Hydrocracking process including switchable reactors with feedstocks containing 200 ppm by weight—2% by weight of asphaltenes
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-065/12
C10G-045/08
C10G-047/12
출원번호
US-0640202
(2009-12-17)
등록번호
US-9523049
(2016-12-20)
우선권정보
FR-08 07270 (2008-12-18)
발명자
/ 주소
Verstraete, Jan Jeroum
Dulot, Hugues
Bertoncini, Fabrice
Sanchez, Eric
출원인 / 주소
IFP Energies nouvelles
대리인 / 주소
Millen White Zelano & Branigan, P.C.
인용정보
피인용 횟수 :
0인용 특허 :
7
초록▼
The invention relates to a process for hydrocracking hydrocarbon feedstocks having 200 ppm by weight to 2% by weight of asphaltenes and/or more than 10 ppm by weight of metals, comprising a hydrodemetallation treatment in at least 2 switchable reaction zones, containing hydrodemetallation catalyst a
The invention relates to a process for hydrocracking hydrocarbon feedstocks having 200 ppm by weight to 2% by weight of asphaltenes and/or more than 10 ppm by weight of metals, comprising a hydrodemetallation treatment in at least 2 switchable reaction zones, containing hydrodemetallation catalyst and optionally hydrodenitrification catalyst, then a hydrorefining treatment to lower the organic nitrogen content, followed by a fixed-bed hydrocracking treatment and a distillation step.
대표청구항▼
1. A process for hydrocracking of hydrocarbon feedstocks containing 200 ppm to 2% by weight of asphaltenes, and/or more than 10 ppm by weight of metals, wherein said feedstock is subjected to a hydrodemetallation treatment between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, wi
1. A process for hydrocracking of hydrocarbon feedstocks containing 200 ppm to 2% by weight of asphaltenes, and/or more than 10 ppm by weight of metals, wherein said feedstock is subjected to a hydrodemetallation treatment between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, with a hydrogen/hydrocarbons ratio of between 200 Nm3/m3 and 2,000 Nm3/m3, said treatment being carried out in at least 2 switchable reactors each containing at least one hydrodemetallation catalyst and optionally containing a hydrodenitrification catalyst, said reactors being arranged in series in order to be used in a cyclic manner comprising successively repeating steps b) and c) defined hereinafter: a) a step in which the reactors are used all together for a duration at most equal to the time for deactivating and/or clogging one of them,b) a step during which at least one of the reactors is by-passed and the catalyst which it contains is regenerated and/or replaced by fresh or regenerated catalyst,c) a step during which the reactors are used all together, the switchable reactor(s), the catalyst of which has been regenerated and/or replaced over the course of the preceding step, being reconnected either in the initial position or in another position among the switchable reactors, and said step being conducted over a duration at most equal to the time for deactivating and/or clogging one of the switchable reactors,then at least a part of the effluent, which is at least partly demetallated and optionally partly denitrified, is hydrorefined in a hydrorefining section containing at least one hydrotreatment catalyst in order to lower the organic nitrogen content to below 20 ppm by weight, the hydrorefining being carried out at a temperature between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, with a hydrogen/hydrocarbons ratio of between 200 Nm3/m3 and 2,000 Nm3/m3,then at least a part of the effluent, which is at least partly denitrified, is hydrocracked in a hydrocracking section containing at least one fixed-bed hydrocracking catalyst, between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, and a hydrogen/hydrocarbons ratio of between 300 Nm3/m3 and 3,000 Nm3/m3,then at least a part of the hydrocracked effluent is distilled by atmospheric distillation in order to obtain at least one gas oil cut, a naphtha cut and an atmospheric residue, said residue optionally being at least partly distilled under vacuum in order to obtain at least one vacuum distillate and a vacuum residue. 2. A process according to claim 1, wherein the switchable reactor, the catalyst of which has been regenerated and/or replaced, is reconnected so as to be in the last position, relative to the flow of the feedstock, in the series of the switchable reactors. 3. A process according to claim 1, wherein the process operates in accordance with one of the following alternatives: the hydrorefining and hydrocracking sections comprise switchable reactors;all the sections comprise switchable reactors and by-passable reactors or catalytic beds;the hydrodemetallation section comprises the switchable reactors and also at least one by-passable reactor or catalytic bed; the hydrorefining (HDR) and hydrocracking (HCK) sections consist of by-passable reactors or catalytic beds;the hydrodemetallation section comprises only the switchable reactors and the hydrorefining and hydrocracking sections comprise a single non-by-passable reactor or catalytic bed. 4. A process according to claim 1, wherein the hydrodemetallation section and/or the hydrorefining section operates with a sequence of 2 or more hydrodemetallation and/or respectively hydrorefining catalysts, and wherein the average diameter of said catalysts decreases in the direction of flow of the feedstock. 