CA1095847A - Thermal hydrocracking of topped heavy oils - Google Patents
Thermal hydrocracking of topped heavy oilsInfo
- Publication number
- CA1095847A CA1095847A CA299,229A CA299229A CA1095847A CA 1095847 A CA1095847 A CA 1095847A CA 299229 A CA299229 A CA 299229A CA 1095847 A CA1095847 A CA 1095847A
- Authority
- CA
- Canada
- Prior art keywords
- heavy
- hydrocracking
- hydrogen
- oil
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/22—Non-catalytic cracking in the presence of hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
THERMAL HYDROCRACKING OF TOPPED HEAVY OILS
Abstract of the Disclosure An improved process is described for the thermal hydrocracking of heavy hydrocarbon oil, such as oils ex-tracted from tar sands. The charge oil in the presence of an excess of hydrogen is passed upwardly through a vertical hydrocracking zone and the effluent emerging from the top of the zone is separated into a gaseous stream and a liquid stream containing heavy hydrocarbons. According to the novel feature, the heavy hydrocarbon charge oil is one which has been topped in a distillation column to an equivalent at-mospheric boiling temperature of at least 350°C. It has been found that the topping of the charge oil results in lower hydrogen consumption per barrel of pitch converted.
Surprisingly, operability of the plant is improved with heavier feed and significantly lower coke formation being experienced.
Abstract of the Disclosure An improved process is described for the thermal hydrocracking of heavy hydrocarbon oil, such as oils ex-tracted from tar sands. The charge oil in the presence of an excess of hydrogen is passed upwardly through a vertical hydrocracking zone and the effluent emerging from the top of the zone is separated into a gaseous stream and a liquid stream containing heavy hydrocarbons. According to the novel feature, the heavy hydrocarbon charge oil is one which has been topped in a distillation column to an equivalent at-mospheric boiling temperature of at least 350°C. It has been found that the topping of the charge oil results in lower hydrogen consumption per barrel of pitch converted.
Surprisingly, operability of the plant is improved with heavier feed and significantly lower coke formation being experienced.
Description
)9~;847 This invention relates to the treatment of hydrocarbon oils and, more particularly, to the hydrocrack-ing of heavy hydrocarbon oils to produce improved products of lower boiling range.
Catalytic hydrocracking processes for the conversion of heavy hydrocarbon oils to light and intermediate naphthas of good quality for reforming feed stocks, fuel oil and gas oil are well known. These heavy hydrocarbon oils can be such materials as petroleum crude oil, atmospheric tar bottoms products, vacuum tar bottoms products, heavy cycle oils, shale oils, coal derived liquids, crude oil residuum, topped crude oils and the heavy bituminous oils extracted from oil sands. Of particular interest are the oils extracted from oil sands and which contain wide boiling range materials from naphthas through kerosene, gas oil, pitch, etc. and which contain a large portion of material boiling above 524C.
The heavy hydrooarbon oils of the above type tend to contain nitrogen and sulphur compounds in exceed-ingly large quantities. In addition, such heavy hydrocarbonfractions frequently contain excessive quantities of metailic contaminants which tend to be extremely detrimental to various catalytic processes that may subsequantly be carried out, such as hydrofining. O~ the metallic contaminants, those containing nickel and vanadium are most co~n, al-though other metals are often present. These metallic con-`taminants, as well as others, are usually present within the ,bituminous material as organo-metallic compounds of relatively j high molecular weight. A considerable quantity of the metallic complexes are linked with asphaltenic material and contains sulphur. Of course, in ~k l~9S847 catalytic hydrocracking procedures, the presence of large quantities of asphaltenic material and metal-containing compounds interferes considerably with the activity of the catalyst with respect to the destructive removal of nitro-genous, sulphurous and oxygenated compounds. A typical Athabasca bitumen may contain 53.1 wt. ~ material boiling above 524C., 4.62 wt. ~ sulphur, 0.34 wt. % nitrogen,and 159 ppm vanadium.
As the reserves of conventional crude oils decline, these heavy oils can be upgraded to meet the demands. In this upgrading, the heavier material is con-verted to lighter fractions and most of the sulphur, nit-rogen and metals can be removed. ~ost existing sys~ems use coking processes which involve removal of carbon re-sulting in about 20~ of material as coke. This represents an excessive waste of resources.
A recent improved procedure is described by Pruden, B.B. et al ( CANMET Report 76-33, Department of Energy, Mines and Resources, Ottawa, Canada ) in which hydrogen and heavy oil are pumped upwardly through an empty tubular reactor in the absence of a hydrocracking catalyst.
