereof. It is. These heavy hydrocarbon oils are
Usually, it contains a large amount of components with a boiling point of 90〓 or higher, and these components also contain large amounts of contaminants such as high molecular weight condensed aromatic hydrocarbon compounds called asphaltenes, heavy metals, sulfur compounds, and nitrogen compounds. ing. Note that asphaltene as used herein refers to n-heptane insoluble matter. Heavy hydrocarbon oils that are particularly effectively treated by the present invention have an API gravity of less than about 20° and a boiling point of 900°C or less.
It contains about 10% by volume or more, especially 20% by volume or more of the above heavy fraction, has a high asphaltene content, and has a high viscosity. Specific examples of the types of heavy hydrocarbon oils that can be advantageously treated in the present invention, together with their properties, are as follows. Venezuelan crude oil (Boscan crude oil) Specific gravity (゜API) 9.4 Viscosity (50℃, CP) 4950 Heptane insoluble content (wt%) 11.9 900 ⁺ Distillate content (vol%) 60 Vanadium (wt-ppm) 1190 Nickel (wt-ppm) 112 Atmospheric residual oil produced in the Middle East (Kafji atmospheric residual oil) Specific gravity (゜API) 11.2 Viscosity (50℃, cp) 3200 Heptane insoluble matter (wt%) 8.6 900 ⁺ distillate content (vol%) 70 Vanadium (wt-ppm) 100 Nickel (wt-ppm) 33 Canadian oil sand bitumen specific gravity (゜API) 9.6 Viscosity (50℃, cp) 3100 Heptane insoluble content (wt%) 7.7 900 〓 ⁺ Distillate content (vol%) 55 Vanadium (wt-ppm) 190 Nickel (wt-ppm) 78 Heavy hydrocarbon oils such as those mentioned above exist abundantly in nature, and are expected to become promising hydrocarbons in the future. Although considered a resource, it is currently only used as extremely low-grade fuel oil or simply as road asphalt. In order to make effective use of such inferior heavy hydrocarbon oil, much research has been focused on developing technology to convert it into high-value-added light hydrocarbon oil, but the economics of the process have been limited. Considering this, a satisfactory technology has not yet been established. Note that the light hydrocarbon oil referred to here refers to a component with a boiling point of 900ⓓ or less. Next, regarding the above-mentioned heavy hydrocarbon oil, techniques that have been conventionally studied in order to increase its added value will be explained as follows. (1) Pyrolysis method In this method, heavy hydrocarbon oil is heated to 350 to 550℃.
It is a method of thermal decomposition under operating conditions of temperature, normal pressure to 50 kg/cm ² pressure, and residence time of 5 minutes to 5 hours. Typical examples include visbreaking method and coking method. The visbreaking method is a method of thermally decomposing heavy hydrocarbon oil under relatively mild conditions in order to reduce its viscosity.The thermal decomposition rate is determined by the thermal stability and storage stability of the resulting oil. limited from the point. On the other hand, the coking method is a method of thermally decomposing heavy hydrocarbon oil under relatively severe conditions to convert it into light hydrocarbon oil and coke. Although it is possible to obtain a light hydrocarbon oil with this method, it is not possible to avoid producing a large amount of coke as a by-product. Moreover, the coke obtained at this time contains a large amount of impurities and cannot be used effectively, and the resulting oil has extremely poor thermal stability and storage stability, so it is necessary to hydrotreat it. Therefore, this method is also unsatisfactory as a method for lightening heavy hydrocarbon oil. In addition, a method is known in which heavy hydrocarbon oil is thermally decomposed in a hydrogen stream for the purpose of suppressing the generation of coke, but although this method can reduce the amount of coke in the produced oil, The thermal decomposition rate of heavy hydrocarbon oils is not sufficient, and the decomposition rate of high molecular weight fractions is particularly small, and no improvement in thermal stability is observed. (2) Catalytic hydrocracking method In this method, heavy hydrocarbon oil is
Temperature, 100~250Kg/ ^cm2 G pressure, 0.1~
Liquid space velocity of 10Hr ^-1 and _H2 /oil ratio 250~2500N
This is a method in which decomposition is performed under operating conditions of / in the presence of a catalyst capable of hydrogenation. This method is generally carried out in a fixed bed or ebullated bed system, but in the case of a fixed bed system, the catalyst layer is likely to be clogged by coking, so the reaction temperature is
Must be kept below 430℃ to avoid coking. Therefore, a sufficient decomposition rate cannot be achieved in the fixed bed system. on the other hand,
In the case of the ebullated bed method, compared to the fixed bed method,
Although it is possible to process at higher temperatures, the problem is that at high temperatures the rate of deterioration of the catalyst due to coking becomes extremely rapid.Moreover, with this method, large amounts of gaseous hydrocarbons are produced and hydrogen consumption is reduced. There is a problem in that the large size significantly impairs the economics of the process. Therefore, for the reasons mentioned above, this catalytic hydrocracking method is also not satisfactory as a method for lightening heavy oil. (3) Combining method of visbreaking and hydrodesulfurization In an attempt to improve the drawbacks of the above methods, a method was proposed that combines visbreaking and desulfurization to achieve product stabilization and desulfurization. There is. In this method, a hydrodesulfurization step is combined after the visbreaking step.
However, such a coupling method merely adds the hydrodesulfurization function of stabilizing and desulfurizing the produced oil to the visbreaking function; the essence of the technology is that the visbreaking It is not beyond the technical scope of engineering.