5. A process according to claim 1, wherein the hydrodemetallation section and/or the hydrorefining section operates with a sequence of 2 or more hydrodemetallation catalysts and/or hydrorefining catalysts, and wherein the activity of said catalysts increases in the direction of flow of the feedstock. 6. A process according to claim 1, wherein each of the switchable reactors of the hydrodemetallation section contains hydrodemetallation catalyst and hydrodenitrification catalyst. 7. A process according to claim 1, wherein, before being hydrocracked, the effluent is subjected to a separation of the gases. 8. A process according to claim 1, wherein the effluent entering on the hydrocracking catalyst has an organic nitrogen content of lower than 10 ppm by weight and an asphaltenes content of lower than 200 ppm by weight. 9. A process according to claim 1, wherein at least a part of the atmospheric residue and/or of the gas oil cut and/or of the vacuum distillate is recycled to the hydrodemetallation section and/or to the hydrocracking section and/or to the hydrorefining section. 10. A process according to claim 1, wherein at least a part of the vacuum residue is recycled to the hydrocracking section and/or to the hydrorefining section. 11. A process according to claim 1, wherein the recycled amount of atmospheric residue and/or gas oil and/or vacuum distillate represents by weight, relative to the fresh feedstock entering the section, about 1 to 60%. 12. A process according to claim 1, wherein the feedstock is demetallated, then hydrorefined and hydrocracked in a reactor or catalytic bed K and the effluent is at least partly distilled in an atmospheric distillation zone in which the atmospheric residue obtained is at least partly hydrocracked in a reactor or catalytic bed K′, which is different from the reactor or catalytic bed K, containing at least one hydrocracking catalyst, and the effluent obtained is at least partly distilled in the distillation zone. 13. A process according to claim 1, wherein the feedstock comprises a vacuum distillate and/or a deasphalted oil. 14. A process according to claim 1, wherein the feedstock comprises a vacuum distillate (VGO) and/or a deasphalted oil (DAO) mixed with effluents obtained from conversion units. 15. A process according to claim 1, wherein there is injected, at the input of at least one of the catalytic beds of the process, reactor or catalytic bed in operation, at least one gas oil having an initial boiling point of between 140° C. and 260° C. and having a final boiling point of between 300° C. and 440° C. or a heavy cycle oil HCO having an initial boiling point of between 300° C. and 450° C. and having a final boiling point of between 400° C. and 600° C. 16. A process according to claim 11, wherein said recycled amount constitutes 10 to 20%. 17. A process according to claim 15, wherein the said at least one gas oil is injected into the input of the first reactor or catalytic bed in operation. 18. A process for hydrocracking of hydrocarbon feedstocks containing 200 ppm to 2% by weight of asphaltenes, and/or more than 10 ppm by weight of metals, wherein said feedstock is subjected to a hydrodemetallation treatment between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, with a hydrogen/hydrocarbons ratio of between 200 Nm3/m3 and 2,000 Nm3/m3, said treatment being carried out in at least 2 switchable reactors each containing at least one hydrodemetallation catalyst and optionally containing a hydrodenitrification catalyst, said reactors being arranged in series in order to be used in a cyclic manner comprising successively repeating steps b) and c) defined hereinafter: a) a step in which the reactors are used all together for a duration at most equal to the time for deactivating and/or clogging one of them,b) a step during which at least one of the reactors is by-passed and the catalyst which it contains is regenerated and/or replaced by fresh or regenerated catalyst,c) a step during which the reactors are used all together, the switchable reactor(s), the catalyst of which has been regenerated and/or replaced over the course of the preceding step, being reconnected either in the initial position or in another position among the switchable reactors, and said step being conducted over a duration at most equal to the time for deactivating and/or clogging one of the switchable reactors,then at least a part of the effluent, which is at least partly demetallated and optionally partly denitrified, is hydrorefined in a hydrorefining section containing at least one hydrotreatment catalyst in order to lower the organic nitrogen content to below 20 ppm by weight, the hydrorefining being carried out at a temperature between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, with a hydrogen/hydrocarbons ratio of between 200 Nm3/m3 and 2,000 Nm3/m3,then at least a part of the effluent, which is at least partly denitrified, is hydrocracked in a hydrocracking section containing at least one fixed-bed hydrocracking catalyst, between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, and a hydrogen/hydrocarbons ratio of between 300 Nm3/m3 and 3,000 Nm3/m3,then at least a part of the hydrocracked effluent is distilled by atmospheric distillation in order to obtain at least one gas oil cut, a naphtha cut and an atmospheric residue, said residue optionally being at least partly distilled under vacuum in order to obtain at least one vacuum distillate and a vacuum