It was found that the high molecular weight compounds hy-drogenate and/or hydrocrack into lower boiling fractions, with simultaneous desulphurization, demetallization and denitrogenation reactions~ ~or this procedure, reaction pressures of up to 3500 psig and temperatures up to 470C
have been employed.
There have been some problems with the previous procedure at lower pressures due to the formation of coke deposits in the reactor. These deposits tend to form at the top of the reactor where the partial pressure of hydrogen 1~9S847 and ash content are the lowest. The use of higher pressures has tended to reduce reactor fouling. At 3500 psig and 470C., the fouling was almost eliminated. ~owever, plant operations at high pressures involve higher capital and operating costs.
Several attempts have been made to reduce coke deposition at lower pressures. The process can be improved by either suppressing the coke formation reactions or pre-venting the coke build up on the reactor walls. For instance, ~/
Khulbe et al Canadian Patent Application Serial No. 291r~S~, filed November 22, 1977 describes a process which can be operated at lower pressures in which recycling a portion of the heavy oil decreases the coke formation. The recycling, however, increases the hydrogen consumption and there was a slight decrease in pitch conversion.
Gregoli et al U.S. Patent 3,905,892, issued September 16, 1975, describes a procedure in which a topped heavy oil such as vacuum residuum ( generally 524C+ material) is upgraded by catalytic hydrocracking using an ebullated bed reactor. Griffiths U.S. Patent 3,380,910, issued April 30, 1968, describes a similar type of process using a fixed bed catalytic reactor. However, the catalysts are poisoned rapidly by metals and coke irrespective of the type of reactor used. Hence the spent catalyst has to be replaced periodically or continuously with fresh catalyst.
Chervenak et al, U.S. patent 3,775,296, issued November 27, 1973, describes non-catalytic hydrocracking of bitumen as obtained from tar sands but that system only operated satisfactorily if the charge oil contained silt and, moreover, it was necessary to operate the system such that a build up of mineral matter developed and a very sub-stantial consumption of hydrogen was used to prevent coke lO9S8~7 formation.
It is the object of the present invention to provide a simplified hydrocracking process which will minimize coke formation while at the same time minimizing hydrogen con-sumption.
S UMMARY OF THE INVENTION
_ In accordance with the present invention, there is described a process for the hydrocracking of a heavy hydro-carbon oil, a substantial portion of which boils above 524C., wherein (a) a feed of said heavy oil in the presence of 500 - 50,000 sc.f. of hydrogen per barrel of heavy oil feed is passed upwardly through a vertical empty column hydrocracking zone maintained at a temperature between about 400 and 490C., a pressure above 500 psig. and a space velocity between about 0.5 and 4.0 volumes of heavy oil per hour per volume of hydrocracking capacity, (b) removing from said hydrocracking zone a mixed effluent containing a gaseous phase comprising hydrogen and vaporous hydrocarbons and a liquid phase comprising heavy hydrocarbons and (c) separating said effluent into a gaseous stream containing hydrogen and vaporous hydrocarbons and a liquid stream containing heavy hydrocarbons. According to the novel feature, the heavy hydrocarbon oil feed to the process is one which has been topped in a distillation column to an equivalent atmospheric boiling temperature of about 350~C or higher, preferably at least 400C.
It has been found that topping the heavy hydrocarbon oil feed in this manner has the effect of both reducing hydrogen consumption and reducing coke formation. It has also been found that at similar reaction conditions, the pitch conversion is improved using the topped charge oil.
Results have shown that the topping improves hydrogen/
1~95847 heavy oil contact because the lower molecular weight compounds are not present to compete with high molecular weight com-pounds for hydrogen. Hence, more hydrogen is available to stabilize the free radicals resulting from cracking thereby reducing the coke formation.
The distillate from the topping operation can be sent directly to a catalytic hydrotreater or mixed with distillate from a hydrocracker to be pumped through a pipe line.
The process of this invention is particularly well suited for the treatment of heavy oils having a large pro-portion, preferably at least 50% by volume, which boils above 524C and which ~ontains a wide boiling range of materials from naphtha through kerosene, gas oil and pitch. It can be operated at pressures in the range of about 500 to 3,500 psig without coke formation in the hydrocracking zone.
The hydrocracking is carried out in a vertical empty column reactor through which the charge oil is moved upward-ly together with the hydrogen. The effluent from the top is preferably separated in a hot separator, e.g. at a temperature of 250 to 490C., and at the same pressure as the hydro-cracking zone. The heavy hydrocarbon oil product from the hot separator can either be recycled or sent for secondary treatment. me mixture of gases and hydrogen from the hot separator is preferably further cooled and separated in a cold separator, with the light oil product being removed and sent for secondary treatment. The gases from the cold receiver are scrubbed to obtain the required degree of hydrogen purity (between 60 and 90~) and recycled back into the system with fresh make-up hydrogen.