In other words, regarding the combined method of visbreaking and hydrodesulfurization, the essence of the technology is to reduce the viscosity of heavy hydrocarbon oil, and this combined method is suitable for lightening heavy hydrocarbon oil. isn't it. In such a bonding method, if the heat treatment conditions in the visbreaking step are made harsher in order to increase the decomposition rate of heavy hydrocarbon oils, condensed polycyclic aromatics such as resins and asphaltenes in heavy hydrocarbon oils may be The compounds further polycondensate to form benzene-insoluble macromolecules that are not naturally present in heavy hydrocarbon oils, which in turn creates significant difficulties in hydroprocessing. . Therefore, in the case of the conventional combined method of visbreaking and hydrodesulfurization,
It is not suitable as a method for lightening heavy hydrocarbon oil. There is also a combination method of hydrodesulfurization and visbreaking in which the steps are combined in a different order (Japanese Patent Publication No. 50-3321). However, even in this method, the thermal decomposition conditions must be relaxed because it is unnecessary to maintain the thermal stability of the product, and therefore it is not suitable as a lightening method. Next, as another aspect, a method has been proposed in which the above-mentioned thermal hydrocracking method is combined with catalytic hydrogenation treatment. However, this method does not contactly treat all of the pyrolysis oil, but only the light fraction that is separated and removed from the pitch fraction of 900 or more, so a large amount of the fraction of 900 or more is left behind. It will come to life. As described above, in the prior art, no method has yet been proposed for lightening heavy hydrocarbon oil economically and with good yield to obtain treated oil with excellent stability. Lightened oil with poor stability is
In addition to producing sludge during storage, which causes layer separation, it also tends to stain the walls of the equipment during further purification. Moreover, such produced oil has poor compatibility with other hydrocarbon oils. The present inventors have devised a method to overcome the drawbacks of the conventional methods described above, to economically and efficiently lighten heavy hydrocarbon oil, and to obtain treated oil with excellent thermal stability and storage stability. As a result of extensive research to develop the technology, we found that when heavy hydrocarbon oil is heat-treated under a specific range of conditions, and the resulting heat-treated oil is further hydrotreated using a specific catalyst under a specific range of conditions. Surprisingly, the present inventors discovered that it is possible to obtain a product oil with a high yield that could not be achieved by conventional lightening methods, and which also has excellent stability and compatibility, leading to the completion of the present invention. . That is, according to the present invention, in producing light hydrocarbon oil from heavy hydrocarbon oil, (i) the heavy hydrocarbon oil is heated at a temperature of 400 to 530°C and a pressure of 0 to 200°C.
Kg/cm ² G, residence time 1 minute to 5 hours, and a step of thermal decomposition at a lightening rate of 15 to 35% by volume, and (ii)
The decomposition product is treated as it is/or after separating and removing the low boiling point fraction, at a temperature of 350 to 450℃ and a pressure of 50℃.
~250Kg/ ^cm2G , liquid hourly space velocity of 0.1~5Hr ^-1 , _H2 /oil ratio 100~2000N/, at least one metal selected from metals of Groups B, B, and B of the periodic table. The catalyst metal component for hydrogenation is a porous inorganic oxide carrier composed of an oxide of at least one element selected from the elements of the periodic table and group (however, the main component is magnesium silicate). (excluding clay minerals with a double-chain structure), and the catalyst metal component is approximately 0.1 to 100% based on the total weight of the catalyst, calculated as an oxide.
a catalyst present in an amount within the range of 30% by weight;
Moreover, (a) the average pore diameter is in the range of approximately 200 to 400 Å, and (b) the pore volume with a pore diameter of 75 Å or more is 0.5 to 400 Å.
The pore volume is in the range of 1.5 cc/g, and the pore diameter is 100 Å or less, and the pore volume is 0.1 cc/g or less, and the pore diameter is 200 to 400.
Å pore volume is 0.2 cc/g or more, pore diameter 1500 Å
The pore volume of the above is 0.03cc/g or less, (c)
The surface area of pores with a pore diameter of 75 Å or more is about 70 m ² /g or more, and (d) catalytic hydrogenation using a catalyst in which the average equivalent diameter of the catalyst particles is in the range of about 0.6 to 5 mm. A method for lightening heavy hydrocarbon oil is provided, which comprises a step of obtaining a produced oil having a toluene insoluble content of 0.5% by weight or less. The processing conditions for the thermal decomposition process of the present invention are at a temperature of 400 to 530.
It is carried out at a pressure of 0 to 200 kg/cm ² G and a residence time of 1 minute to 5 hours. More preferably, the temperature is 430
～500℃, pressure 5～180Kg/ ^cm2G , residence time 10 minutes～
It is desirable to carry out the pyrolysis under conditions in the range of 2 hours. Note that the residence time is the value obtained by dividing the reaction section cavity volume in the thermal decomposition step by the feedstock oil flow rate in terms of 60〓. Alternatively, a method may be adopted in which a gaseous medium is injected together with the raw material oil into the thermal decomposition process, thereby reducing coke formation. As the gaseous medium it is possible to use heated steam, hydrogen and nitrogen, as well as one or a mixture of the gases and volatile components produced by the process of the invention. The present invention works effectively with the combination of the thermal cracking and the hydrotreating described below, because the lightening rate in the thermal cracking process (heavy components in the feedstock (≧900〓)
decomposition rate to light components (<900〓) of 15% by volume
In view of the above, it is preferable to set the amount to 25% by volume or more. Further, the upper limit of this lightening rate is set to about 35% by volume or less in view of the amount of substances (particularly toluene-insoluble components) that are generated in this thermal decomposition step and that cause deterioration of thermal stability and storage stability. In addition, in the thermal decomposition process, a tubular heating furnace (coil heater), a tubular reactor (tubular reactor)
Alternatively, either a chamber or drum type reaction system may be used. Furthermore, the thermal decomposition step may be divided into a first thermal decomposition step and a second thermal decomposition step, and a two-stage treatment method may be adopted. When carrying out the two-stage thermal decomposition, it is carried out by combining any of the above-mentioned reaction methods and appropriately setting the processing conditions for each step within the above-mentioned range of thermal decomposition. For example, when performing the first pyrolysis using a tube heating furnace in this process, the processing conditions are a temperature of 450~
530℃, normal pressure ~200Kg/ ^cm2G , residence time ~1 minute
It is desirable to carry out the heating for 20 minutes, and primary decomposition can be carried out within a range that does not cause clogging of the heating tube due to coking. In addition, the second pyrolysis step involves temperature
It is desirable to carry out the treatment at a temperature of 400 to 500°C, a pressure of normal pressure to 200 kg/cm ² G, and a residence time of 5 minutes to 5 hours.
In the case of the second stage pyrolysis, the second cracking can also be carried out while bringing the first cracked oil from the first pyrolysis step into contact with the gaseous medium described above. In the decomposition conditions in the thermal decomposition process, the temperature is
At temperatures below 400°C, the rate of decomposition reaction is slow and it takes a very long time to complete the desired lightening reaction, making it impractical; at temperatures above 530°C, the rate of polycondensation is too fast, resulting in pitfalls. Coking proceeds, which not only produces a large amount of substances that are difficult to process in the subsequent catalytic hydrogenation process, but also makes it difficult to control the reactions and operations in the thermal cracking process. Pressure has a great effect on the polycondensation, gasification, and coking reactions that occur as a side effect of heat treatment, and the higher the pressure, the lower the amount of gas produced. yield is improved. In addition, the reaction pressure has a large influence as a factor governing whether the reaction occurs in a gas phase or in a gas-liquid mixed phase.
