CA2150205A1 - Process for hydrotreating heavy hydrocarbon oil - Google Patents
Process for hydrotreating heavy hydrocarbon oilInfo
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- CA2150205A1 CA2150205A1 CA 2150205 CA2150205A CA2150205A1 CA 2150205 A1 CA2150205 A1 CA 2150205A1 CA 2150205 CA2150205 CA 2150205 CA 2150205 A CA2150205 A CA 2150205A CA 2150205 A1 CA2150205 A1 CA 2150205A1
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- oil
- oils
- heavy hydrocarbon
- hydrotreating
- additive
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Abstract
A novel hydrotreating process is provided, which comprises hydrotreating a mixed oil of a heavy hydrocarbon oil feedstock and at least one additive oil or partially aromatic ring-hydrogenated oil thereof in an amount of 0.3 to 15% by weight with respect to the feedstock, at a temperature of 330 to 460°C, a hydrogen partial pressure of 50 to 250 Kg/cm2, a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr-1 in the presence of a hydrotreating catalyst, the additive oil being selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction. According to the process, coke formation, which cause clogging of heat exchangers, an increase in the pressure drop of preheaters, and a decrease in catalytic activity, can be greatly reduced.
Description
TITLE OF THE INVENTION
PROCESS FOR HYDROTREATING HEAVY HYDROCARBON OIL
BACKGROUND OF THE INVENTION
- 5 1. Field of the Invention This invention relates to a process for hydrotreating a heavy hydrocarbon oil (or so-called heavy hydrocarbon oil feedstock) with greatly reduced carbonaceous material formation, and more particularly, to a process for hydrotreating a heavy hydrocarbon oil wherein the formation of carbonaceous material can be reduced by incorporating a small amount of specific additive oil into the heavy hydrocarbon oil.
PROCESS FOR HYDROTREATING HEAVY HYDROCARBON OIL
BACKGROUND OF THE INVENTION
- 5 1. Field of the Invention This invention relates to a process for hydrotreating a heavy hydrocarbon oil (or so-called heavy hydrocarbon oil feedstock) with greatly reduced carbonaceous material formation, and more particularly, to a process for hydrotreating a heavy hydrocarbon oil wherein the formation of carbonaceous material can be reduced by incorporating a small amount of specific additive oil into the heavy hydrocarbon oil.
2. Background Art A problem associated with the conventional process for the hydrotreatment of asphaltene-containing heavy hydrocarbon oils, such as atmospheric residual oils or vacuum residual oils, is the formation of carbonaceous material (coke) which causes clogging of heat exchangers thereby increasing the pressure drop of preheaters and deactivating the catalyst, thus deteriorating the quality of the product.
Several reports have appeared, showing that the hydrotreatment of a heavy hydrocarbon oil ln the presence of a hydrogen-donating substance is effective for controlling 215020!j the formation of coke. Recycling of part of the hydrotreated oil from the reactor has been practiced in this respect;
however, in these conventional processes, a great amount of hydrogen-donating substance needs to be added or recycling of a great amount of hydrotreated oil is required, in addition to the fact that the effect of these additives for controlling the formation of coke is still insufficient.
A principal object of the present invention is to provide an improved process for hydrotreating a heavy hydrocarbon oil so that remarkably less carbonaceous material (coke) will form thereby allowing the hydrotreating operation to continue for longer periods of time in a stable state and to solve the problems associated with the formation of coke.
SUMMARY OF THE INVENTION
The applicant of the invention has intensively researched to solve the foregoing problems, and as a result, has found that the formation of carbonaceous material may be greatly reduced by incorporating a small amount of specific additive oil into the heavy hydrocarbon oil. The present inventions are based on this finding.
That is, the first aspect of the present invention is directed to a process for hydrotreating a heavy hydrocarbon oil, wherein the process comprises hydrotreating a mixed oil of the heavy hydrocarbon oil and at least one 21s0205 additive oil in an amount of 0.3 to 15% by weight with respect to the feedstock at a temperature of 330 to 460C, a hydrogen partial pressure of 50 to 250 Kg/cm , a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr in the presence of a hydrotreating catalyst, the additive oil being selected.from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction.