For a better understanding of the invention, reference is made to the accompanying drawings, in which:
1~9~84~
Fig. 1 illustrates diagrammatically a preferred process sequence;
Fig. 2 is a plot of pitch conversion v. reaction 'cemperature for different charge oils; and Fig. 3 is a plot of hydrogen consumed v. pitch con-version for different charge oils.
Looking now at Figure 1, heavy hydrocarbon oil feed is fed from feed tank 10 through feed pump 11 and inlet line 12 into the bottom of empty tower 13. Recycled hydrogen and make-up hydrogen from line 30 is simultaneously fed into the tower 13 through line 12. A gas-liquid mixture is withdrawn from the top of the tower 13 through line 14 and introduced into hot separator 15. In the hot separator, the effluent from tower 13 is separated into a gaseous stream 18 and a liquid stream 16. The liquid stream 16 is in the form of heavy oil which is collected at 17. This heavy oil product 17 is either sent for secondary treatment or a portion thereof may be recycled back into inlet lin~ 12.
The gaseous stream from hot separator 15 is carried by way of line 18 into a cold separator 19. Within this separator, the product is separated into a gaseous stream rich in hydrogen which is drawn off through line 22 and a light oil product which is drawn off through line 20 and collected at 21. This light oil product is then sent to secondary treatment.
The hydrogen rich stream 22 is passed through a packed scrubbing tower 23 where it is scrubbed by means of a scrubbing liquid 24 which is recycled through the tower by means of pump 25 and recycle loop 26. The scrubbed hydrogen rich stream emerges from the scrubber via line 27 and is combined with fresh make-up hydrogen added through 1~9;~847 line 28 and recycled through recycle gas pump 29 and line 30 back to tower 13.
Certain preferred embodiments of this invention will now be further illustrated by the following non-limitative examples.
Example 1 An Athabasca bitumen was obtained having the properties set out in Table 1 below:
Table 1 ___ Details of AnalYsis 1. Specific gravity, 15/15C. 1.014
Catalytic hydrocracking processes for the conversion of heavy hydrocarbon oils to light and intermediate naphthas of good quality for reforming feed stocks, fuel oil and gas oil are well known. These heavy hydrocarbon oils can be such materials as petroleum crude oil, atmospheric tar bottoms products, vacuum tar bottoms products, heavy cycle oils, shale oils, coal derived liquids, crude oil residuum, topped crude oils and the heavy bituminous oils extracted from oil sands. Of particular interest are the oils extracted from oil sands and which contain wide boiling range materials from naphthas through kerosene, gas oil, pitch, etc. and which contain a large portion of material boiling above 524C.
The heavy hydrooarbon oils of the above type tend to contain nitrogen and sulphur compounds in exceed-ingly large quantities. In addition, such heavy hydrocarbonfractions frequently contain excessive quantities of metailic contaminants which tend to be extremely detrimental to various catalytic processes that may subsequantly be carried out, such as hydrofining. O~ the metallic contaminants, those containing nickel and vanadium are most co~n, al-though other metals are often present. These metallic con-`taminants, as well as others, are usually present within the ,bituminous material as organo-metallic compounds of relatively j high molecular weight. A considerable quantity of the metallic complexes are linked with asphaltenic material and contains sulphur. Of course, in ~k l~9S847 catalytic hydrocracking procedures, the presence of large quantities of asphaltenic material and metal-containing compounds interferes considerably with the activity of the catalyst with respect to the destructive removal of nitro-genous, sulphurous and oxygenated compounds. A typical Athabasca bitumen may contain 53.1 wt. ~ material boiling above 524C., 4.62 wt. ~ sulphur, 0.34 wt. % nitrogen,and 159 ppm vanadium.
As the reserves of conventional crude oils decline, these heavy oils can be upgraded to meet the demands. In this upgrading, the heavier material is con-verted to lighter fractions and most of the sulphur, nit-rogen and metals can be removed. ~ost existing sys~ems use coking processes which involve removal of carbon re-sulting in about 20~ of material as coke. This represents an excessive waste of resources.
A recent improved procedure is described by Pruden, B.B. et al ( CANMET Report 76-33, Department of Energy, Mines and Resources, Ottawa, Canada ) in which hydrogen and heavy oil are pumped upwardly through an empty tubular reactor in the absence of a hydrocracking catalyst.