By applying pressure, a greater proportion of the feedstock remains in the liquid phase in the heating tube, resulting in better heat transfer, less local overheating, and less coke formation. This effect is even more remarkable when thermal decomposition is performed using a gaseous medium, and especially when a hydrogen-containing gas is used as a medium, in addition to the above effects, thermal hydrogenation reaction (Thermal Hydrocracking)
This significantly reduces coking. on the other hand,
In terms of equilibrium, all decomposition reactions are reactions in which the number of moles increases, and a reduction in partial pressure by low pressure or the use of a diluent is advantageous for equilibrium. Therefore, the optimum pressure in the thermal decomposition process varies depending on the properties of the raw oil, the reaction temperature, etc., but in the method of the present invention, the optimum pressure is 0 to 0.
It is desirable to set it within the range of 200Kg/cm ² G.
Residence time has a clear correlation with reaction temperature, with shorter residence times being used at higher temperatures. Also,
As the residence time increases, the number of cracked products increases, but the polycondensation reaction gradually becomes more significant, and the amount of coke that is difficult to process in the subsequent catalytic hydrogenation treatment increases. Therefore, it is desirable that the residence time range employed in the method of the present invention is from 1 minute to 5 hours, preferably from 10 minutes to 2 hours. Additionally, the effluent from the pyrolysis step may require a quenching operation to stop the thermal reaction within a suitable reaction time before being fed to the subsequent catalytic hydrogenation step. The rush operation may involve injecting a cooling medium directly into the effluent or indirectly cooling it using a suitable heat exchanger. In the case of direct cooling, a hydrogen- or nitrogen-enriched gas, steam or a part of the product produced according to the invention can be recycled and used as the cooling medium. Further, the decomposition products from the thermal decomposition process are sent as they are, only the gas component, or after separating and removing the light hydrocarbon fraction, to the catalytic hydrogenation process. Whether to hydrotreat only the gas component or the heavy fraction separated from the light fraction from the product, or to supply the entire effluent from the heat treatment process to the hydrotreatment process depends on the raw material oil. properties and
It may be selected as appropriate depending on the properties of the target product, whether the thermal decomposition step and the hydrogenation step are to be carried out continuously, etc. The separation method can be carried out using commonly used gas-liquid separators, distillation columns, etc. In addition, when the thermal cracking process and the hydrotreating process are carried out simultaneously, high-purity hydrogen gas is used to simultaneously replenish the amount of hydrogen consumed in the hydrotreating process and rapidly cool the thermal decomposition products. An effective method is to inject hydrogen between the pyrolysis step and the hydrotreating step, in which case some or all of the hydrogen-rich gas obtained from the gas-liquid separator after the hydrotreating step is heated. It is desirable to adopt a method in which the material is recycled to the decomposition step and the thermal decomposition step is subjected to thermal hydrogenation treatment in a hydrogen atmosphere. The catalyst used in the hydrotreating step of the present invention is
At least one catalyst metal component for hydrogenation selected from metals of Groups B, B, and B of the periodic table, and an oxide of at least one element selected from elements of groups B and B of the periodic table. A catalyst composited with a porous inorganic oxide carrier composed of (excluding clay minerals with a double-chain structure mainly composed of magnesium silicate), in which the catalyst metal component is calculated as an oxide, The catalyst is present in an amount in the range of about 0.1 to 30% by weight based on the total weight of the catalyst, and (a) the average pore diameter is in the range of about 200 to 400 Å; (b) the pore diameter is 75 Å. The pore volume is
In the range of 0.5 to 1.5 cc/g, and with a pore diameter of 100
Pore volume of Å or less is 0.1cc/g or less, pore diameter is 200
~400Å pore volume 0.2cc/g or more, pore diameter 1500
The pore volume of Å or more is 0.03cc/g or less,
(c) The surface area of pores with a pore diameter of 75 Å or more is approximately 70 m ² /g
(d) The average equivalent diameter of the catalyst particles is in the range of about 0.6 to 5 mm. As used herein, the value of average pore diameter APD is defined by the following formula, with units of Å
This is the value expressed as . APD=4×PV×10 ⁴ /SA (1) In the formula, PV and SA represent the total pore volume and total surface area of pores with a pore diameter of 75 Å or more per unit weight of catalyst, respectively. The units were cc/g and m ² /g, respectively. From now on, if you are not particular about it, the pore value is 75 per gram of catalyst.
The total pore volume and total surface area having pores of Å or larger are simply referred to as the pore volume and surface area of the catalyst, respectively. Pore diameter, pore volume, and surface area values were determined using the Mercury-Pressier porosimeter model.
70 (manufactured by Carlo Erba, Milan, Italy) using the so-called mercury intrusion method (for details, see E.
W.WASHBURN, Rroc.Natl Acad.Sci., 7,
P.115 (1921), HLRITTER, LEDRAKE,
Ind.Eng.Chem.Anal., 17 , P.782, P.787 (1945),
LCDRAKE, Ind.Eng.Chem., 41 , P.780
(1949), and HPGRACE.J.Amer.Inst.Chem.