residue, wherein the hydrodemetallation and hydrorefining treatments operate with a catalytic system comprising at least two catalysts, one for hydrodemetallation and the other for hydrorefining,said catalysts comprise at least one support comprising a porous refractory oxide, at least one group VIB metal, and at least two group VIII metals, of which one is the majority promoter called VIII-1 and the other or others are called co-promoter VIII-i wherein i is between 2 and 5 and, in these catalysts, the group VIII elements are present in the proportions defined by the atomic ratio [VIII-1/(VIII-1+. . . +VIII-i)] of between 0.5 and 0.85 and at least one hydrodemetallation catalyst and at least one hydrorefining catalyst have an identical atomic ratio;the hydrodemetallation catalyst(s) has/have a group VIB metal or metals content of between 2 and 9% by weight of trioxide of the group VIB metal or metals relative to the total mass of the catalyst, and the sum of the group VIII metals contents is between 0.3 and 2% by weight of the oxide of the group VIII metals relative to the total mass of the catalyst,the hydrorefining catalyst(s) has/have a group VIB metal or metals content which is strictly higher than 9 and lower than 17% by weight of trioxide of the group VIB metal or metals relative to the total mass of the catalyst, and the sum of the group VIII metals contents is strictly higher than 2 and lower than 5% by weight of the oxide of the group VIII metals relative to the total mass of the catalyst. 19. A process according to claim 18, wherein said catalytic system is contained in the first switchable input reactor(s) of the hydrodemetallation (HDM) section and in the first input reactor(s) or the first input catalytic bed(s) of the hydrorefining (HDR) section. 20. A process according to claim 19, wherein the hydrorefining (HDR) section generally comprises a by-passable reactor or reactors or a by-passable catalytic bed or beds which are downstream of the reactor(s) or of the catalytic bed(s) containing said catalytic system, and which contain a catalyst or catalysts having metals contents higher than those of the catalytic system. 21. A process for hydrocracking of hydrocarbon feedstocks containing 200 ppm to 2% by weight of asphaltenes, and/or more than 10 ppm by weight of metals, wherein said feedstock is subjected to a hydrodemetallation treatment between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, with a hydrogen/hydrocarbons ratio of between 200 Nm3/m3 and 2,000 Nm3/m3, said treatment being carried out in at least 2 switchable reactors each containing at least one hydrodemetallation catalyst and optionally containing a hydrodenitrification catalyst, said reactors being arranged in series in order to be used in a cyclic manner comprising successively repeating steps b) and c) defined hereinafter: a) a step in which the reactors are used all together for a duration at most equal to the time for deactivating and/or clogging one of them,b) a step during which at least one of the reactors is by-passed and the catalyst which it contains is regenerated and/or replaced by fresh or regenerated catalyst,c) a step during which the reactors are used all together, the switchable reactor(s), the catalyst of which has been regenerated and/or replaced over the course of the preceding step, being reconnected either in the initial position or in another position among the switchable reactors, and said step being conducted over a duration at most equal to the time for deactivating and/or clogging one of the switchable reactors,then at least a part of the effluent, which is at least partly demetallated and optionally partly denitrified, is hydrorefined in a hydrorefining section containing at least one hydrotreatment catalyst in order to lower the organic nitrogen content to below 20 ppm by weight, the hydrorefining being carried out at a temperature between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, with a hydrogen/hydrocarbons ratio of between 200 Nm3/m3 and 2,000 Nm3/m3,then at least a part of the effluent, which is at least partly denitrified, is hydrocracked in a hydrocracking section containing at least one fixed-bed hydrocracking catalyst, between 300° C. and 450° C., under a total pressure of from 50 to 300 bar, and a hydrogen/hydrocarbons ratio of between 300 Nm3/m3 and 3,000 Nm3/m3,then at least a part of the hydrocracked effluent is distilled by atmospheric distillation in order to obtain at least one gas oil cut, a naphtha cut and an atmospheric residue, said residue optionally being at least partly distilled under vacuum in order to obtain at least one vacuum distillate and a vacuum residue, wherein the fixed-bed hydrocracking catalyst is a supported catalyst. 22. A process according to claim 1, wherein at least one of the switchable reactors contains a hydrodenitrofication catalyst. 23. A process according to claim 1, conducted substantially continuously in a series of connected reactors.
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이 특허에 인용된 특허 (7)
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Billon Alain,FRX ; Morel Frederic,FRX ; Kressmann Stephane,FRX ; Kim Sun Dong,KRX ; Ha Sung Ki,KRX ; Heor Haen,KRX, Process for hydrotreatment of a heavy hydrocarbon fraction using permutable reactors and introduction of a middle distillate.
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