It was found that the high molecular weight compounds hy-drogenate and/or hydrocrack into lower boiling fractions, with simultaneous desulphurization, demetallization and denitrogenation reactions~ ~or this procedure, reaction pressures of up to 3500 psig and temperatures up to 470C
have been employed.
There have been some problems with the previous procedure at lower pressures due to the formation of coke deposits in the reactor. These deposits tend to form at the top of the reactor where the partial pressure of hydrogen 1~9S847 and ash content are the lowest. The use of higher pressures has tended to reduce reactor fouling. At 3500 psig and 470C., the fouling was almost eliminated. ~owever, plant operations at high pressures involve higher capital and operating costs.
Several attempts have been made to reduce coke deposition at lower pressures. The process can be improved by either suppressing the coke formation reactions or pre-venting the coke build up on the reactor walls. For instance, ~/
Khulbe et al Canadian Patent Application Serial No. 291r~S~, filed November 22, 1977 describes a process which can be operated at lower pressures in which recycling a portion of the heavy oil decreases the coke formation. The recycling, however, increases the hydrogen consumption and there was a slight decrease in pitch conversion.
Gregoli et al U.S. Patent 3,905,892, issued September 16, 1975, describes a procedure in which a topped heavy oil such as vacuum residuum ( generally 524C+ material) is upgraded by catalytic hydrocracking using an ebullated bed reactor. Griffiths U.S. Patent 3,380,910, issued April 30, 1968, describes a similar type of process using a fixed bed catalytic reactor. However, the catalysts are poisoned rapidly by metals and coke irrespective of the type of reactor used. Hence the spent catalyst has to be replaced periodically or continuously with fresh catalyst.
Chervenak et al, U.S. patent 3,775,296, issued November 27, 1973, describes non-catalytic hydrocracking of bitumen as obtained from tar sands but that system only operated satisfactorily if the charge oil contained silt and, moreover, it was necessary to operate the system such that a build up of mineral matter developed and a very sub-stantial consumption of hydrogen was used to prevent coke lO9S8~7 formation.
It is the object of the present invention to provide a simplified hydrocracking process which will minimize coke formation while at the same time minimizing hydrogen con-sumption.
S UMMARY OF THE INVENTION
_ In accordance with the present invention, there is described a process for the hydrocracking of a heavy hydro-carbon oil, a substantial portion of which boils above 524C., wherein (a) a feed of said heavy oil in the presence of 500 - 50,000 sc.f. of hydrogen per barrel of heavy oil feed is passed upwardly through a vertical empty column hydrocracking zone maintained at a temperature between about 400 and 490C., a pressure above 500 psig. and a space velocity between about 0.5 and 4.0 volumes of heavy oil per hour per volume of hydrocracking capacity, (b) removing from said hydrocracking zone a mixed effluent containing a gaseous phase comprising hydrogen and vaporous hydrocarbons and a liquid phase comprising heavy hydrocarbons and (c) separating said effluent into a gaseous stream containing hydrogen and vaporous hydrocarbons and a liquid stream containing heavy hydrocarbons. According to the novel feature, the heavy hydrocarbon oil feed to the process is one which has been topped in a distillation column to an equivalent atmospheric boiling temperature of about 350~C or higher, preferably at least 400C.
It has been found that topping the heavy hydrocarbon oil feed in this manner has the effect of both reducing hydrogen consumption and reducing coke formation. It has also been found that at similar reaction conditions, the pitch conversion is improved using the topped charge oil.
Results have shown that the topping improves hydrogen/
1~95847 heavy oil contact because the lower molecular weight compounds are not present to compete with high molecular weight com-pounds for hydrogen. Hence, more hydrogen is available to stabilize the free radicals resulting from cracking thereby reducing the coke formation.
The distillate from the topping operation can be sent directly to a catalytic hydrotreater or mixed with distillate from a hydrocracker to be pumped through a pipe line.
The process of this invention is particularly well suited for the treatment of heavy oils having a large pro-portion, preferably at least 50% by volume, which boils above 524C and which ~ontains a wide boiling range of materials from naphtha through kerosene, gas oil and pitch. It can be operated at pressures in the range of about 500 to 3,500 psig without coke formation in the hydrocracking zone.
The hydrocracking is carried out in a vertical empty column reactor through which the charge oil is moved upward-ly together with the hydrogen. The effluent from the top is preferably separated in a hot separator, e.g. at a temperature of 250 to 490C., and at the same pressure as the hydro-cracking zone. The heavy hydrocarbon oil product from the hot separator can either be recycled or sent for secondary treatment. me mixture of gases and hydrogen from the hot separator is preferably further cooled and separated in a cold separator, with the light oil product being removed and sent for secondary treatment. The gases from the cold receiver are scrubbed to obtain the required degree of hydrogen purity (between 60 and 90~) and recycled back into the system with fresh make-up hydrogen.