It is described in literature such as Engrs., 2 , P. 307 (1956). ). In this case, the surface tension of mercury is 474dyne/cm at 25℃, and the contact angle used is
140°, and the absolute mercury pressure was varied from 1 to 2000 Kg/cm ² . At this time, the pore diameter of 75 Å or more is expressed by the following formula: pore diameter (unit: Å) = 150000/absolute mercury pressure (unit: Kg/cm ² ). Average equivalent diameter ACD of catalyst particles used in the present invention
The value of is defined by the following formula, in mm
This is the value expressed as . ACD = 6 × (average volume of catalyst particles, unit mm ³ ) / (average outer surface of catalyst particles, unit mm ² ) (2) The values of the average volume and average outer surface of catalyst particles used here are The average particle diameter is measured by an appropriate method, and the value is expressed by the volume and outer surface area equivalent to a sphere having the average particle diameter. Measurement methods in this case include, for example, the direct measurement method, sieve separation method, and sedimentation method.Specific measurement methods are detailed in Powder Engineering Research Edition, "Particle Size Measurement Techniques," Nikkan Kogyo Shimbunsha (1975). Are listed. The catalyst used in the present invention is a composite catalyst consisting of a specific metal component for hydrogenation and a porous inorganic oxide carrier composed of a specific element, but the physical properties of the catalyst are as described above. The biggest feature is that it is defined within a specific range. That is, in the catalyst of the present invention, when it is finally used as a catalyst, physical properties, especially properties related to the catalyst pore structure such as average pore diameter, pore volume, pore distribution, and surface area, and the average of catalyst particles are required. The equivalent diameter plays an important role in effectively hydrotreating the product oil obtained by thermally decomposing heavy hydrocarbon oil, and in the present invention, these properties are determined within a specific range. By limiting the catalyst to It has a selectivity suitable for desulfurization and demetallization of thermal decomposition products including products, provides a product oil with excellent stability, and furthermore, its activity is maintained stably for a substantially long period of time,
Furthermore, we have found an optimal catalyst that has sufficient mechanical strength as a shaped catalyst. The characteristics and effects of the catalyst used in the hydrogenation process of the present invention will be specifically explained below. When heavy hydrocarbon oil is thermally decomposed to make it lighter, pitch-like substances are produced to a greater or lesser extent by polycondensation reactions. In addition, the S, N, and metal components in the raw oil are generally concentrated in the pitch, and at the same time,
It contains a large amount of solvent-insoluble matter such as n-heptane-insoluble matter, toluene-insoluble matter, or pyridine-insoluble matter. Toluene-insoluble matter is a polycondensation polymer compound produced by thermal polymerization of high-molecular hydrocarbons such as asphaltene in the feedstock oil, and its content is determined by the stability of the hydrotreated oil against heat or storage and the presence of other hydrocarbons. Closely related to compatibility with oil. That is, the toluene insoluble content is 0.5wt% or less, especially 0.15wt%
% or less has practically satisfactory stability and compatibility. The catalyst used in the catalytic hydrogenation process of the present invention is
It is an optimal catalyst for hydrotreating the above-mentioned pyrolysis product oil to obtain stable and high quality product oil. In the various hydrogenation reactions involved in the catalytic hydrogenation of oil produced from the pyrolysis process of heavy hydrocarbon oil, the rate is generally determined by the diffusion of the catalyst into the pores, but the Focusing on the hydrogenation or hydrocracking of unstable polymeric polycondensation compounds with molecular weights in the thousands that exist in Compatible catalysts have different pore sizes. In order for macromolecules such as n-heptane-insoluble matter and toluene-insoluble matter to easily diffuse into the active sites within the pores of the catalyst, it is more effective to increase the size of the pores. However, as the pore diameter of the catalyst increases, the active surface area within the pores decreases, and the overall reaction rate decreases. The pore size range showing good activity for hydrogenation or hydrogenolysis of the asphaltene content increased by thermal decomposition and the toluene insoluble content generated by thermal decomposition is the average pore diameter of the catalyst in the range of about 200 to 400 Å. When the average pore diameter is less than about 200 Å, the rate of diffusion within the pores is large, so hydrogen is not effective for reactions such as decomposition of asphaltenes and toluene insolubles, as well as desulfurization and demetallization of heavy pitt fractions. No effect of chemical treatment.
In particular, when the content of asphaltenes and heavy metals in the pyrolysis oil is high, these small and medium pores are easily reduced by the accumulation of metals and coke, further inhibiting the diffusion of asphaltenes into the pores. At the same time, coke and metal deposits begin to block the pore entrances. Therefore, such catalysts with small to medium pores can retain active surfaces within the pores when used for a short period of time for thermally decomposed oils with high contents of asphaltene and heavy metals. However, since empty pores are formed inside the catalyst that have completely lost any substantial catalytic function, it cannot be used as a catalyst of any practical use. For this reason, the average pore diameter is approximately 200Å.
The following pores are not effective for thermal decomposition of heavy hydrocarbon oils containing a lot of asphaltene and heavy metals.
In addition, from the perspective of improving catalyst utilization efficiency, the pore diameter is approximately 200% of the total pore volume of the catalyst.
The smaller the pore volume is, the better. Specifically, the pore volume with a pore diameter of about 100 Å or less is preferably about 0.1 cc/g or less, particularly 0.08 cc/g or less.
On the other hand, pores with a pore diameter of approximately 400 Å or more are large enough for asphaltene diffusion, but conversely, because the pores are too large, the pore surface area rapidly decreases as the pore diameter increases. At the same time,
Asphaltene decomposition reaction activity per total packed catalyst volume decreases, and as the pores become larger, asphaltene stays longer in the pores, resulting in more coke being deposited on the pore surface. Pore surface activity decreases due to coke poisoning. For the above reasons, the most effective catalyst for the hydrocracking process of the present invention has a pore diameter of approximately 200 to 400.
Å, and the larger the pore volume within that range, the more efficient the packed catalyst will be. In the case of the present invention, the pore volume with a pore diameter of about 200-400 Å is
It is desirable that the amount is about 0.2 cc/g or more, preferably about 0.3 cc/g or more. That is, a highly active catalyst for hydrogenolysis is a catalyst having a large number of pores with a pore diameter in the range of about 200 Å or more and about 400 Å or less. The surface area SA of the catalyst is preferably defined to be about 70 m ² /g or more in order to obtain a preferable catalytic activity. The size of catalyst particles is generally known to be a very important factor in reactions dominated by pore diffusion (for details, see PH
EMMETT, “Catalysis”, vol., Reinhold
Publishing Corporation New York (1955) and CNSatterfield, “Mass Transfer in
“Heterogeneous Catalysis”, MITPress,
Massachusetts (1970)), the present invention is also characterized in that the size of the catalyst particles is defined in relation to the pore diameter. The reaction activity in hydrogenation treatment decreases exponentially as the catalyst particle diameter increases; however, if the catalyst particle diameter exceeds the above-mentioned average equivalent diameter, the catalyst particles are too large and a satisfactory catalytic activity cannot be achieved. However, if the catalyst particles are too small, it becomes difficult to use them in reaction systems such as fixed bed, moving bed, and boiling bed, which have conventionally been widely used as catalytic hydrotreating equipment for heavy hydrocarbon oils. for example,
If the catalyst particles are too small, various disadvantages occur in the fixed bed system, such as an increase in the pressure difference between the catalyst beds, pulverization of the catalyst during use, and agglomeration of the catalyst due to interparticle precipitation of heavy metals and coke. Therefore, when used in these commonly used reaction systems, the average equivalent diameter of the catalyst particles is preferably in the range of about 0.6 to 5 mm. Furthermore, from the viewpoint of industrial use, an important requirement that an optimal catalyst should have is that it has sufficient mechanical strength. In general, compressive strength (Crushing Strength) and surface abrasion loss (Abrasion Loss) are used to express the mechanical strength of a catalyst for shaped catalysts, but the pore volume PV is in the range of 0.5 to 1.5cc/g. This is necessary to ensure the desired compressive strength. If the total volume of pores with a pore diameter of 1500 Å or more is large, the decrease in compressive strength and the degree of surface abrasion will be extremely large.From the perspective of the strength of the industrial catalyst, the pore volume with a pore diameter of 1500 Å or more is approximately 0.03 cc/ g or less. Giant pores with a pore diameter of 1500 Å or more are only related to the cracking properties of the catalyst, and hardly contribute to the asphaltene decomposition activity. Therefore, it is preferable to minimize the presence of such giant pores. Further, the carrier material of the catalyst used in the hydrogenation treatment of the present invention is a porous inorganic oxide composed of an oxide of at least one element selected from the elements selected from the groups and groups of the periodic table. These include, for example, oxides of single elements such as alumina, silica, titania, boria, zirconia, silica-alumina, silica-magnesia, alumina-magnesia, alumina-titania, silica-titania, alumina-boria. , alumina-zirconia, silica-zirconia, and other complex element oxides.These oxides may be used singly or in combination.