The second aspect of the invention is directed to a process for hydrotreating a heavy hydrocarbon oil, wherein the process comprises hydrotreating a mixed oil of the heavy hydrocarbon oil and at least one partially aromatic ring-hydrogenated additive oil in an amount of 0.3 to 15% by weight with respect to the heavy hydrocarbon oil, at a temperature of 330 to 460C, a hydrogen partial pressure of 50 to 250 Kg/cm , a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr in the presence of a hydrotreating catalyst, the additive oil being selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in further detail hereinbelow.
The term "heavy hydrocarbon oil" refers to a 2l~o2os petroleum hydrocarbon oil, 50% by weight or more of which boils at 350C or higher. Examples of such heavy hydrocarbon oils include atmospheric residual oils obtained by topping crudes, and vacuum residual oils obtained from the atmospheric residual oils by vacuum distillation.
The term "hydrotreating" refers to one of those including hydrodesulfurization, hydrodemetallization, hydrodenitrogenation and hydrocracking.
The hydrotreating is usually performed at a temperature of 330 to 460C, preferably at 360 to 440C, more preferably at 380 to 420C, and a hydrogen partial pressure of 50 to 250 Kg/cm , preferably 70 to 200 Kg/cm , more preferably 100 to 150 Kg/cm in the presence of a catalyst.
Usually an LHSV of 0.1 to 4.0 hr , preferably 0.2 to 1.0 hr may be employed.
In the hydrotreating of the present invention, any conventional hydrotreating catalyst may be used. Examples of the catalyst include a catalyst comprising particles containing one or more of the metals selected from Group V
through Group VIII metal components of the Periodic Table supported on carrier particles such as alumina, silica-alumina, or a cationic exchange zeolite. Oxides or sulfides of these metals may be also used. Examples of these metals include nickel, cobalt, molybdenum, vanadium, wolfram, and mixtures thereof.
215020~
Any type of hydrotreating reactor such as a fixed-bed, moving-bed, or fluidized-bed may be employed.
In the present invention, an additive oil selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction is added to the heavy hydrocarbon oil, 50~ by weight or more of the additive oil boiling at 250C or higher, preferably at 250 to 600C. Preferred percentage (~) of the aromatic carbons of the additive oil is 60 or more.
The additive oil may be employed as mixtures thereof.
Further, instead of oils obtained by coal liquefaction, powdered coal before liquefaction may be employable in the present invention.
According to the first aspect of the present invention, there is provided a process for hydrotreating a heavy hydrocarbon oil wherein an additive oil selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction is blended with the heavy hydrocarbon oil without any pretreatment, such as a thermal treatment, of the additive oil.
The additive oil is present in an amount of 0.3 to 15~ by weight, preferably 0.5 to 8% by weight on the basis of the heavy hydrocarbon oil.
Although any blending technique may be used, the foregoing additive oil is preferably fed into the reactor separately from the heavy hydrocarbon oil or after being blended with the heavy hydrocarbon oil.
According to the second aspect of the present invention, there is provided a process for hydrotreating a heavy hydrocarbon oil wherein the foregoing additive oil is partially aromatic ring-hydrogenated prior to being charged into the hydrotreating reactor.
The partial hydrogenation of aromatic rings is carried out so that a percentage of the aromatic carbon atom of the resulting hydrogenated oil will be within the range of from 5 to 50~, preferably 10 to 40%. The foregoing percentage is represented by the following formula (1):
Percentage (%) of aromatic carbon atom =
(Number of aromatic ring carbon atoms present in given oil amount (g))/(Total number of carbon atoms present in given oil amount (g))xlOO ................................. (1) Any method for the partial hydrogenation of aromatic rings may be used. Usually the aromatic rings are partially hydrogenated in the presence of a hydrogenation catalyst in a pressurized hydrogen atmosphere.
Any conventional hydrogenation catalyst such as one suitable for use in hydrotreating a petroleum fraction may be 215020~
used herein. More particularly, a catalyst comprising particles containing one or more of the metals selected from Group V through Group VIII metal components of the Periodic Table supported on inorganic carrier particles is employed.
Oxides or sulfides of these metal components may also be used. Examples of such metal components include nickel, cobalt, molybdenum, vanadium, and wolfram. Examples of such inorganic carriers include alumina, silica-alumina, a cation exchange zeolite, kieselguhr, and the like.