For a better understanding of the invention, reference is made to the accompanying drawings, in which:
1~9~84~
Fig. 1 illustrates diagrammatically a preferred process sequence;
Fig. 2 is a plot of pitch conversion v. reaction 'cemperature for different charge oils; and Fig. 3 is a plot of hydrogen consumed v. pitch con-version for different charge oils.
Looking now at Figure 1, heavy hydrocarbon oil feed is fed from feed tank 10 through feed pump 11 and inlet line 12 into the bottom of empty tower 13. Recycled hydrogen and make-up hydrogen from line 30 is simultaneously fed into the tower 13 through line 12. A gas-liquid mixture is withdrawn from the top of the tower 13 through line 14 and introduced into hot separator 15. In the hot separator, the effluent from tower 13 is separated into a gaseous stream 18 and a liquid stream 16. The liquid stream 16 is in the form of heavy oil which is collected at 17. This heavy oil product 17 is either sent for secondary treatment or a portion thereof may be recycled back into inlet lin~ 12.
The gaseous stream from hot separator 15 is carried by way of line 18 into a cold separator 19. Within this separator, the product is separated into a gaseous stream rich in hydrogen which is drawn off through line 22 and a light oil product which is drawn off through line 20 and collected at 21. This light oil product is then sent to secondary treatment.
The hydrogen rich stream 22 is passed through a packed scrubbing tower 23 where it is scrubbed by means of a scrubbing liquid 24 which is recycled through the tower by means of pump 25 and recycle loop 26. The scrubbed hydrogen rich stream emerges from the scrubber via line 27 and is combined with fresh make-up hydrogen added through 1~9;~847 line 28 and recycled through recycle gas pump 29 and line 30 back to tower 13.
Certain preferred embodiments of this invention will now be further illustrated by the following non-limitative examples.
Example 1 An Athabasca bitumen was obtained having the properties set out in Table 1 below:
Table 1 ___ Details of AnalYsis 1. Specific gravity, 15/15C. 1.014
2. Sulphur (bomb), % by wt., 4.62
3. Ash, % by wt., 0.62
4. Conradson carbon residue, % by wt.,14.1
5. Pentane insolubles, % by wt., 15.6
6. Benzene insolubles, % by wt., 0.69
7. Carbon, % by wt., 82. 47
8. Hydrogen, % by wt., 9.97
9. Nitrogen, % by wt., 0. 34
10. Viscosity cSt at 38C., 1754 3 at 50C., 5 899 at 54C., 3601 at 99C., 189.0
11. Vanadium content, ppm 159
12. Pitch content (524C ), % by wt., 53.1 This material which was designated 2-AB-77 was a 260C bitumen obtained from Great Canadian Oil Sands, Fort MacMurray, Alberta. It was topped in a continuous distillation column to obtain 343C material and 427C
material. The properties of these two topped bitumens are - 1~95847 given in Table 2 below:
Table 2 343C.+ 427C.+
~ . .
1. Specific gravity, 15/15C., 1.023 1.06 2. Sulfur (bomb), % by wt., 4.97 5.53 3. Ash, % by wt., 0.66 1.21 4. Conradson carbon residue, ~ by wt., 15.0 19.8 5. Pentane insolubles, ~ by wt., 17.0 26.4 6. Benzene insolubles, % by wt.,0.54 1.2 7. Carbon, % by wt., 83.32 82.2 8. Hydrogen, % by wt., 10.27 9.5 9. Nitrogen, % by wt., 0.44 0.75 10. Viscosity, cSt (kinematic centistokes) at 54C., 13136 at 99C., 413 11. Vanadium content, ppm 184 257 12. Pitch content (524C ), % by wt., 58.2 83.5 It will be seen from the above table that the 343C
material had only a slightly higher concentration of pitch, 58.2%, compared with 53.1~ for the bitumen as received. On the other hand, the 427C. material contained 83.5% pitch.
The thermal hydrocracking of these topped materials was carried out at reaction conditions shown below:
Pressure psig 1500 Liquid hourly space velocity 2.0 Recycle gas rate scf/bbl 3480 Recycle gas purity (hydrogen) vol.~ 85 Using a reaction sequence as shown in Figure 1, thermal hydrocracking was carried out at temperatures of 420, 430, 440 and 450C.
The results obtained are tabulated in Table 3 and 10958~17 are also illustrated by Figure 2.