Applied as a mixture of more than one species. A catalytic metal component for hydrogenation, which is one of the constituent components of the catalyst, contains at least one transition metal selected from metals of Groups B, B, and B of the periodic table, and is particularly preferably ,vanadium,
molybdenum, tungsten, chromium, cobalt,
Contains nickel or copper. These catalyst components are effective in either the metal state, metal oxide, or metal sulfide state, and may also exist in a form in which a part of the metal component is bonded to the catalyst carrier by ion exchange or the like. The content of this metal component should be in an amount ranging from about 0.1 to 30% by weight, calculated as oxides, based on the total weight of the catalyst. If the metal content is less than about 0.1% by weight as an oxide, the activity of the catalyst will be insufficient and coking will easily occur, shortening the life of the catalyst. Moreover, if it is more than 30% by weight, the cost will increase and the catalyst surface area will decrease. The "periodic table" referred to in this specification is
“Websters 7th New Collegiate Dictionary”
C&C Merriam Company, Springfield,
This is the periodic table described on page 628 of Massachusetts, USA (1965). The catalytic metal component controls the activities of various reactions associated with the hydrotreatment of pyrolysis product oil from pyrolysis in the method of the present invention, such as hydrogenation, hydrocracking, demetalization, desulfurization, and denitrification. The selection and combination of metal components are arbitrarily determined depending on the reaction of particular interest in the hydrogenation treatment. Next, as described above, the method for producing the hydrotreating catalyst used in the method of the present invention is to achieve optimal catalytic activity,
Any conventional manufacturing method can be used as long as it can produce a catalyst with a specific pore structure, especially average pore diameter, pore volume, and pore distribution in order to obtain stability and strength. May be used. Next, the reaction method in the hydrotreating method of the present invention is determined by appropriately selecting the catalyst shape, etc.
It can be carried out in a conventional flow reaction system such as a fixed bed, moving bed, fluidized bed or ebullated bed, and the hydrogenation process can be carried out without the reaction product and catalyst flowing out together from the reaction zone. Further, the reactant may be supplied to the reaction section from either the upper or lower part of the reactor.
In other words, the flow of gas and liquid in the reactor is cocurrent upward flow,
It does not matter which method is used, downward flow. The shape of the catalyst particles may be granular, spherical, or cylindrical; however, when hydrotreating oil produced by thermal decomposition of heavy hydrocarbon oil with a high content of asphaltene and heavy metals, hollow cylindrical shapes are preferred. It is desirable to use elongated extruded catalysts that are non-circular in shape or cross-section, for example ellipsoidal, trilobal, multilobed, or have a surface with at least one or more grooves along its length. When such an irregularly shaped catalyst is used in a fixed bed, the porosity inside the reactor increases, which not only reduces the pressure loss in the catalyst layer, but also significantly reduces the clogging of the catalyst layer due to coke and metal deposits between the catalyst particles. It has a soothing effect. Regarding the treatment conditions in the hydrogenation treatment of the present invention, the temperature is 350 to 450°C, preferably 370 to 430°C, and the hydrogen pressure is 50 to 250 Kg/ ^cm2G , preferably 80 to 200Kg/ ^cm2.
G, liquid space velocity 0.1~5Hr ^-1 , preferably 0.2~
3Hr ^-1 . If the reaction temperature is less than 350°C, the catalyst activity will not be sufficiently exhibited and the reaction conversion rate in the hydrogenation process will not reach a practical level. Also, if the temperature exceeds 450℃,
Due to the polycondensation reaction of asphaltene, asphaltene does not decrease, but on the contrary tends to increase. Furthermore, the coking reaction becomes more intense, resulting in a decrease in the quality of the resulting oil, such as poor stability, and a decrease in catalyst activity.
Furthermore, it causes agglomeration of catalyst particles. Hydrogen pressure is 50
If it is less than Kg/cm ² G, coke will be generated so much that it will be extremely difficult to maintain normal activity of the catalyst.
If it exceeds 250 Kg/cm ² G, the hydrocracking reaction becomes intense, increasing hydrogen consumption, decreasing the yield of product oil, and increasing the cost of the reactor and other related equipment, making it impractical from an economic point of view. be exposed. When the liquid hourly space velocity is less than 0.1 Hr ^-1 , the residence time of the oil becomes longer and the heavy components in particular are affected by heat and deteriorate, resulting in a decline in the quality of the product oil.On the other hand, when it exceeds 5 Hr ^-1 , the oil only passes once. The reaction conversion rate per reaction is low and becomes impractical. The mixing ratio of pyrolysis product oil and hydrogen or hydrogen-containing gas to be supplied to the reaction section is 100 to 2000 volumes of hydrogen at 15°C per volume of pyrolysis product oil at 15°C at 1 atm (100 to 2000N/); Preferably 500~
It is done at 1000N/. This is 100N/
If it is less than that, hydrogen will be depleted in the reaction part and at the same time the transfer of hydrogen to the liquid will be poor, causing a coking reaction and the like, which will have an adverse effect on the properties of the catalyst and product oil. On the other hand, if it exceeds 2000 N/, there is no problem in terms of reaction, but it does not improve the method of the present invention in any way. The cost of the compressor used for hydrogen circulation increases as the amount of circulating hydrogen gas increases;
If it exceeds 2000N/, it becomes extremely expensive.
