CA1292715C - Process for the upgrading of heavy hydrocarbon oils (hydrogen transfer residue cracking) - Google Patents
Process for the upgrading of heavy hydrocarbon oils (hydrogen transfer residue cracking)Info
- Publication number
- CA1292715C CA1292715C CA000545937A CA545937A CA1292715C CA 1292715 C CA1292715 C CA 1292715C CA 000545937 A CA000545937 A CA 000545937A CA 545937 A CA545937 A CA 545937A CA 1292715 C CA1292715 C CA 1292715C
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- Canada
- Prior art keywords
- atmospheric
- catalytic thermal
- distillate
- thermal hydrogenation
- 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.)
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Classifications
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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
Abstract
A B S T R A C T
PROCESS FOR THE UPRGRADING OF HEAVY HYDROCARBON OILS
A process for upgrading a heavy hydrocarbon oil by involving a non-catalytic thermal hydrogenation zone and a hydrodemetallization zone wherein at least part of the hydrodemetallized product is subjected to atmospheric distillate and at least part of an atomospheric distillate obtained is recycled to the non-catalytic thermal hydrogenation zone.
PROCESS FOR THE UPRGRADING OF HEAVY HYDROCARBON OILS
A process for upgrading a heavy hydrocarbon oil by involving a non-catalytic thermal hydrogenation zone and a hydrodemetallization zone wherein at least part of the hydrodemetallized product is subjected to atmospheric distillate and at least part of an atomospheric distillate obtained is recycled to the non-catalytic thermal hydrogenation zone.
Description
l~:r~
PROC~SS FOR TH~ UPGRADING OF ~I~AVY HYDROCARBON OILS
The present invention relates to a process for the upgrading of heavy hydrocarbon oils as well as to hydrocarbon oils thus upgraded.
Heavy hydrocarbon oils and in particular residues obtained therefrom need further treatment in order to render them suitable for use in further processing into valuable products. Basically, the refiner has the choice between carbon removal and hydrogen addition for upgrading heavy material having an unfavourable hydrogen/carbon (H/C) ratio.
Coking is a well-known, relatively inexpensive, process but it suffers inherently from low liquid yield due to coke formation.
Alternatively, hydrogen addition routes offer much better liquid yields but need more complex equipment and are therefore more capital intensive.
Since heavy hydrocarbons generally contain rather large amounts of metal contaminants it is often necessary to subject them to a hydrodemetallization treatment which in essence is a catalytic treatment wherein the metals are substantially removed. The catalysts normally applied are also active, to some extent, as hydroconversion catalysts. The hydrodemetallization process which requires periodical catalyst replacement is typically suited for partial conversion of heavy material which necessitates the presence of further equipment, in particular a catalytic cracker, to obtain a bottomless synthetic crude.
It would thus be useful to be able to increase the total conversion level of the material subjected to catalytic hydro-demetallization, in particular to such an extent that treatment in catalytic cracker would no longer be required.
It is known from Japanese unexamined published patent applica-tion 60170695 to subject heavy hydrocarbon oils to a hydrogenation treatment carried out in two zones using a hydrogen donor obtained l~Z7iS
by hydrogenation of aromatic compounds in the first (thermal) zone and gaseous hydrogen and a solid catalyst in the second zone to effect catalytic hydrogenation. The use of hydrogen donor materials which have to be rehydrogenated after use is well known in the art as exemp]ified by IJ.S. patent specifications 2,953,513 and 4,294,686.
It is a severe disadvantage of such processes, however, that either an extraneous donor material (which should also be easily rehydrogenatable) has to be introduced into the process such as rather low boiling naphthenic compounds which are converted into aromatic compounds during the non-catalytic thermal hydrogenation and subsequently rehydrogenated and recycled, or that additional internal or external hydrogenation facilities and catalysts are required to provide the required hydrogen transfer material.
It has now been found that part of the product obtained after a hydrodemetallization treatment can be used advantageously to support the non-catalytic thermal hydrogenation of heavy hydrocarbon oils. It appears that high conversion levels can be achieved which may be attributed to the favourable H/C ratio of part of the atmospheric distillate obtained after hydrodemetallization.
The present invention thus relates to a process for upgrading heavy hydrocarbon oils involving a non-catalytic thermal hydrogenation zone and a hydrodemetallization zone wherein at least part of the hydrodemetallized product is subjected to atmospheric distillation and wherein at least part of an atmospheric distillate obtained is recycled to the non-catalytic thermal hydrogenation zone.