Table 3 Feed Reaction Pitch H2 Consumed H2 Consumed Temp. C. Conv. feed Pitch converted _. ... ___ ..
2-AB-77 430 42.6 34.7 154 260C. 440 58.5 47.9 155 450 66.3 60.5 172 343C.+ 420 32.9 28.8 151 430 40.3 34.7 148 440 54.9 48.7 153 450 68.6 64.9 163 427C.+ 430 53.0 47.9 108 440 59.5 50.8 102 450 69.5 71.5 1~
It is clearly seen from Figure 2 that the pitch converted per unit time is higher by a factor of 2.0 for 427C~ feed. These results indicate that topped feed requires a smaller capacity reactor and that topping actually improves pitch conversion. From table 3 it is also seen that hydrogen consumed/ton of pitch converted is much lower for the heavier (427C. ) feed.
The properties of the distillate material (260-427C.) obtained by topping the feed stock are shown in Table 4 below 1~95~
Table 4 ~ .
Boiling range, C., 260-427 Gravity, 15/15C. 0.917 Sulphur, % by wt. 2.28 Vanadium, ppm 17 Conradson carbon 0.025 residue (CCR), % by wt.
Carbon, % by wt., 84.32 Hydrogen , ~ by wt. 11.65 Nitrogen, ppm 399 Ash, ~ by wt., nil It will be seen from the above table that the material is low in sulfur, nitrogen, CCR and metals and this material can be directly hydrotreated. This also shows that sending material (260-427C.) through the thermal hydrocracking step is unnecessary.
Example 2 An in-situ bitumen was obtained from the Cold Lake district of Alberta and this was topped in a continuous distillation column to obtain 343C. and 427C.+ material.
It was found that the 343C.+ material contained 63.8 wt.%
pitch and the 427C.+ material contained 78.5 wt. % pitch.
The thermal hydrocracking of these charge stocks was carried out at reaction conditions as follows:
Pressure, psig. 2000 Liquid hourly space velocity l.S
Recycle gas rate, scf/bbl. 70~0 Recycle gas purity(hydrogen)vol.% ~5 Using the same system as in Example l, thermal hydro-cracking was carried out at temperatures between 410 and 430C.
10958~7 Results were tabulated in Table 5 below and illustrated by Figure 3.
Table S
Feed Reaction Pitch H Consumed m H consumed m3 Temperature Conversion ~ I/t of feed ~PI/t of C. wt. % pitch conv.
_ _ ._ . I
343C.~ 420 38. 7 19 . 980. 7 425 44.4 27. 3 96.4 + 430 50.6 35.9 111.1 427C. 410 29.7 15.9 68.1 420 41.1 27.4 84.8 _ _ 54.5 40. 6 94. 8 me above results again show that pitch conversion is significantly higher with higher topping temperatures.
Also, the hydrogen consumed per unit weight of pitch con-verted for pitch conversion above 40~ is lower for charge stocks topped at higher temperatures.
material. The properties of these two topped bitumens are - 1~95847 given in Table 2 below:
Table 2 343C.+ 427C.+
~ . .
1. Specific gravity, 15/15C., 1.023 1.06 2. Sulfur (bomb), % by wt., 4.97 5.53 3. Ash, % by wt., 0.66 1.21 4. Conradson carbon residue, ~ by wt., 15.0 19.8 5. Pentane insolubles, ~ by wt., 17.0 26.4 6. Benzene insolubles, % by wt.,0.54 1.2 7. Carbon, % by wt., 83.32 82.2 8. Hydrogen, % by wt., 10.27 9.5 9. Nitrogen, % by wt., 0.44 0.75 10. Viscosity, cSt (kinematic centistokes) at 54C., 13136 at 99C., 413 11. Vanadium content, ppm 184 257 12. Pitch content (524C ), % by wt., 58.2 83.5 It will be seen from the above table that the 343C
material had only a slightly higher concentration of pitch, 58.2%, compared with 53.1~ for the bitumen as received. On the other hand, the 427C. material contained 83.5% pitch.
The thermal hydrocracking of these topped materials was carried out at reaction conditions shown below:
Pressure psig 1500 Liquid hourly space velocity 2.0 Recycle gas rate scf/bbl 3480 Recycle gas purity (hydrogen) vol.~ 85 Using a reaction sequence as shown in Figure 1, thermal hydrocracking was carried out at temperatures of 420, 430, 440 and 450C.
The results obtained are tabulated in Table 3 and 10958~17 are also illustrated by Figure 2.
Table 3 Feed Reaction Pitch H2 Consumed H2 Consumed Temp. C. Conv. feed Pitch converted _. ... ___ ..