is the practical upper limit for hydrogen circulation. Even if hydrogen sulfide is contained in the hydrogen-rich circulating gas supplied to the reaction section, it not only does not have any adverse effect, but also tends to accelerate the reaction if it is contained in an appropriate amount. This is because the catalyst used in the present invention interacts with hydrogen sulfide in some way under the above reaction conditions, and hydrogen sulfide plays a certain role in maintaining catalyst activity. It is within the scope of the present invention to contain up to 10 mol%. After being treated under the above reaction conditions in the hydrotreating step, the catalyst-free reaction product is sent to a gas-liquid separation step where it is separated into a hydrogen-rich gas and a reaction product consisting essentially only of liquid. Ru. The gas-liquid separation method and equipment may be those used in normal fixed bed, ebullated bed, etc. desulfurization processes;
There are no particular regulations. In addition, the hydrogen-rich gas can be recycled to a pyrolysis process or a hydrogenation process,
It may also be used as a quenching medium for pyrolysis products. In addition, when treating heavy hydrocarbons containing a large amount of asphaltenes and heavy metals by the method of the present invention to obtain a light hydrocarbon oil substantially free of asphaltenes and heavy metals in high yield, hydrogen treatment is recommended. separating the reaction product from the step into a light fraction substantially free of asphaltenes and heavy metals and a heavy fraction containing asphaltenes and heavy metals in a separation step;
It is advantageous to circulate all or part of the heavy fraction back to the thermal cracking or hydrotreating step. According to this method, pyrolysis product oil containing a large amount of asphaltene can be continuously converted into light oil that does not contain asphaltene and heavy metals. In the case of such a circulation treatment method, hydrogen consumption and catalyst consumption are significantly reduced, and the advantage is that the yield of light oil is high. The separation means in this separation step does not need to be special, and commonly used methods such as distillation and solvent deasphalting can be used. When a solvent deasphalting method is employed in the separation process, the solvent used is a low molecular weight hydrocarbon such as methane, ethane, propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexane, etc. species or more, with which the liquid reaction product is brought into countercurrent contact. The operating conditions for solvent deasphalting are a temperature of 10 to 250 ℃.
C., preferably 50 to 150.degree. C., and a pressure of 3 to 100 atm, preferably 10 to 50 atm. In addition, by treating the method of the present invention using only the above-mentioned catalyst, a product oil with improved quality can be obtained, but this product oil has unique characteristics that are different from those obtained by conventional methods. It was found that it has the following properties. In other words, the molecular weight of the hydrocarbons contained in the produced oil is approximately distributed in the range of approximately 200 to 2000, and the asphaltene that remains slightly in the produced oil has a considerably lower molecular weight than that in the pyrolysis produced oil. Moreover, the sulfur and heavy metal contents in the residual asphaltene are significantly reduced, and compared to the distribution of sulfur, nitrogen, etc. in the pyrolysis product oil, these components in the product oil are more abundant in the light distillate. to be distributed. Furthermore, this produced oil has unique properties that are different from hydrotreated oil obtained by conventional methods, regardless of the properties of the pyrolysis produced oil. In other words, according to the method of the present invention, even if the first stage thermal decomposition is quite severe in order to obtain lightened oil with a good yield, the product oil obtained by the second stage hydrotreatment has stability and compatibility. A product with no solubility problems can be obtained. In other words, the product oil obtained by further refining the hydrotreated oil has excellent stability, and the residual oil of the hydrotreated oil has excellent compatibility, so it can be used as a raw material for mixing with various heavy oils. Moreover, the obtained heavy oil does not produce sludge during storage and has excellent stability. As mentioned above, by employing the method of the present invention, it is possible to decompose heavy hydrocarbon oil to make it lighter, and also to efficiently perform demetallization, desulfurization, etc., and to obtain a product with a reduced Conradson carbon content, resulting in added value. The resulting product oil can be used as a feedstock oil for obtaining high-grade gasoline by catalytic cracking, etc., or to obtain kerosene, jet fuel oil, diesel oil, etc. by hydrocracking etc. It is ideal as a raw material oil. The present inventors have focused on the fact that the produced oil obtained by the method of the present invention has such unique properties, and have conducted various studies on hydrogenation treatment to further improve the quality of this produced oil. We have developed a two-stage hydrotreating method for pyrolysis of heavy hydrocarbon oil, which is extremely advantageous industrially. That is, the method of the present invention includes a method in which the product oil obtained from the pyrolysis step is treated in the following two-stage hydrotreating step. (a) Pyrolysis product oil at a temperature of 350 to 450℃ and hydrogen pressure
A step of hydrogenating the hydrogen obtained in step (a) by contacting it with the above-mentioned hydrogen-treating catalyst under hydrogenating conditions of 50 to 250 atmospheres and a liquid hourly space velocity of 0.1 to 5.0 Hr ^-1 ; At least a portion of the chemically treated oil is heated at a temperature of 350 to 450°C and under hydrogen pressure.
Under hydrogen conversion treatment conditions of 50 to 250 atm and a liquid hourly space velocity of 0.1 to 5.0 Hr ^-1 , the porous alumina-containing support was
As the metal component for hydrogenation, at least one selected from oxides and sulfides of metals in group B of the periodic table and at least one selected from oxides and sulfides of metals in group B. Composite, average pore diameter of about 80 to 200 Å, pore volume of pores of 75 Å or more, PV of about 0.4 to 1.5 cc/g, and surface area of SA of about 100 to 1.5 cc/g, with pores of 75 Å or more in diameter.
400 m ² /g of contact with a catalyst to carry out hydrogen conversion treatment. In the second hydrogenation treatment step (b), the hydrogenation metal component supported on the carrier is at least one selected from oxides and sulfides of metals in group B of the periodic table; It is a combination with at least one selected from the group metal oxides and sulfides. More preferably, it is a combination of at least one selected from oxides and sulfides of chromium, molybdenum, and tungsten and at least one selected from oxides and sulfides of cobalt and nickel. These metal components include approximately 2 to 40% by weight of the group B metal component (A) and approximately 2 to 40% by weight of the group B metal component (B), calculated as oxides based on the total weight of the catalyst. Ingredients are approximately 0.1-10% by weight
It is desirable that the amount of the compound be contained or supported. In addition to the above metal components, as a promoter component,
Further promoting denitrification and the reaction of reducing the Conradson carbon content by compounding at least one compound selected from the group of titanium, boron, phosphorus, and fluorine, or boron phosphate, or boron fluoride. You can also do it. Advantageously, the amount of the promoter component is about 1 to 30% by weight, calculated as oxide based on the total weight of the catalyst. The catalyst manufacturing method applied to the second stage hydrotreating step (b) is based on the pore structure of the final catalyst, especially the average pore diameter of about 80 to 200 Å, and the pore volume PV of 75 Å or more. Approximately 0.4 to 1.5 cc/g and surface area SA of pores with a pore diameter of 75 Å or more is approximately 100 to 400 m ² /g
Any known manufacturing method may be used as long as it falls within the range of . Further, the treatment method, treatment conditions, catalyst particle size and shape of the second stage hydrogen treatment step (b) are the same as those described above regarding the hydrogen treatment using the catalyst of the present invention. The catalyst carrier used in the second stage hydrotreating step (b) is an alumina-containing carrier, usually 70% by weight alumina.