It has also been found that the process according to the present invention is preferably carried out in a hydrogen-rich environment. The presence of a hydrogen-rich environment has the additional advantage that a significant reduction in operation pressure in the non-catalytic thermal treatment can be realized.
The hydrogen-rich environment to be maintained in the non-catalytic thermal treatment can be obtained - in addition to the contribution from the recycled atmospheric distillate obtained after the hydro-demetallization step - by introducing hydrogen into the vessel in which the non-catalytic thermal hydrogenation is or will be carried out and/or by introducing one or more fresh or recycled streams comprising a favourable H/C molar ratio, for instance a hydrogen-transfer medium which is capable of releasing the required amount of hydrogen during the non-catalytic thermal treatment. It is preferred to carry out the non-catalytic thermal treatment in the presence of a hydrogen-rich environment containing the recycled atmospheric distillate described hereinbefore and molecular hydrogen.
If desired streams originating from the process and having a favourable H/C ratio may also contribute to the hydrogen-rich environment, for instance hydrogen-donor materials as known from the state of the art.
The process according to the present invention will now be illustrated by means of the following Figures (I-V) wherein similar numbers have similar meanings in each of the Figures.
In Figure I the upgrading of a residual fraction is described by subjecting it to a non-catalytic thermal hydrogenation in a hydrogen-rich environment, subjecting the product obtained to a hydrodemetallization treatment, and subjecting the product obtained to an atmospheric distillation and recycling at least part of an atmospheric distillate to the non-catalytic thermal hydrogenation zone;
In Figure II a process is described as depicted in Figure I, but wherein an atmospheric residue is used as starting material which is sub;ected to a vacuum distillation and wherein the vacuum distillate together with non-recycled product(s) of the atmospheric distillation unit to which the hydrodemetallization effluent has been subjected forms a reconstituted crude;
In Figure III a process is described as depicted in Figure II, but wherein the product obtained in the non-catalytic thermal hydrogenation is subjected to an atmospheric distillation prior to the hydrodemetallization treatment and wherein the atmospheric distiIlate thus obtained forms part of the reconstituted crude;
In Figure IV a process is described as depicted in Figure III, but wherein part of thc atmospheric distillate obtained in the 71~i distillation of the product obtained in the non-catalytic thermal hydrogenation is subjected to a (catalytic) hydrogenation treatment and wherein the product of said hydrogenation treatment is at least partly recycled to the non-catalytic thermal hydrogenation zone, the part not being recycled forming part of the reconstituted crude; and In Figure V a process is described as depicted in Figure III
or Figure IV, but wherein the hydrocarbon oil to be treated is firstly subjected to atmospheric distillation and wherein the atmospheric residue obtained after distillation of the product of the non-catalytic thermal hydrogenation is subjected to vacuum distillation prior to the hydrodemetallization treatment.
In the process as described in Figure I a starting material 1 which may be an atmospheric distillate, a vacuum distillate or a residual material is introduced into a non-catalytic thermal hydrogenation vessel 10 which is operated at a pressure in the range of from 45 to 90 bar and at a temperature in the range from 380 to 430 C.
The product obtained in the non-catalytic thermal hydrogenation is transported via line 3 to the hydrodemetallization vessel 20 to which fresh or make up hydrogen is introduced via line 4. Suitable hydrodemetallization catalysts comprise Group V, Group VI and/or Group VIII metals or metal compounds on a carrier. Preference is given to the use of one or more of nickel and cobalt as Group VIII
metal (compounds), vanadium as Group V metal (compound) and one or more of molybdenum and tungsten as Group VI metal (compounds).
Suitable carriers comprise silica, alumina and silica-alumina. The metals having hydrogenating activity are normally used in amounts between 0.1 and 30% by weight. The hydrodemetallization treatment is normally carried out at a temperature in the range of from 370 to 450 C, a hydrogen partial pressure of between 50 and 250 bar and at a space velocity between 0.05 and 10 kg/l.h. Hydrodemetal-lized product is obtained via line 5 and subjected to an atmospheric distillation in unit 30 with a view to obtain apart from a small gas make (line 6) at least two atmospheric distillates, one of which is at least partly recycled via line 7 to 12~Z715 the feed to be subjected to the non-catalytic thermal hydrogenation in vessel 10 via line 1. The other fraction 8 serves, optionally with the remainder of the first distillate 7 as the product of the process according to the present invention. Preferably a fraction boiling between 150 and 370 C, in particular between 200 and 370 ~C is used as recycle stream 7 since it has a H/C ratio which can be used advantageously in the non-catalytic thermal hydrogenation.
The amount of material to be recycled depends to some extent on the severity applied in the non-catalytic hydrogenation. In general at least 35 %v of the 150 to 370 C distillate will be recycled, preferably between 40 and 60 %v. Part or all of the atmospheric residue (line 9) can be combined with the product stream 8 via line 11 to form part of the reconstituted crude. If desired, part or all of the atmospheric residue may be discarded via line 9.
The hydrogen-rich environment preferred to be maintained in the process according to the present invention is provided for by line 2 which represents the introduction of hydrogen and/or a hydrogen-transfer medium containing component to vessel 10. The hydrogen supplied to the vessel may be fresh or recycled hydrogen which need not to be of 100% purity. Streams containing a substantial amount of hydrogen (e.g. at least 70 %v) can be suitably applied.
The hydrogen-transfer medium to be introduced as such or in combination with hydrogen can be any of a number of well-known hydrogen-transfer media, either generated on purpose or readily available to the refiner. If desired, the hydrogen-transfer media may be mixed with the feedstock and/or the recycled atmospheric distillate prior to introduction into the non-catalytic thermal hydrogenation zone.
In the process as depicted in Figure II an atmospheric residue 12 is used as the starting material. It is firstly subjected to a vacuum distillation in unit 40 from which a vacuum distillate is obtained which is transported via line 13 to contribute to the reconstituted crude. The vacuum residue obtained is fed through line 1 to the non-catalytic thermal hydrogenation vessel 10. The 12~271S
reconstituted crude obtained when using this embodiment of the process according to the present invention comprises at least the vacuum distillate 13 and at least one distillate obtained after the hydrodemetallization treatment~ via line 8, and optionally part of a further atmospheric distillate via line 7 and an atmospheric residue via line 11.
The process as depicted in Figure III is closely related to the process depicted in Figure II with the difference that a further atmospheric distillation unit 50 is present between the non-catalytic thermal hydrogenation zone 10 and the hydrodemetall-ization zone 20 which allows the production of a further atmospheric distillate 15 which suitably via line 13, but separate if desired, contributes to the reconstituted crude.
In the process depicted in Figure IV a further embodiment is incorporated which can be used suitably in addition to the various processes described thusfar. Not only is the atmospheric distillation unit 50 used to produce the atmospheric distillate 15 and the atmospheric residue 3 to be hydrodemetallized, but it also serves to produce a further distillate fraction 16 which is led to a hydrogenation unit 60. The hydrogenation unit is suitably operated at a temperature between 300 and 370 C and at a hydrogen pressure betweer. 30 and 90 bar to increase the amount of transferable hydrogen in the distillate fraction 17 which is at least in part recycled to the non-catalytic thermal hydrogenation vessel 10, preferably via line 1. If desired, part of the product of the hydrogenation treatment may be collected via line 18 to form part of the reconstituted crude. The hydrogen required in unit 60 can be introduced either by units supplying lines 2 or 4 or can be introduced separately (not shown).
In the process depicted in Figure V a further embodiment is incorporated wherein a crude material is introduced via line 12 into atmospheric distillation unit 70 which allows production of an atmospheric distillate which can be used as such, as part of the reconstituted crude or can be used (as depicted in Figure V) as part of the feed to be subjected to non-catalytic thermal lS
hydrogenation via line 22. Use is made in particular of this fraction as co-feed for the non-catalytic thermal hydrogenation step because o its favourable H/C ratio. A further feature of the process depicted in Figure V resides in the presence of a vacuum distillation unit ôO to obtain a further (vacuum) distillate fraction 24 from the atmospheric residue 23. The vacuum residue 3 is subjected to hydrodemetallization in unit 20. It is, of course, also possible to carry out the embodiment depicted in Figure V
without the hydrogenation stage in vessel 60.
It will be clear that the preferred embodiment of the process according to the present invention resides in the use of molecular hydrogen together with at least part of a fraction of the distillate obtained after hydrodemetallization as the hydrogen-rich environment.
By also making use of the atmospheric distillate via line Z2 which has not been subjected to any hydrotreatment but which has an intrinsically high H/C ratio, and optionally a re-hydrogenated distillate via line 17 a large variety of hydrotreatment conditions can be provided for in the non-catalytic thermal treatment stage 10. This also allows a high degree of flexibility in determining the composition of the final product as well as the preferred boiling point range and amount of atmospheric distillate ex hydrodemetallization to be recycled.
Example Based on Figure V as described hereinabove 100 pbw of Peace River bitumen can be upgraded by subjecting it to atmospheric distillation yielding 2 pbw of 200 C material to be collected as reconstituted crude, 19 pbw of 200-370 C material to be used in the non-catalytic thermal hydrogenation and 79 pbw of atmospheric residue. This atmospheric residue is then subjected to vacuum distillation to yield 24 pbw of vacuum distillate to be collected as part of reconstituted crude and 55 pbw of vacuum residue to be processed in the non-catalytic thermal hydrogenation unit. The feed to this unit amounts to 116 pbw containing also 15 pbw recycled vacuum residue obtained after the hydrodemetallization treatment, 7 pbw of a 200-370 C atmospheric distillate obtained after lZ~2~715 hydrodemetallization and 20 pbw atmospheric distillate obtained as discussed hereinafter. The non-catalytic thermal hydrogenation is carried out at a temperature of 420 C and a pressure of 60 bar.
Thc effluent from the non-catalytic thermal hydrogenation treatment is subjected to distillation yielding 4 pbw of gaseous products, 14 pbw of 200 C materia1, 52 pbw of 200-370 C of which 20 pbw is recycled to the non-catalytic thermal hydrogenation zone and 32 pbw is collected to form part of reconstituted crude, 12 pbw of 370-520 C material also forming part of reconstituted crude and 34 pbw of residue which is subjected to hydrodemetallization.
The hydrodemetallization is carried out at 405 C and an operating pressure of 150 bar using a commercially available Ni/Mo on alumina catalyst. The effluent from the hydrodemetallization treatment is then subjected to distillation to yield 2 pbw of gaseous products, 2 pbw of 200 C material contributing to recon-stituted crude, 7 pbw of 200-370 C which is recycled to the non-catalytic thermal hydrogenation unit to serve as the atmospheric distillate ex hydrodemetallization, 8 pbw of 370-520 ~C material also forming part of reconstituted crude and 15 pbw of residue which is recycled to the non-catalytic thermal hydrogenation unit.
If desired, the vacuum distillates obtained prior to and after the non-catalytic thermal hydrogenation can be subjected, either together or separate to a hydrogenation treatment using standard hydrogenation catalysts to increase the quality of the reconstituted crude. A similar treatment can be carried out on the atmospheric distillates boiling predominantly in the naphtha mode obtained prior to and/or after the non-catalytic thermal hydrogenation.
PROC~SS FOR TH~ UPGRADING OF ~I~AVY HYDROCARBON OILS
The present invention relates to a process for the upgrading of heavy hydrocarbon oils as well as to hydrocarbon oils thus upgraded.
Heavy hydrocarbon oils and in particular residues obtained therefrom need further treatment in order to render them suitable for use in further processing into valuable products. Basically, the refiner has the choice between carbon removal and hydrogen addition for upgrading heavy material having an unfavourable hydrogen/carbon (H/C) ratio.
Coking is a well-known, relatively inexpensive, process but it suffers inherently from low liquid yield due to coke formation.
Alternatively, hydrogen addition routes offer much better liquid yields but need more complex equipment and are therefore more capital intensive.
Since heavy hydrocarbons generally contain rather large amounts of metal contaminants it is often necessary to subject them to a hydrodemetallization treatment which in essence is a catalytic treatment wherein the metals are substantially removed. The catalysts normally applied are also active, to some extent, as hydroconversion catalysts. The hydrodemetallization process which requires periodical catalyst replacement is typically suited for partial conversion of heavy material which necessitates the presence of further equipment, in particular a catalytic cracker, to obtain a bottomless synthetic crude.
It would thus be useful to be able to increase the total conversion level of the material subjected to catalytic hydro-demetallization, in particular to such an extent that treatment in catalytic cracker would no longer be required.
It is known from Japanese unexamined published patent applica-tion 60170695 to subject heavy hydrocarbon oils to a hydrogenation treatment carried out in two zones using a hydrogen donor obtained l~Z7iS
by hydrogenation of aromatic compounds in the first (thermal) zone and gaseous hydrogen and a solid catalyst in the second zone to effect catalytic hydrogenation. The use of hydrogen donor materials which have to be rehydrogenated after use is well known in the art as exemp]ified by IJ.S. patent specifications 2,953,513 and 4,294,686.
It is a severe disadvantage of such processes, however, that either an extraneous donor material (which should also be easily rehydrogenatable) has to be introduced into the process such as rather low boiling naphthenic compounds which are converted into aromatic compounds during the non-catalytic thermal hydrogenation and subsequently rehydrogenated and recycled, or that additional internal or external hydrogenation facilities and catalysts are required to provide the required hydrogen transfer material.
It has now been found that part of the product obtained after a hydrodemetallization treatment can be used advantageously to support the non-catalytic thermal hydrogenation of heavy hydrocarbon oils. It appears that high conversion levels can be achieved which may be attributed to the favourable H/C ratio of part of the atmospheric distillate obtained after hydrodemetallization.
The present invention thus relates to a process for upgrading heavy hydrocarbon oils involving a non-catalytic thermal hydrogenation zone and a hydrodemetallization zone wherein at least part of the hydrodemetallized product is subjected to atmospheric distillation and wherein at least part of an atmospheric distillate obtained is recycled to the non-catalytic thermal hydrogenation zone.
It has also been found that the process according to the present invention is preferably carried out in a hydrogen-rich environment. The presence of a hydrogen-rich environment has the additional advantage that a significant reduction in operation pressure in the non-catalytic thermal treatment can be realized.
The hydrogen-rich environment to be maintained in the non-catalytic thermal treatment can be obtained - in addition to the contribution from the recycled atmospheric distillate obtained after the hydro-demetallization step - by introducing hydrogen into the vessel in which the non-catalytic thermal hydrogenation is or will be carried out and/or by introducing one or more fresh or recycled streams comprising a favourable H/C molar ratio, for instance a hydrogen-transfer medium which is capable of releasing the required amount of hydrogen during the non-catalytic thermal treatment. It is preferred to carry out the non-catalytic thermal treatment in the presence of a hydrogen-rich environment containing the recycled atmospheric distillate described hereinbefore and molecular hydrogen.
If desired streams originating from the process and having a favourable H/C ratio may also contribute to the hydrogen-rich environment, for instance hydrogen-donor materials as known from the state of the art.
The process according to the present invention will now be illustrated by means of the following Figures (I-V) wherein similar numbers have similar meanings in each of the Figures.
In Figure I the upgrading of a residual fraction is described by subjecting it to a non-catalytic thermal hydrogenation in a hydrogen-rich environment, subjecting the product obtained to a hydrodemetallization treatment, and subjecting the product obtained to an atmospheric distillation and recycling at least part of an atmospheric distillate to the non-catalytic thermal hydrogenation zone;
In Figure II a process is described as depicted in Figure I, but wherein an atmospheric residue is used as starting material which is sub;ected to a vacuum distillation and wherein the vacuum distillate together with non-recycled product(s) of the atmospheric distillation unit to which the hydrodemetallization effluent has been subjected forms a reconstituted crude;
In Figure III a process is described as depicted in Figure II, but wherein the product obtained in the non-catalytic thermal hydrogenation is subjected to an atmospheric distillation prior to the hydrodemetallization treatment and wherein the atmospheric distiIlate thus obtained forms part of the reconstituted crude;
In Figure IV a process is described as depicted in Figure III, but wherein part of thc atmospheric distillate obtained in the 71~i distillation of the product obtained in the non-catalytic thermal hydrogenation is subjected to a (catalytic) hydrogenation treatment and wherein the product of said hydrogenation treatment is at least partly recycled to the non-catalytic thermal hydrogenation zone, the part not being recycled forming part of the reconstituted crude; and In Figure V a process is described as depicted in Figure III
or Figure IV, but wherein the hydrocarbon oil to be treated is firstly subjected to atmospheric distillation and wherein the atmospheric residue obtained after distillation of the product of the non-catalytic thermal hydrogenation is subjected to vacuum distillation prior to the hydrodemetallization treatment.
In the process as described in Figure I a starting material 1 which may be an atmospheric distillate, a vacuum distillate or a residual material is introduced into a non-catalytic thermal hydrogenation vessel 10 which is operated at a pressure in the range of from 45 to 90 bar and at a temperature in the range from 380 to 430 C.
The product obtained in the non-catalytic thermal hydrogenation is transported via line 3 to the hydrodemetallization vessel 20 to which fresh or make up hydrogen is introduced via line 4. Suitable hydrodemetallization catalysts comprise Group V, Group VI and/or Group VIII metals or metal compounds on a carrier. Preference is given to the use of one or more of nickel and cobalt as Group VIII
metal (compounds), vanadium as Group V metal (compound) and one or more of molybdenum and tungsten as Group VI metal (compounds).
Suitable carriers comprise silica, alumina and silica-alumina. The metals having hydrogenating activity are normally used in amounts between 0.1 and 30% by weight. The hydrodemetallization treatment is normally carried out at a temperature in the range of from 370 to 450 C, a hydrogen partial pressure of between 50 and 250 bar and at a space velocity between 0.05 and 10 kg/l.h. Hydrodemetal-lized product is obtained via line 5 and subjected to an atmospheric distillation in unit 30 with a view to obtain apart from a small gas make (line 6) at least two atmospheric distillates, one of which is at least partly recycled via line 7 to 12~Z715 the feed to be subjected to the non-catalytic thermal hydrogenation in vessel 10 via line 1. The other fraction 8 serves, optionally with the remainder of the first distillate 7 as the product of the process according to the present invention. Preferably a fraction boiling between 150 and 370 C, in particular between 200 and 370 ~C is used as recycle stream 7 since it has a H/C ratio which can be used advantageously in the non-catalytic thermal hydrogenation.
The amount of material to be recycled depends to some extent on the severity applied in the non-catalytic hydrogenation. In general at least 35 %v of the 150 to 370 C distillate will be recycled, preferably between 40 and 60 %v. Part or all of the atmospheric residue (line 9) can be combined with the product stream 8 via line 11 to form part of the reconstituted crude. If desired, part or all of the atmospheric residue may be discarded via line 9.
The hydrogen-rich environment preferred to be maintained in the process according to the present invention is provided for by line 2 which represents the introduction of hydrogen and/or a hydrogen-transfer medium containing component to vessel 10. The hydrogen supplied to the vessel may be fresh or recycled hydrogen which need not to be of 100% purity. Streams containing a substantial amount of hydrogen (e.g. at least 70 %v) can be suitably applied.
The hydrogen-transfer medium to be introduced as such or in combination with hydrogen can be any of a number of well-known hydrogen-transfer media, either generated on purpose or readily available to the refiner. If desired, the hydrogen-transfer media may be mixed with the feedstock and/or the recycled atmospheric distillate prior to introduction into the non-catalytic thermal hydrogenation zone.
In the process as depicted in Figure II an atmospheric residue 12 is used as the starting material. It is firstly subjected to a vacuum distillation in unit 40 from which a vacuum distillate is obtained which is transported via line 13 to contribute to the reconstituted crude. The vacuum residue obtained is fed through line 1 to the non-catalytic thermal hydrogenation vessel 10. The 12~271S
reconstituted crude obtained when using this embodiment of the process according to the present invention comprises at least the vacuum distillate 13 and at least one distillate obtained after the hydrodemetallization treatment~ via line 8, and optionally part of a further atmospheric distillate via line 7 and an atmospheric residue via line 11.
The process as depicted in Figure III is closely related to the process depicted in Figure II with the difference that a further atmospheric distillation unit 50 is present between the non-catalytic thermal hydrogenation zone 10 and the hydrodemetall-ization zone 20 which allows the production of a further atmospheric distillate 15 which suitably via line 13, but separate if desired, contributes to the reconstituted crude.
In the process depicted in Figure IV a further embodiment is incorporated which can be used suitably in addition to the various processes described thusfar. Not only is the atmospheric distillation unit 50 used to produce the atmospheric distillate 15 and the atmospheric residue 3 to be hydrodemetallized, but it also serves to produce a further distillate fraction 16 which is led to a hydrogenation unit 60. The hydrogenation unit is suitably operated at a temperature between 300 and 370 C and at a hydrogen pressure betweer. 30 and 90 bar to increase the amount of transferable hydrogen in the distillate fraction 17 which is at least in part recycled to the non-catalytic thermal hydrogenation vessel 10, preferably via line 1. If desired, part of the product of the hydrogenation treatment may be collected via line 18 to form part of the reconstituted crude. The hydrogen required in unit 60 can be introduced either by units supplying lines 2 or 4 or can be introduced separately (not shown).
In the process depicted in Figure V a further embodiment is incorporated wherein a crude material is introduced via line 12 into atmospheric distillation unit 70 which allows production of an atmospheric distillate which can be used as such, as part of the reconstituted crude or can be used (as depicted in Figure V) as part of the feed to be subjected to non-catalytic thermal lS
hydrogenation via line 22. Use is made in particular of this fraction as co-feed for the non-catalytic thermal hydrogenation step because o its favourable H/C ratio. A further feature of the process depicted in Figure V resides in the presence of a vacuum distillation unit ôO to obtain a further (vacuum) distillate fraction 24 from the atmospheric residue 23. The vacuum residue 3 is subjected to hydrodemetallization in unit 20. It is, of course, also possible to carry out the embodiment depicted in Figure V
without the hydrogenation stage in vessel 60.
It will be clear that the preferred embodiment of the process according to the present invention resides in the use of molecular hydrogen together with at least part of a fraction of the distillate obtained after hydrodemetallization as the hydrogen-rich environment.
By also making use of the atmospheric distillate via line Z2 which has not been subjected to any hydrotreatment but which has an intrinsically high H/C ratio, and optionally a re-hydrogenated distillate via line 17 a large variety of hydrotreatment conditions can be provided for in the non-catalytic thermal treatment stage 10. This also allows a high degree of flexibility in determining the composition of the final product as well as the preferred boiling point range and amount of atmospheric distillate ex hydrodemetallization to be recycled.
Example Based on Figure V as described hereinabove 100 pbw of Peace River bitumen can be upgraded by subjecting it to atmospheric distillation yielding 2 pbw of 200 C material to be collected as reconstituted crude, 19 pbw of 200-370 C material to be used in the non-catalytic thermal hydrogenation and 79 pbw of atmospheric residue. This atmospheric residue is then subjected to vacuum distillation to yield 24 pbw of vacuum distillate to be collected as part of reconstituted crude and 55 pbw of vacuum residue to be processed in the non-catalytic thermal hydrogenation unit. The feed to this unit amounts to 116 pbw containing also 15 pbw recycled vacuum residue obtained after the hydrodemetallization treatment, 7 pbw of a 200-370 C atmospheric distillate obtained after lZ~2~715 hydrodemetallization and 20 pbw atmospheric distillate obtained as discussed hereinafter. The non-catalytic thermal hydrogenation is carried out at a temperature of 420 C and a pressure of 60 bar.
Thc effluent from the non-catalytic thermal hydrogenation treatment is subjected to distillation yielding 4 pbw of gaseous products, 14 pbw of 200 C materia1, 52 pbw of 200-370 C of which 20 pbw is recycled to the non-catalytic thermal hydrogenation zone and 32 pbw is collected to form part of reconstituted crude, 12 pbw of 370-520 C material also forming part of reconstituted crude and 34 pbw of residue which is subjected to hydrodemetallization.
The hydrodemetallization is carried out at 405 C and an operating pressure of 150 bar using a commercially available Ni/Mo on alumina catalyst. The effluent from the hydrodemetallization treatment is then subjected to distillation to yield 2 pbw of gaseous products, 2 pbw of 200 C material contributing to recon-stituted crude, 7 pbw of 200-370 C which is recycled to the non-catalytic thermal hydrogenation unit to serve as the atmospheric distillate ex hydrodemetallization, 8 pbw of 370-520 ~C material also forming part of reconstituted crude and 15 pbw of residue which is recycled to the non-catalytic thermal hydrogenation unit.
If desired, the vacuum distillates obtained prior to and after the non-catalytic thermal hydrogenation can be subjected, either together or separate to a hydrogenation treatment using standard hydrogenation catalysts to increase the quality of the reconstituted crude. A similar treatment can be carried out on the atmospheric distillates boiling predominantly in the naphtha mode obtained prior to and/or after the non-catalytic thermal hydrogenation.
Claims (10)
1. A process for upgrading a heavy hydrocarbon oil involving a non-catalytic thermal hydrogenation zone and a hydrodemetallization zone which comprises subjecting at least part of the hydrodemetallized product to atmospheric distillation and recycling at least part of an atmospheric distillate obtained to the non-catalytic thermal hydrogenation zone.
2. A process according to claim 1 wherein the non-catalytic thermal hydrogenation is carried out in the presence of molecular hydrogen.
3. A process according to claim 1 wherein part of an atmospheric distillate having a boiling range from 150-370°C is recycled to the non-catalytic thermal hydrogenation zone.
4. A process according to claim 3 wherein between 40 and 60%v of the atmospheric distillate is recycled to the non-catalytic thermal hydrogenation zone.
5. A process according to claim 1, 2, 3 or 4, wherein an atmospheric residue is subjected to a vacuum distillation to produce a vacuum residue to be passed through the non-catalytic thermal hydrogenation zone and a vacuum distillate which is collected together with non-recycled distillate product(s) obtained by atmospheric distillation to form reconstituted crude.
6. A process according to claim 5 wherein the effluent from the non-catalytic thermal hydrogenation is subjected to an atmospheric distillation to produce an atmospheric residue to be passed through the hydrodemetallization zone and an atmospheric distillate which is at least partly collected to form part of reconstituted crude.
7. A process according to claim 5 wherein a heavy hydrocarbon oil is subjected to an atmospheric distillation to produce an atmospheric distillate which is passed through the non-catalytic thermal hydrogenation zone and an atomospheric residue which is subjected to a vacuum distillation to produce a vacuum distillate which is collected to form part of reconstituted crude and a vacuum residue which is passed through the non-catalytic thermal hydrogenation zone.
8. A process according to claim 6 or 7 wherein part of the atmospheric distillate produced from the effluent from the non-catalytic thermal hydrogenation zone is subjected to a hydrogenation treatment and thereafter at least partly recycled to the non-catalytic thermal hydrogenation zone.
9. A process according to claim 1, 2, 3, 4, 6 or 7 wherein the non-catalytic thermal hydrogenation is carried out at a pressure in the range of from 45 to 90 bar and at a temperature in the range from 380 to 450°C.
10. A process according to claim 1, 2, 3, 4, 6 or 7 wherein the hydrodemetallization treatment is carried out at a pressure in the range of from 50 to 250 bar and at a temperature in the range from 370 to 450°C
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8621490A GB2194794B (en) | 1986-09-05 | 1986-09-05 | Process for the upgrading of heavy hydrocarbon oils |
| GB8621490 | 1986-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1292715C true CA1292715C (en) | 1991-12-03 |
Family
ID=10603769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545937A Expired - Fee Related CA1292715C (en) | 1986-09-05 | 1987-09-02 | Process for the upgrading of heavy hydrocarbon oils (hydrogen transfer residue cracking) |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1292715C (en) |
| GB (1) | GB2194794B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2751232B1 (en) | 2011-08-31 | 2016-11-16 | ExxonMobil Chemical Patents Inc. | Upgrading hydrocarbon pyrolysis products |
| US9102884B2 (en) | 2012-08-31 | 2015-08-11 | Exxonmobil Chemical Patents Inc. | Hydroprocessed product |
| US9090835B2 (en) | 2012-08-31 | 2015-07-28 | Exxonmobil Chemical Patents Inc. | Preheating feeds to hydrocarbon pyrolysis products hydroprocessing |
| US9243193B2 (en) | 2013-03-14 | 2016-01-26 | Exxonmobil Research And Engineering Company | Fixed bed hydrovisbreaking of heavy hydrocarbon oils |
| WO2016099787A1 (en) | 2014-12-17 | 2016-06-23 | Exxonmobil Chemical Patents Inc. | Methods and systems for treating a hydrocarbon feed |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3114990A1 (en) * | 1980-04-21 | 1982-02-04 | Institut Français du Pétrole, 92502 Rueil-Malmaison, Hauts-de-Seine | METHOD FOR CONVERTING HEAVY DUTY HYDROCARBON OILS TO LIGHTER FRACTIONS |
| JPS57123290A (en) * | 1981-01-25 | 1982-07-31 | Chiyoda Chem Eng & Constr Co Ltd | Method for converting heavy hydrocarbon oil into light fractions |
| DE3204546A1 (en) * | 1982-02-10 | 1983-08-18 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR CONVERTING NON-DISTILLABLE RESIDUES OF MIXED OR PARAFFIN-BASED HYDROCARBON PIPES |
| US4451354A (en) * | 1983-01-03 | 1984-05-29 | Exxon Research And Engineering Co. | Process for upgrading hydrocarbonaceous oils |
-
1986
- 1986-09-05 GB GB8621490A patent/GB2194794B/en not_active Expired - Fee Related
-
1987
- 1987-09-02 CA CA000545937A patent/CA1292715C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB8621490D0 (en) | 1986-10-15 |
| GB2194794A (en) | 1988-03-16 |
| GB2194794B (en) | 1990-07-11 |
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