2-AB-77 430 42.6 34.7 154 260C. 440 58.5 47.9 155 450 66.3 60.5 172 343C.+ 420 32.9 28.8 151 430 40.3 34.7 148 440 54.9 48.7 153 450 68.6 64.9 163 427C.+ 430 53.0 47.9 108 440 59.5 50.8 102 450 69.5 71.5 1~
It is clearly seen from Figure 2 that the pitch converted per unit time is higher by a factor of 2.0 for 427C~ feed. These results indicate that topped feed requires a smaller capacity reactor and that topping actually improves pitch conversion. From table 3 it is also seen that hydrogen consumed/ton of pitch converted is much lower for the heavier (427C. ) feed.
The properties of the distillate material (260-427C.) obtained by topping the feed stock are shown in Table 4 below 1~95~
Table 4 ~ .
Boiling range, C., 260-427 Gravity, 15/15C. 0.917 Sulphur, % by wt. 2.28 Vanadium, ppm 17 Conradson carbon 0.025 residue (CCR), % by wt.
Carbon, % by wt., 84.32 Hydrogen , ~ by wt. 11.65 Nitrogen, ppm 399 Ash, ~ by wt., nil It will be seen from the above table that the material is low in sulfur, nitrogen, CCR and metals and this material can be directly hydrotreated. This also shows that sending material (260-427C.) through the thermal hydrocracking step is unnecessary.
Example 2 An in-situ bitumen was obtained from the Cold Lake district of Alberta and this was topped in a continuous distillation column to obtain 343C. and 427C.+ material.
It was found that the 343C.+ material contained 63.8 wt.%
pitch and the 427C.+ material contained 78.5 wt. % pitch.
The thermal hydrocracking of these charge stocks was carried out at reaction conditions as follows:
Pressure, psig. 2000 Liquid hourly space velocity l.S
Recycle gas rate, scf/bbl. 70~0 Recycle gas purity(hydrogen)vol.% ~5 Using the same system as in Example l, thermal hydro-cracking was carried out at temperatures between 410 and 430C.
10958~7 Results were tabulated in Table 5 below and illustrated by Figure 3.
Table S
Feed Reaction Pitch H Consumed m H consumed m3 Temperature Conversion ~ I/t of feed ~PI/t of C. wt. % pitch conv.
_ _ ._ . I
343C.~ 420 38. 7 19 . 980. 7 425 44.4 27. 3 96.4 + 430 50.6 35.9 111.1 427C. 410 29.7 15.9 68.1 420 41.1 27.4 84.8 _ _ 54.5 40. 6 94. 8 me above results again show that pitch conversion is significantly higher with higher topping temperatures.
Also, the hydrogen consumed per unit weight of pitch con-verted for pitch conversion above 40~ is lower for charge stocks topped at higher temperatures.
Claims (9)
1. In a process for hydrocracking a heavy hydrocarbon oil, a substantial proportion of which boils above 524°C., wherein (a) a feed of said heavy oil in the presence of 500 - 50,000 s.c.f. of hydrogen per barrel of heavy oil feed is passed upwardly through a vertical empty column hydrocracking zone maintained at a temperature between about 400 and 490°C., a pressure above 500 psig.
and a space velocity between about 0.5 and 4.0 volumes of heavy oil per hour per volume of hydrocracking capacity, (b) removing from said hydrocracking zone a mixed effluent containing a gaseous phase comprising hydrogen and vaporous hydrocarbons and a liquid phase comprising heavy hydrocarbons and (c) separating said effluent into a gaseous stream containing hydrogen and vaporous hydrocarbons and a liquid stream containing heavy hydrocarbons, the improvement which comprises utilizing as the heavy hydrocarbon oil feed a heavy oil topped in a distillation column to an equivalent atmospheric boiling temperature of at least 350°C.
and a space velocity between about 0.5 and 4.0 volumes of heavy oil per hour per volume of hydrocracking capacity, (b) removing from said hydrocracking zone a mixed effluent containing a gaseous phase comprising hydrogen and vaporous hydrocarbons and a liquid phase comprising heavy hydrocarbons and (c) separating said effluent into a gaseous stream containing hydrogen and vaporous hydrocarbons and a liquid stream containing heavy hydrocarbons, the improvement which comprises utilizing as the heavy hydrocarbon oil feed a heavy oil topped in a distillation column to an equivalent atmospheric boiling temperature of at least 350°C.
2. A process according to claim 1 wherein the heavy hydrocarbon oil feed is topped to an equivalent atmospheric boiling temperature of at least 400°C.