Among the carriers containing the above, alumina and silica-alumina are preferably used. In addition, in the case of industrially advantageous two-stage treatment, the first
Either asphaltenes or heavy components containing heavy metals are physically separated from the product oil obtained by the stage hydrotreating, or asphaltenes or heavy metals are removed from the product oil obtained by the second stage hydrotreating. It is also possible to physically separate the heavy fractions containing , and to circulate the heavy fractions again to the first and/or second stage hydrogenation process or thermal decomposition process. Note that the process of separating the produced oil into a light fraction and a heavy fraction does not require any special method, as shown above, and can be carried out by a method such as a distillation method or a solvent deasphalting method. can. The above-described two-stage hydrotreating method according to the present invention includes:
Furthermore, even when processing inferior heavy oil containing extremely large amounts of asphaltenes and heavy metals, or when the product specifications of the produced oil are extremely strict, it is possible to efficiently decompose heavy hydrocarbon oil and make it lighter. This is an excellent method that can be used to convert virtually all of the oil into low-sulfur, high-quality desulfurized oil. Next, one embodiment of the present invention will be described with reference to the drawings. In FIG. 1, feedstock is sent through line 1, mixed with hydrogen-rich gas supplied from line 10, and fed through line 2 to pyrolysis step 3. The reaction product subjected to the thermal decomposition treatment in the thermal decomposition step 3 passes through line 4, is mixed and quenched with make-up hydrogen from line 5, and then passes through line 6.
It is sent to the hydrogenation treatment step 7 through. The reaction product subjected to hydrogenation in the hydrogenation step 7 passes through a line 8 and is sent to a gas-liquid separation step 9. In the gas-liquid separation step 9, the gas is separated into a hydrogen-rich gas and a liquid reaction product. The hydrogen-rich gas is recycled to the pyrolysis step 3 via line 10. On the other hand, the liquid product is taken out of the system as a product through line 11, or is subjected to an appropriate post-treatment such as hydrodesulfurization in order to further improve product specifications. The method of lightening heavy hydrocarbon oil according to the present invention has been described above, but in order to explain the present invention in more detail, specific examples will be given below. This specific example specifically explains the present invention, and includes:
The present invention is not limited to these specific examples. Next, the present invention will be explained in more detail with reference to Examples. Example 1 An example of the implementation of the present invention using vacuum residue oil from Khafji crude oil produced in the Middle East as the raw material is shown below. The properties of the raw material oil are as shown in Table 1.
6.8゜API, viscosity is 2320C.P. at 100℃, and 900
It is one of the typical heavy hydrocarbon oils containing 95.0vol% of boiling point fractions.

【table】

[Table] First, the raw material oil was heated at a flow rate of 500 c.c./Hr, and the hydrogen to oil ratio was 600 N/, that is, the hydrogen flow rate was 300 N/H.
After mixing with hydrogen-rich gas so that Hr.
After preheating to 350°C with a heater, it was supplied to the thermal decomposition process. The thermal decomposition process has an inner diameter of 7 mmφ and a length of 2.2 m.
A coil tube reactor was installed in a heated fluidized bath, and the temperature of the heated fluidized bath was controlled so that the temperature at the tube outlet was 485°C. The pressure also depends on the gas pressure at the outlet of the subsequent hydrotreating process.
140Kg/cm ² G by line control valve
was held. The residence time in the pyrolysis step in this case is approximately 5.7 minutes. The product oil from the pyrolysis step is then directly quenched with high purity hydrogen gas before being sent to the next hydrotreating step. This pyrolysis product oil had a lightening rate of 35% by volume, had a toluene insoluble content of about 4wt%, and was unstable. The hydrogen gas flow rate for the rapid cooling was about 200 N/Hr, and the total amount of hydrogen supplied to the hydrogenation process including this was about 1000 N/Hr. The mixture of pyrolysis products and hydrogen is then sent to a hydrotreating step at 408°C. The hydrotreating step consists of a downflow gas-liquid cocurrent isothermal fixed bed reactor packed with catalyst. The catalyst used was extrusion molded using alumina as a carrier material, supporting Co and Mo. Hydrotreating conditions are temperature 405℃, pressure 140Kg/
cm ² G, LHSV0.33Hr ^-1 , H ₂ /oil ratio approx. 1000N/
It is. The catalyst was obtained as follows. Place deionized water 5 in a stainless steel container that can be heated externally with a mantle heater and heat it to 95℃.
Aluminum nitrate (Al
(NO ₃ ) ₃ ·9H ₂ O) 1Kg was dissolved in water to give a concentration of 2.5, and 500 c.c. of the aqueous solution was added. Then the contents were heated to 95℃
was held at While stirring this solution, 14% by weight aqueous ammonia was added to adjust the pH to 8. Thereafter, the mixture was aged in a boiling state for 1 hour to produce a seed alumina hydrosol. Next, 500 c.c. of the aluminum nitrate aqueous solution was added to this hydrosol and maintained for 5 minutes. The pH at that time was 4. After that, after confirming that the temperature of the contents is 95℃ or higher,
% by weight of aqueous ammonia was added to adjust the pH to 9, and the mixture was held again for 30 minutes. This pH variation operation was repeated nine more times. Thereafter, the mixture was aged in a boiling state for 1 hour to obtain an alumina hydrogel. To wash the hydrogel, it was dispersed in deionized water and dehydrated using a vacuum filtration device. After repeating this washing operation three times, the mixture was dehydrated using a vacuum filter to obtain a cake containing approximately 25% by weight in terms of Al ₂ O ₃ . This cake is 1.0mm
After molding into a columnar shape (diameter 1 mm) using an extrusion molding machine having a die with φ holes, the molded product was dried at about 120°C for 2 hours, and then calcined in an electric furnace at 550°C for 3 hours. Next, this calcined product was used as a carrier, and molybdenum and cobalt were supported as hydrogenation metal components in the following manner. ammonium molybdate
Add 400 ml of warm water to 151.9 g, then add an aqueous solution obtained by dissolving 160.5 g of cobalt nitrate in 400 ml of distilled water, mix, and then add ammonia water with a concentration of 25% by weight.
Added 500ml. 35 ml of this liquid was taken, diluted with 5 ml of distilled water, and evenly sprayed on and impregnated with 50 g of the previously obtained calcined material, left sealed overnight, and then air-dried at room temperature. Next, dry with hot air at 120℃ for 3 hours.
A catalyst was obtained by calcining at 600° C. for 3 hours in an air stream. The properties of the obtained catalyst are shown in Table 2. The product obtained from the hydrotreating step was separated into a hydrogen-rich gas and a substantially liquid reaction product in a gas-liquid separator. The separation conditions in the gas-liquid separator were substantially equal to the pressure in the hydrotreating reactor, and the temperature was 150°C. The hydrogen-rich gas was used in a cleaning device to remove impurities such as hydrogen sulfide and ammonia, and then recycled to the thermal decomposition process. In addition, in order to avoid an unreasonable increase in the concentration of light hydrocarbon gas in the circulating gas, a certain amount of a portion of the circulating gas was discharged to the outside of the system. The liquid reaction product was further depressurized and sent to a gas-liquid separation tank, where it was separated into cracked gas and lightened product oil. Details of the properties of the produced oil after approximately 1000 hours are shown in Table 3 along with the stability and compatibility test results. In addition, the thermal stability test
According to ASTMD1661, UOP method 614 is used for toluene insoluble matter.
80, and the compatibility test was conducted according to ASTM D2781. Comparative Example 1 A comparative example in which the same raw material oil as in Example 1 was used and only thermal decomposition treatment was performed is shown below. The experiment was carried out by directly connecting the thermal decomposition process and the gas-liquid separation process without using the hydrogenation process in the apparatus of Example 1, and only the conditions for the thermal decomposition process and the gas-liquid separation process were carried out. The test was carried out under the same conditions as in Example 1. The properties of the resulting oil are shown in Table 3. As is clear from the results shown in Table 3, although thermal decomposition treatment alone achieves a certain degree of weight reduction,
The thermal stability of the produced oil is extremely poor, the content of n-heptane insolubles is much higher than that of the raw oil, and the resulting oil is of poor quality with almost no reduction in sulfur and heavy metal content. Examples 2 to 4 Lightening was carried out in exactly the same manner as in Example 1, except that catalysts having the properties shown in Table 2 were used in place of the catalyst used in Example 1. The results are shown in Table 4. Comparative Examples 2-3 Lightening was carried out in exactly the same manner as in Example 1, except that instead of the catalyst used in Example 1, a catalyst having the properties shown in Table 2 was used.
The properties of the resulting oil are shown in Table 3. As is clear from the results shown in Table 4, when catalysts with average pore diameters of 150 Å and 125 Å (Comparative Examples 2 and 3) were used, the resulting oils had poor stability and poor compatibility. On the other hand, the average pore size
According to the method of the present invention using a catalyst of 200 Å or more, a product oil with excellent stability and compatibility can be obtained.

【table】

【table】

【table】

[Table] Comparative Example 4 An experiment was conducted in the same manner as in Example 1, except that the residence time in the thermal decomposition step was about 8 minutes and the lightening rate was 45% by volume. In this case, the toluene insoluble content in the pyrolysis product oil is 7wt.
It was %. The product oil obtained from the hydrocracking process has a lightening rate of 55%, contains 0.8wt% of toluene insoluble matter,
It was unstable.

[Brief explanation of drawings]

FIG. 1 is a process diagram for carrying out the present invention.
Give an example. 3... Thermal decomposition step, 7... Hydrogenation step, 9... Gas-liquid separation step.

Claims (1)

[Scope of Claims] 1. In producing light hydrocarbon oil from heavy hydrocarbon oil, (i) The heavy hydrocarbon oil is subjected to residence at a temperature of 400 to 530°C and a pressure of 0 to 200 Kg/cm ² G. A step of thermally decomposing the product for a time of 1 minute to 5 hours at a lightening rate of 15 to 35% by volume, and (ii) the decomposition product is used as it is or after the low boiling point fraction is separated and removed, at a temperature of 350%. ~450℃, pressure 50~250Kg/ ^cm2G , liquid space velocity 0.1~5Hr ^-1 ,
At least one hydrogenation catalytic metal component selected from metals of groups B, B, and B of the periodic table is added under conditions of an H ₂ /oil ratio of 100 to 2000 N/. A catalyst composited with a porous inorganic oxide carrier composed of an oxide of at least one element selected from among the elements (excluding clay minerals with a double-chain structure mainly composed of magnesium silicate). a catalyst in which the catalytic metal component is present in an amount in the range of about 0.1 to 30% by weight, calculated as an oxide, based on the total weight of the catalyst, and (a) the average pore diameter is about (b) The pore diameter is 75 Å or more and the pore volume is 0.5 to 1.5.
cc/g, and the pore diameter is 100 Å or less, the pore volume is 0.1 cc/g or less, and the pore diameter is 200 Å or less.
The volume of pores with a diameter of ~400 Å is 0.2 cc/g or more, the volume of pores with a pore diameter of 1500 Å or more is 0.03 cc/g or less, (c) the surface area of pores with a pore diameter of 75 Å or more is approximately 70
m ² /g or more, and (d) toluene insoluble matter is removed by catalytic hydrogenation using a catalyst whose catalyst particles have an average equivalent diameter in the range of about 0.6 to 5 mm.
A method for lightening heavy hydrocarbon oil, characterized by comprising a step of obtaining produced oil of 0.5% by weight or less. 2. The method according to claim 1, wherein in the pyrolysis step, a gaseous medium is injected together with the raw material oil to perform the pyrolysis treatment. 3. The method of claim 2, wherein the gaseous medium is a hydrogen-rich gas. 4. The method according to claim 1, wherein the feedstock is a heavy hydrocarbon oil having a specific gravity of about 20° API or less and containing at least 10 vol% or more of a heavy fraction with a boiling point of 900 F or more. 5 Heavy distillates with a boiling point of 900F or higher in the feedstock are
At least on a volumetric basis to fractions with boiling points below 900F
The method according to claim 1, characterized in that the conversion is 30% or more.