Aromatic ring-hydrogenation catalysts may also be preferably employed. Examples of the catalyst include a catalyst comprising particles containing one or more of the metal components, such as nickel, nickel oxide, nickel-copper, platinum, platinum oxide, platinum-rhodium, platinum-lithium, rhodium, palladium, cobalt, ruthenium, or Raney-cobalt, supported on inorganic carrier particles.
Examples of such inorganic carriers include active carbon, alumina, silica-alumina, kieselguhr, zeolite, and the like.
Preferred conditions for partially hydrogenating aromatic rings are as follows: a temperature of 300 to ~00C
and a pressure of 30 to 150 Kg/cm , when a catalyst for use in hydrotreating a petroleum fraction is employed; a temperature of 150 to 300C and a pressure of 30 to 150 kg/cm , when a catalyst for use in hydrogenating aromatic rings is employed.
2l5o2o5 Any type of apparatus such as a fixed-bed, moving-bed, fluidized-bed or a batch type apparatus may be employed.
The partially aromatic ring-hydrogenated oil thus obtained is charged into a hydrotreating reactor.
The partially aromatic ring-hydrogenated oil to be added to the heavy hydrocarbon oil is present in an amount of 0.3 to 15% by weight, preferably 0.5 to 8% by weight with respect to the weight of the heavy hydrocarbon oil. The hydrogenated oil may be charged into the reactor separately from the heavy hydrocarbon oil, or charged after being blended with the heavy hydrocarbon oil.
The partially aromatic ring-hydrogenated oil according to the present invention has remarkable hydrogen-donating properties, and can effectively control the formation of carbonaceous material even when added to the heavy hydrocarbon oil in a small amount.
In addition, the specific oil as an additive in accordance with the present invention is further converted to aromatic ring-hydrogenated substances of high hydrogen-donating activity in the hydrogenation reactor, whereby the formation of carbonaceous material can be reduced likewise.
The invention will be further illustrated by the following examples but in no way limited by the examples.
2~0205 A Middle East topped crude having properties as specified in Table 1 was treated in a downward fixed-bed reactor (internal diameter; 10 mm, height; 0.5 m, catalyst volume; 30 cm ) in the presence of a commercially available Ni-Mo/silica-alumina catalyst at a temperature of 413C, a hydrogen partial pressure of 165 atm, and a LHSV of 0.50 hr~1. In this experiment, an additive oil obtained by the procedure that follows was added to the heavy hydrocarbon oil in an amount of 3% by weight with respect to the heavy hydrocarbon oil.
That is, the foregoing specific additive oil was obtained from a decrystallized anthracene oil by removing the fraction boiling up to 250C. The resulting oil was determined to contain 89~ by weight aromatic carbons.
The hydrotreating was continued for about 260 hr.
The properties, amount of dried sludge and toluene insolubles of the resulting product after 240 hr are set forth in Table 2.
The procedure in Example 1 was followed with the exception that an additive oil obtained by the procedure that follows was added to the heavy hydrocarbon oil in an amount of 3% by weight with respect to the heavy hydrocarbon oil.
~ 1 5020~
That is, the additive oil was obtained by hydrogenating the substance used as the additive oil in Example 1 at a temperature of 380C, a hydrogen partial pressure of 120 atm for 40 min in the presence of a commercially available hydrodesulfurization catalyst (Co-Mo/alumina type) in an autoclave. The resulting hydrotreated additive oil was added to the heavy hydrocarbon oil without further removing the low-boiling fractions. The additive oil thus obtained was determined to contain 31% by weight aromatic carbons by means of H-NMR and C-NMR.
The properties, amount of dried sludge and toluene insolubles of the resulting product are set forth in Table 2.
The procedure in Example 1 was followed with the exception that an additive oil obtained by the procedure that follows was added.
That is, the additive oil was obtained by distilling a tar-sand oil to recover the fraction boiling at between 300 and 550C. The additive oil was determined to contain 82% by weight aromatic carbons.
The properties, amount of dried sludge and toluene insolubles of the resulting product are also set forth in Table 2.
The procedure in Example 1 was followed with the exception that an additive oil obtained by the procedure that follows was added in an amount of 1.5% by weight with respect to the heavy hydrocarbon oil feedstock.
That is, the additive oil was obtained by hydrogenating the substance used as the additive oil in Example 3 in an autoclave at 350C, a hydrogen partial pressure of 130 atm for 60 min in the presence of a commercially available catalyst (Co-Mo/alumina type) for use in hydrodesulfurizing a petroleum fraction.
Fractions boiling below 300C were removed from the resulting hydrotreated oil by distillation. The additive oil thus obtained was determined to contain 32% aromatic carbons by means of H-NMR and C-NMR.
The properties, amount of dried sludge and toluene insolubles of the resulting product are also set forth in Table 2.
The procedure in Example l was followed, but without addition of the additive oil.
The properties, amount of dried sludge and toluene insolubles of the resulting product are also set forth in Table 2.
21502~5 -Table 1 Heavy Hydrocarbon Oil Arabian Heavy Atmospheric Feedstock Residual Oil (Topped Crude) Density (15C) 0.995 Viscosity (cSt, 50C) 4.120 Conradson Carbon Residue 15.0 (% by weight) n-Heptane Insolubles 0.95 (% by weight) Distillation Characteristics ( C) 5/10% 380/413 S (% by weight) 4.40 N (ppm by weight) 2400 V (ppm by weight) 93 Ni (ppm by weight) 35 Table 2 Properties of Hydrotreated Product Oils Examples Compr.
Exam.
Density (15C) 0.992 0.989 0.983 0.989 0.980 Desulfurization 94.2 94.6 94.0 94.0 95.1 (%) Demetallization 95.1 96.0 95.2 95.0 96.5 (V, Ni, %) Amount of dried 0.06 0.05 0.07 0.04 0.71 sludge (~ by weight) Toluene 0.04 0.03 0.04 0.02 0.20 Insolubles (% by weight) 2l5o2~
A Middle East vacuum residual oil (Table 3) was hydrocracked at 415C, a hydrogen partial pressure of 170 atm, and a LHSV of 0.3 hr~~ in the presence of a commercially available hydrocracking catalyst (Ni-Co-Mo/silica-alumina type) in the same apparatus and the same catalyst volume as used in Example 1. A 250-600C fraction obtained from a bitumen-derived oil by distillatlon was added to the heavy hydrocarbon oil in an amount of 2.5% by weight with respect to the heavy hydrocarbon oil.
The properties, amount of dried sludge and toluene insolubles of the resulting hydrocracked product are set forth in Table 4.
The procedure in Examples 5 was followed, but without addition of the additive oil.
The properties, amount of dried sludge and toluene insolubles of the resulting hydrocracked product are also set forth in Table 4.
2l5o2o~
Table 3 Heavy Hydrocarbon OilArabian Heavy Vacuum Feedstock Residual Oil Density (15C) 1.030 Viscosity (cSt, 120C) 924.2 Conradson Carbon Residue22.31 (% by weight) n-Heptane Insolubles 8.4 (% by weight) S (% by weight) 5 N (ppm by weight) 4030 V (ppm by weight) 140 Ni (ppm by weight) 47 Table 4 Properties of Hydrocracked Product Oils Example Compr.
Example Density (15C) 0.990 0.987 % of Cracking (565C) 85 82 Desulfurization (%) 81 84 Demetallization (V, Ni, %) 87 90 Amount of dried sludge 0.09 1.58 (% by weight) Toluene Insolubles 0.07 0.41 (% by weight) As is evident from the results in Comparative Example 1 as set forth in Table 2, when an Arabian Heavy atmospheric residual oil is severely hydrotreated, a significant amount of carbonaceous material forms; however, when an additive oil in accordance with the present invention is added to the heavy hydrocarbon oil in an amount of 1.5% by weight, the amount of dried sludge and toluene insolubles can be reduced greatly. Although partially hydrogenated additive oils (Examples 2 and 4) of the present invention prove more effective for controlling the formation of coke than additive oils not previously hydrogenated, a fairly good controlling effect on the formation of coke can be observed even when the additive oil of the invention is added without being hydrogenated in advance (Examples 1 and 3).
In addition, it is also found that additive oils of the present invention produce the intended effect when an Arabian Heavy vacuum residual oil is hydrocracked as shown in table 4.
Several reports have appeared, showing that the hydrotreatment of a heavy hydrocarbon oil ln the presence of a hydrogen-donating substance is effective for controlling 215020!j the formation of coke. Recycling of part of the hydrotreated oil from the reactor has been practiced in this respect;
however, in these conventional processes, a great amount of hydrogen-donating substance needs to be added or recycling of a great amount of hydrotreated oil is required, in addition to the fact that the effect of these additives for controlling the formation of coke is still insufficient.
A principal object of the present invention is to provide an improved process for hydrotreating a heavy hydrocarbon oil so that remarkably less carbonaceous material (coke) will form thereby allowing the hydrotreating operation to continue for longer periods of time in a stable state and to solve the problems associated with the formation of coke.
SUMMARY OF THE INVENTION
The applicant of the invention has intensively researched to solve the foregoing problems, and as a result, has found that the formation of carbonaceous material may be greatly reduced by incorporating a small amount of specific additive oil into the heavy hydrocarbon oil. The present inventions are based on this finding.
That is, the first aspect of the present invention is directed to a process for hydrotreating a heavy hydrocarbon oil, wherein the process comprises hydrotreating a mixed oil of the heavy hydrocarbon oil and at least one 21s0205 additive oil in an amount of 0.3 to 15% by weight with respect to the feedstock at a temperature of 330 to 460C, a hydrogen partial pressure of 50 to 250 Kg/cm , a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr in the presence of a hydrotreating catalyst, the additive oil being selected.from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction.
The second aspect of the invention is directed to a process for hydrotreating a heavy hydrocarbon oil, wherein the process comprises hydrotreating a mixed oil of the heavy hydrocarbon oil and at least one partially aromatic ring-hydrogenated additive oil in an amount of 0.3 to 15% by weight with respect to the heavy hydrocarbon oil, at a temperature of 330 to 460C, a hydrogen partial pressure of 50 to 250 Kg/cm , a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr in the presence of a hydrotreating catalyst, the additive oil being selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in further detail hereinbelow.
The term "heavy hydrocarbon oil" refers to a 2l~o2os petroleum hydrocarbon oil, 50% by weight or more of which boils at 350C or higher. Examples of such heavy hydrocarbon oils include atmospheric residual oils obtained by topping crudes, and vacuum residual oils obtained from the atmospheric residual oils by vacuum distillation.
The term "hydrotreating" refers to one of those including hydrodesulfurization, hydrodemetallization, hydrodenitrogenation and hydrocracking.
The hydrotreating is usually performed at a temperature of 330 to 460C, preferably at 360 to 440C, more preferably at 380 to 420C, and a hydrogen partial pressure of 50 to 250 Kg/cm , preferably 70 to 200 Kg/cm , more preferably 100 to 150 Kg/cm in the presence of a catalyst.
Usually an LHSV of 0.1 to 4.0 hr , preferably 0.2 to 1.0 hr may be employed.
In the hydrotreating of the present invention, any conventional hydrotreating catalyst may be used. Examples of the catalyst include a catalyst comprising particles containing one or more of the metals selected from Group V
through Group VIII metal components of the Periodic Table supported on carrier particles such as alumina, silica-alumina, or a cationic exchange zeolite. Oxides or sulfides of these metals may be also used. Examples of these metals include nickel, cobalt, molybdenum, vanadium, wolfram, and mixtures thereof.
215020~
Any type of hydrotreating reactor such as a fixed-bed, moving-bed, or fluidized-bed may be employed.
In the present invention, an additive oil selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction is added to the heavy hydrocarbon oil, 50~ by weight or more of the additive oil boiling at 250C or higher, preferably at 250 to 600C. Preferred percentage (~) of the aromatic carbons of the additive oil is 60 or more.
The additive oil may be employed as mixtures thereof.
Further, instead of oils obtained by coal liquefaction, powdered coal before liquefaction may be employable in the present invention.
According to the first aspect of the present invention, there is provided a process for hydrotreating a heavy hydrocarbon oil wherein an additive oil selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction is blended with the heavy hydrocarbon oil without any pretreatment, such as a thermal treatment, of the additive oil.
The additive oil is present in an amount of 0.3 to 15~ by weight, preferably 0.5 to 8% by weight on the basis of the heavy hydrocarbon oil.
Although any blending technique may be used, the foregoing additive oil is preferably fed into the reactor separately from the heavy hydrocarbon oil or after being blended with the heavy hydrocarbon oil.
According to the second aspect of the present invention, there is provided a process for hydrotreating a heavy hydrocarbon oil wherein the foregoing additive oil is partially aromatic ring-hydrogenated prior to being charged into the hydrotreating reactor.
The partial hydrogenation of aromatic rings is carried out so that a percentage of the aromatic carbon atom of the resulting hydrogenated oil will be within the range of from 5 to 50~, preferably 10 to 40%. The foregoing percentage is represented by the following formula (1):
Percentage (%) of aromatic carbon atom =
(Number of aromatic ring carbon atoms present in given oil amount (g))/(Total number of carbon atoms present in given oil amount (g))xlOO ................................. (1) Any method for the partial hydrogenation of aromatic rings may be used. Usually the aromatic rings are partially hydrogenated in the presence of a hydrogenation catalyst in a pressurized hydrogen atmosphere.
Any conventional hydrogenation catalyst such as one suitable for use in hydrotreating a petroleum fraction may be 215020~
used herein. More particularly, a catalyst comprising particles containing one or more of the metals selected from Group V through Group VIII metal components of the Periodic Table supported on inorganic carrier particles is employed.
Oxides or sulfides of these metal components may also be used. Examples of such metal components include nickel, cobalt, molybdenum, vanadium, and wolfram. Examples of such inorganic carriers include alumina, silica-alumina, a cation exchange zeolite, kieselguhr, and the like.
Aromatic ring-hydrogenation catalysts may also be preferably employed. Examples of the catalyst include a catalyst comprising particles containing one or more of the metal components, such as nickel, nickel oxide, nickel-copper, platinum, platinum oxide, platinum-rhodium, platinum-lithium, rhodium, palladium, cobalt, ruthenium, or Raney-cobalt, supported on inorganic carrier particles.
Examples of such inorganic carriers include active carbon, alumina, silica-alumina, kieselguhr, zeolite, and the like.
Preferred conditions for partially hydrogenating aromatic rings are as follows: a temperature of 300 to ~00C
and a pressure of 30 to 150 Kg/cm , when a catalyst for use in hydrotreating a petroleum fraction is employed; a temperature of 150 to 300C and a pressure of 30 to 150 kg/cm , when a catalyst for use in hydrogenating aromatic rings is employed.
2l5o2o5 Any type of apparatus such as a fixed-bed, moving-bed, fluidized-bed or a batch type apparatus may be employed.
The partially aromatic ring-hydrogenated oil thus obtained is charged into a hydrotreating reactor.
The partially aromatic ring-hydrogenated oil to be added to the heavy hydrocarbon oil is present in an amount of 0.3 to 15% by weight, preferably 0.5 to 8% by weight with respect to the weight of the heavy hydrocarbon oil. The hydrogenated oil may be charged into the reactor separately from the heavy hydrocarbon oil, or charged after being blended with the heavy hydrocarbon oil.
The partially aromatic ring-hydrogenated oil according to the present invention has remarkable hydrogen-donating properties, and can effectively control the formation of carbonaceous material even when added to the heavy hydrocarbon oil in a small amount.
In addition, the specific oil as an additive in accordance with the present invention is further converted to aromatic ring-hydrogenated substances of high hydrogen-donating activity in the hydrogenation reactor, whereby the formation of carbonaceous material can be reduced likewise.
The invention will be further illustrated by the following examples but in no way limited by the examples.
2~0205 A Middle East topped crude having properties as specified in Table 1 was treated in a downward fixed-bed reactor (internal diameter; 10 mm, height; 0.5 m, catalyst volume; 30 cm ) in the presence of a commercially available Ni-Mo/silica-alumina catalyst at a temperature of 413C, a hydrogen partial pressure of 165 atm, and a LHSV of 0.50 hr~1. In this experiment, an additive oil obtained by the procedure that follows was added to the heavy hydrocarbon oil in an amount of 3% by weight with respect to the heavy hydrocarbon oil.
That is, the foregoing specific additive oil was obtained from a decrystallized anthracene oil by removing the fraction boiling up to 250C. The resulting oil was determined to contain 89~ by weight aromatic carbons.
The hydrotreating was continued for about 260 hr.
The properties, amount of dried sludge and toluene insolubles of the resulting product after 240 hr are set forth in Table 2.
The procedure in Example 1 was followed with the exception that an additive oil obtained by the procedure that follows was added to the heavy hydrocarbon oil in an amount of 3% by weight with respect to the heavy hydrocarbon oil.
~ 1 5020~
That is, the additive oil was obtained by hydrogenating the substance used as the additive oil in Example 1 at a temperature of 380C, a hydrogen partial pressure of 120 atm for 40 min in the presence of a commercially available hydrodesulfurization catalyst (Co-Mo/alumina type) in an autoclave. The resulting hydrotreated additive oil was added to the heavy hydrocarbon oil without further removing the low-boiling fractions. The additive oil thus obtained was determined to contain 31% by weight aromatic carbons by means of H-NMR and C-NMR.
The properties, amount of dried sludge and toluene insolubles of the resulting product are set forth in Table 2.
The procedure in Example 1 was followed with the exception that an additive oil obtained by the procedure that follows was added.
That is, the additive oil was obtained by distilling a tar-sand oil to recover the fraction boiling at between 300 and 550C. The additive oil was determined to contain 82% by weight aromatic carbons.
The properties, amount of dried sludge and toluene insolubles of the resulting product are also set forth in Table 2.
The procedure in Example 1 was followed with the exception that an additive oil obtained by the procedure that follows was added in an amount of 1.5% by weight with respect to the heavy hydrocarbon oil feedstock.
That is, the additive oil was obtained by hydrogenating the substance used as the additive oil in Example 3 in an autoclave at 350C, a hydrogen partial pressure of 130 atm for 60 min in the presence of a commercially available catalyst (Co-Mo/alumina type) for use in hydrodesulfurizing a petroleum fraction.
Fractions boiling below 300C were removed from the resulting hydrotreated oil by distillation. The additive oil thus obtained was determined to contain 32% aromatic carbons by means of H-NMR and C-NMR.
The properties, amount of dried sludge and toluene insolubles of the resulting product are also set forth in Table 2.
The procedure in Example l was followed, but without addition of the additive oil.
The properties, amount of dried sludge and toluene insolubles of the resulting product are also set forth in Table 2.
21502~5 -Table 1 Heavy Hydrocarbon Oil Arabian Heavy Atmospheric Feedstock Residual Oil (Topped Crude) Density (15C) 0.995 Viscosity (cSt, 50C) 4.120 Conradson Carbon Residue 15.0 (% by weight) n-Heptane Insolubles 0.95 (% by weight) Distillation Characteristics ( C) 5/10% 380/413 S (% by weight) 4.40 N (ppm by weight) 2400 V (ppm by weight) 93 Ni (ppm by weight) 35 Table 2 Properties of Hydrotreated Product Oils Examples Compr.
Exam.
Density (15C) 0.992 0.989 0.983 0.989 0.980 Desulfurization 94.2 94.6 94.0 94.0 95.1 (%) Demetallization 95.1 96.0 95.2 95.0 96.5 (V, Ni, %) Amount of dried 0.06 0.05 0.07 0.04 0.71 sludge (~ by weight) Toluene 0.04 0.03 0.04 0.02 0.20 Insolubles (% by weight) 2l5o2~
A Middle East vacuum residual oil (Table 3) was hydrocracked at 415C, a hydrogen partial pressure of 170 atm, and a LHSV of 0.3 hr~~ in the presence of a commercially available hydrocracking catalyst (Ni-Co-Mo/silica-alumina type) in the same apparatus and the same catalyst volume as used in Example 1. A 250-600C fraction obtained from a bitumen-derived oil by distillatlon was added to the heavy hydrocarbon oil in an amount of 2.5% by weight with respect to the heavy hydrocarbon oil.
The properties, amount of dried sludge and toluene insolubles of the resulting hydrocracked product are set forth in Table 4.
The procedure in Examples 5 was followed, but without addition of the additive oil.
The properties, amount of dried sludge and toluene insolubles of the resulting hydrocracked product are also set forth in Table 4.
2l5o2o~
Table 3 Heavy Hydrocarbon OilArabian Heavy Vacuum Feedstock Residual Oil Density (15C) 1.030 Viscosity (cSt, 120C) 924.2 Conradson Carbon Residue22.31 (% by weight) n-Heptane Insolubles 8.4 (% by weight) S (% by weight) 5 N (ppm by weight) 4030 V (ppm by weight) 140 Ni (ppm by weight) 47 Table 4 Properties of Hydrocracked Product Oils Example Compr.
Example Density (15C) 0.990 0.987 % of Cracking (565C) 85 82 Desulfurization (%) 81 84 Demetallization (V, Ni, %) 87 90 Amount of dried sludge 0.09 1.58 (% by weight) Toluene Insolubles 0.07 0.41 (% by weight) As is evident from the results in Comparative Example 1 as set forth in Table 2, when an Arabian Heavy atmospheric residual oil is severely hydrotreated, a significant amount of carbonaceous material forms; however, when an additive oil in accordance with the present invention is added to the heavy hydrocarbon oil in an amount of 1.5% by weight, the amount of dried sludge and toluene insolubles can be reduced greatly. Although partially hydrogenated additive oils (Examples 2 and 4) of the present invention prove more effective for controlling the formation of coke than additive oils not previously hydrogenated, a fairly good controlling effect on the formation of coke can be observed even when the additive oil of the invention is added without being hydrogenated in advance (Examples 1 and 3).
In addition, it is also found that additive oils of the present invention produce the intended effect when an Arabian Heavy vacuum residual oil is hydrocracked as shown in table 4.
Claims (4)
1. A process for hydrotreating a heavy hydrocarbon oil, wherein the process comprises hydrotreating a mixed oil of the heavy hydrocarbon oil and at least one additive oil in an amount of 0.3 to 15% by weight with respect to the heavy hydrocarbon oil, at a temperature of 330 to 460°C, a hydrogen partial pressure of 50 to 250 Kg/cm2, a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr-1 in the presence of a hydrotreating catalyst, the additive oil being selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction.
2. A process according to claim 1 wherein 50% by weight or more of said additive oil boils at 250 °C or higher.
3. A process for hydrotreating a heavy hydrocarbon oil, wherein the process comprises hydrotreating a mixed oil of the heavy hydrocarbon oil and at least one partially aromatic ring-hydrogenated additive oil in an amount of 0.3 to 15% by weight with respect to the heavy hydrocarbon oil, at a temperature of 330 to 460°C, a hydrogen partial pressure of 50 to 250 Kg/cm2, a liquid hourly space velocity (LHSV) of 0.1 to 4.0 hr-1 in the presence of a hydrotreating catalyst, the additive oil being selected from the group consisting of coal-tar oils, tar-sand oils, oil shale- or bitumen-derived oils, and oils obtained by coal liquefaction.
4. A process according to claim 3 wherein 50% by weight or more of said additive oil boils at 250 °C or higher.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-136726 | 1994-05-27 | ||
| JP13672694A JPH07316566A (en) | 1994-05-27 | 1994-05-27 | Hydrogenation treatment of heavy oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2150205A1 true CA2150205A1 (en) | 1995-11-28 |
Family
ID=15182071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2150205 Abandoned CA2150205A1 (en) | 1994-05-27 | 1995-05-25 | Process for hydrotreating heavy hydrocarbon oil |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07316566A (en) |
| CA (1) | CA2150205A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007050477A1 (en) * | 2005-10-24 | 2007-05-03 | Shell Internationale Research Maatschappij B.V. | Methods of hydrotreating a liquid stream to remove clogging compounds |
| US7651605B2 (en) | 2004-08-27 | 2010-01-26 | Nippon Oil Corporation | Process of hydrotreating heavy hydrocarbon oil |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5314355B2 (en) * | 2008-08-08 | 2013-10-16 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing hydrocarbon oil |
| CN104673366B (en) * | 2015-02-04 | 2017-02-01 | 新疆独山子天利实业总公司 | Method for preventing ethylene cracking mixed deca-carbon from becoming green in hydrogenation process |
| CN104650973B (en) * | 2015-02-13 | 2016-06-01 | 华电重工股份有限公司 | A kind of two-stage method coal tar hydrogenation process |
-
1994
- 1994-05-27 JP JP13672694A patent/JPH07316566A/en active Pending
-
1995
- 1995-05-25 CA CA 2150205 patent/CA2150205A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7651605B2 (en) | 2004-08-27 | 2010-01-26 | Nippon Oil Corporation | Process of hydrotreating heavy hydrocarbon oil |
| WO2007050477A1 (en) * | 2005-10-24 | 2007-05-03 | Shell Internationale Research Maatschappij B.V. | Methods of hydrotreating a liquid stream to remove clogging compounds |
| EA013513B1 (en) * | 2005-10-24 | 2010-06-30 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method for producing crude products with subsurface heat treatment in situ |
| US8151880B2 (en) | 2005-10-24 | 2012-04-10 | Shell Oil Company | Methods of making transportation fuel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07316566A (en) | 1995-12-05 |
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