3. A process according to claim 1 wherein the hydro-cracking is conducted at a pressure in the range of 500 to 3,500 psig.
4. A process according to claim 1 wherein the mixed effluent is separated in a hot separating zone at a tem-perature of about 250 to 490°C. and at the pressure of the hydrocracking zone.
5. A process according to claim 4 wherein at least part of the heavy hydrocarbon stream from the hot sep-arating zone is recycled to the hydrocracking zone.
6. A process according to claim 5 wherein at least part of the heavy hydrocarbon stream from the hot separating zone is sent to secondary treatment.
7. A process according to claim 5 wherein the gaseous stream from the hot separator is cooled and separated in a low temperature separator into a gaseous stream containing hydrogen and a liquid product stream contain-ing light oil.
8. A process according to claim 7 wherein the hydrogen separated is scrubbed and recycled to the hydrocracking zone.
9. A process according to claim 1, wherein the heavy hydrocarbon oil is bitumen obtained from tar sands or heavy oils.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA299,229A CA1095847A (en) | 1978-03-17 | 1978-03-17 | Thermal hydrocracking of topped heavy oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA299,229A CA1095847A (en) | 1978-03-17 | 1978-03-17 | Thermal hydrocracking of topped heavy oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1095847A true CA1095847A (en) | 1981-02-17 |
Family
ID=4111025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA299,229A Expired CA1095847A (en) | 1978-03-17 | 1978-03-17 | Thermal hydrocracking of topped heavy oils |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1095847A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4389303A (en) * | 1979-12-12 | 1983-06-21 | Metallgesellschaft Aktiengesellschaft | Process of converting high-boiling crude oils to equivalent petroleum products |
| DE3221822A1 (en) * | 1982-06-09 | 1983-12-15 | Minister of Energy, Mines and Resources, Ottawa, Ontario | Process for hydrocracking heavy oil |
-
1978
- 1978-03-17 CA CA299,229A patent/CA1095847A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4389303A (en) * | 1979-12-12 | 1983-06-21 | Metallgesellschaft Aktiengesellschaft | Process of converting high-boiling crude oils to equivalent petroleum products |
| DE3221822A1 (en) * | 1982-06-09 | 1983-12-15 | Minister of Energy, Mines and Resources, Ottawa, Ontario | Process for hydrocracking heavy oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4214977A (en) | Hydrocracking of heavy oils using iron coal catalyst | |
| US4252634A (en) | Thermal hydrocracking of heavy hydrocarbon oils with heavy oil recycle | |
| US4370221A (en) | Catalytic hydrocracking of heavy oils | |
| US4299685A (en) | Hydrocracking of heavy oils/fly ash slurries | |
| US4969988A (en) | Antifoam to achieve high conversion in hydroconversion of heavy oils | |
| US6004453A (en) | Hydrocracking of heavy hydrocarbon oils with conversion facilitated by recycle of both heavy gas oil and pitch | |
| CA2131261C (en) | Hydrocracking of heavy hydrocarbon oils with heavy hydrocarbon recycle | |
| US4695369A (en) | Catalytic hydroconversion of heavy oil using two metal catalyst | |
| US4376695A (en) | Simultaneous demetalization and hydrocracking of heavy hydrocarbon oils | |
| US5972202A (en) | Hydrotreating of heavy hydrocarbon oils with control of particle size of particulate additives | |
| US3622498A (en) | Slurry processing for black oil conversion | |
| US4606809A (en) | Hydroconversion of heavy oils | |
| CA2111665C (en) | Hydrocracking of heavy asphaltenic oil in presence of an additive to prevent coke formation | |
| US3622495A (en) | Multiple-stage slurry processing for black oil conversion | |
| CA1317585C (en) | Hydrocracking of heavy oils in presence of iron-coal slurry | |
| US4435280A (en) | Hydrocracking of heavy hydrocarbon oils with high pitch conversion | |
| US4557822A (en) | Hydroconversion process | |
| CA1202588A (en) | Hydrocracking of heavy oils in presence of dry mixed additive | |
| US4659452A (en) | Multi-stage hydrofining process | |
| CA1124195A (en) | Hydrocracking of heavy hydrocarbon using synthesis gas | |
| US3622499A (en) | Catalytic slurry process for black oil conversion with hydrogen and ammonia | |
| CA1095847A (en) | Thermal hydrocracking of topped heavy oils | |
| CA1117887A (en) | Catalytic hydrocracking of heavy oils | |
| US3530062A (en) | Catalytic conversion of hydrocarbon mixtures containing asphaltenes | |
| US3963604A (en) | Combination process for hydrorefining an asphaltenic hydrocarbonaceous charge stock |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |