Regenerator for regenerating catalysts under different operating conditions
09708552 ยท 2017-07-18
Assignee
Inventors
Cpc classification
B01J38/16
PERFORMING OPERATIONS; TRANSPORTING
B01J38/22
PERFORMING OPERATIONS; TRANSPORTING
B01J8/125
PERFORMING OPERATIONS; TRANSPORTING
B01J8/0015
PERFORMING OPERATIONS; TRANSPORTING
B01J38/44
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J38/44
PERFORMING OPERATIONS; TRANSPORTING
B01J8/00
PERFORMING OPERATIONS; TRANSPORTING
B01J8/12
PERFORMING OPERATIONS; TRANSPORTING
B01J38/16
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention concerns a moving bed catalyst regenerator (1) comprising a vessel (2) extending in a vertical direction, said vessel being divided into at least two regeneration zones extending along the vertical height of said vessel, in which particles of catalyst move under gravity, in which each regeneration zone comprises, in succession and in the order in which the catalysts move: a) a combustion section (CO); b) an oxychlorination section (O) disposed below the combustion section and comprising means for bringing catalyst from the combustion section (CO) to the oxychlorination section (O); c) a calcining section (CA) disposed below the oxychlorination section; characterized in that the regeneration zones are separated from each other by a separation means which is impermeable to catalysts and to gases in a manner such that the catalysts of each of the zones are capable of being regenerated under different operating conditions.
Claims
1. A moving bed catalyst regenerator (1) comprising a vessel (2) extending in a vertical direction, said vessel being divided into at least two regeneration zones extending along the vertical height of said vessel, in which particles of catalyst move under gravity, in which each regeneration zone comprises, in succession and in the order in which the catalysts move: a) a combustion section (CO); b) an oxychlorination section (O) disposed below the combustion section and comprising means for bringing catalyst from the combustion section (CO) to the oxychlorination section (O); c) a calcining section (CA) disposed below the oxychlorination section; characterized in that the regeneration zones are separated from each other by a separation means which is impermeable to catalysts and to gases in a manner such that the catalysts of each of the zones are capable of being regenerated under different operating conditions.
2. The regenerator according to claim 1, in which each of the combustion sections comprises an annular space defined by two sieves which are permeable to gas and impermeable to catalysts in which the catalyst moves under gravity.
3. The regenerator according to claim 2, in which the sieves are selected from a screen and a perforated plate.
4. The regenerator according to claim 1, in which each of the combustion sections is formed by a portion of an annular space (30), the annular space (30) being defined by two sieves (9, 9) which are permeable to gas and impermeable to catalysts and divided into portions by separation means (34) which are impermeable to catalysts and to gas.
5. The regenerator according to claim 1, in which each oxychlorination section is obtained by partitioning a zone of the vessel (2) into compartments (22, 22) by a separation means (23) which is impermeable to catalysts and to gas.
6. The regenerator according to claim 1, in which each calcining section is obtained by partitioning a zone of the vessel (2) into compartments (26, 26) by a separation means (27) which is impermeable to catalysts and to gas.
7. The regenerator according to claim 1, in which the oxychlorination section is separated from the calcining section by a mixing section which is configured to carry out mixing of oxychlorination gas with calcining gas.
8. A continuous catalytic reforming unit (40) comprising: at least a first reaction zone (41) and at least a second reaction zone (42), the first and second reaction zones respectively containing at least a first moving bed of catalyst and at least a second moving bed of catalyst; a regenerator (1) according to claim 1, which is capable of simultaneously and separately regenerating the catalysts of the first and second reaction zones (41, 42) under different operating conditions.
9. The catalytic reforming unit (40) according to claim 8, in which the first and second reaction zones (41, 42) are disposed in a vertical stack in a reactor.
10. The catalytic reforming unit (40) according to claim 8, in which the first and second reaction zones (41, 42) are respectively disposed in at least a first reactor and at least a second reactor which are arranged side by side.
11. The catalytic reforming unit (40) according to claim 8, in which the composition of the catalyst of the first reaction zone (41) is different from that of the catalyst of the second reaction zone (42).
12. A process for catalytic reforming of a hydrocarbon feed, comprising the following steps: a) treating the hydrocarbon feed in the presence of hydrogen in at least a first reaction zone (41) comprising at least one moving bed of a first catalyst; b) continuously and separately withdrawing an effluent and the first catalyst from the first reaction zone (41); c) treating the effluent obtained from the first reaction zone (41) in the presence of hydrogen in at least a second reaction zone (42) comprising at least one moving bed of a second catalyst; d) continuously and separately withdrawing a reformate and the second catalyst from the second reaction zone (42); e) sending the first and second catalysts from the first and second reaction zones to a regenerator (1) according to claim 1 and regenerating said first and second catalysts under different operating conditions; f) separately sending the regenerated catalysts to the respective first and second reaction zones (41, 42).
13. The process according to claim 12, in which the composition of the catalyst for the first reaction zone (41) differs from that of the catalyst for the second reaction zone (42).
14. The process according to claim 12, in which the flows of the feed, the effluents and the catalysts are as co-currents in a downward direction.
15. The process according to claim 12, in which the first and second reaction zones (41, 42) are disposed in a vertical configuration in a reactor with the first reaction zone (41) being located above the second reaction zone (42).
16. The process according to claim 12, in which the first and second reaction zones (41, 42) are disposed side by side respectively in at least a first reactor and at least a second reactor.
17. A moving bed catalyst regenerator (1) comprising a vessel (2) extending in a vertical direction, said vessel being divided into at least two regeneration zones extending along the vertical height of said vessel, in which particles of catalyst move under gravity, in which each regeneration zone comprises, in succession and in the order in which the catalysts move: a) a combustion section (CO); b) an oxychlorination section (O) disposed below the combustion section and comprising a conduit for bringing catalyst from the combustion section (CO) to the oxychlorination section (O); c) a calcining section (CA) disposed below the oxychlorination section; characterized in that the regeneration zones are separated from each other in a manner such that the catalysts of each of the zones are capable of being regenerated under different operating conditions.
18. The regenerator according to claim 17, in which each of the combustion sections is formed by a portion of an annular space (30), the annular space (30) being defined by two sieves (9, 9) which are permeable to gas and impermeable to catalysts and divided into portions by one or more separation plates (34) which are impermeable to catalysts and to gas.
19. The regenerator according to claim 17, in which each oxychlorination section is obtained by partitioning a zone of the vessel (2) into compartments (22, 22) by a plate (23) which is impermeable to catalysts and to gas.
20. The regenerator according to claim 17, in which each calcining section is obtained by partitioning a zone of the vessel (2) into compartments (26, 26) by a plate (27) which is impermeable to catalysts and to gas.
Description
DETAILED DESCRIPTION OF THE INVENTION
(1) Other characteristics and advantages of the invention will become apparent from the following description made with reference to the drawings, in which:
(2)
(3)
(4)
(5)
(6)
(7)
(8) In
(9) The catalysts respectively introduced into the reactor 1 via the conduits 3 and 3 arrive in the reservoirs 4 and 4 which can supply the combustion sections CO of the regenerator with catalysts. The reservoirs 4 and 4 are separated from each other by a separation means 6 which is impermeable to catalysts and to gas, for example a metal plate.
(10) In the example of
(11) Referring to
(12) As can be seen in
(13) Alternatively, and as indicated in
(14) In accordance with another embodiment shown in
(15) As indicated in
(16)
(17) Referring now to
(18) In accordance with another embodiment, the combustion section CO may be arranged in a manner such that the combustion gas moves from the inside to the outside through the zones (or compartments) 8, 8, 14 and 14. Alternatively, the combustion sections CO may be arranged in a manner such that the gas flow is injected at the bottom of said sections and is evacuated from the head of said sections.
(19) Given that the combustion zones are isolated from each other by a separation means which is impermeable to gas, different operating conditions may be applied in order to carry out the combustion of the coke as a function of the quantity of coke deposited on the catalysts moving in the combustion zones.
(20) Referring to
(21) The oxychlorination sections O of the regeneration zones act to recharge the grains of catalyst with chlorine and to redisperse the active metal at its surface in order to improve the distribution of said metal in the grains of catalyst. In each oxychlorination section O, the catalysts flow in the respective zones (or compartments) 22 and 22 inside the reactor. The zones (or compartments) 22 and 22 are separated by a separation means 23 which is impermeable to catalysts and to gas, thereby forming two independent oxychlorination compartments in order to treat the catalysts separately and under different operating conditions (for example with different rates of flow of the catalyst or different flow rates of reactive gas or different temperatures, or even with different gas compositions). As can be seen in
(22) The catalysts arriving at the bottom of the oxychlorination compartments 22 and 22 continue to flow in the respective calcining sections CA which also comprise a calcining compartment 26, 26. The calcining compartments 26 and 26 are separated from each other by a separation means 27 which is impermeable to the catalysts and to the gas, such that the catalysts in each compartment can be treated under different operating conditions (different catalyst flow rates or different reactive gas flow rates or different temperatures, also with different gas compositions). The specific purpose of the calcining section CA is to dry the grains of catalyst. The calcining compartments 26 and 26 of the calcining section CA are provided with conduits 28 and 28 for injecting a calcining gas. The calcining gas is generally air, or air depleted in oxygen, and may be at a temperature in the range 400 C. to 550 C. The calcining gases which are introduced via the conduits 28 and 28 may have the same or a different composition.
(23) In order to distribute the calcining gas in a homogeneous manner in the bed of catalyst of the compartments 26 and 26, the conduits 28 and 28 may respectively open into a space 29 and 29 disposed at the periphery of the vessel 2. The spaces 29 and 29 are open at their lower portion located at the bottom of the compartments of the calcining section CA so that the gas injected via the conduits 28 and 28 is distributed in the beds of catalyst over the whole of the periphery from the bottom of the compartments 26 and 26. The injected calcining gas thus moves in an upwards direction, as a counter-current to the gravitational flow of the catalyst, through the compartments 26 and 26 then through the compartments 22 and 22, thereby mixing with the oxychlorination gas, and is evacuated from the vessel 2 via the conduit 25. Alternatively, the calcining gas may be evacuated directly from the calcining compartments 26 and 26 without encountering the oxychlorination section. Alternatively, the calcining gas leaving each of the zones may be re-mixed before being redistributed into each of the oxychlorination zones (or compartments) 22 and 22.
(24) It is also possible to provide a mixing section between the oxychlorination section and the calcining section. The mixing section comprises, for example, a distributor plate designed to homogeneously mix the calcining gas with the oxychlorination gas and to distribute the gas mixture in a homogeneous manner.
(25)
(26) Referring to
(27) The plate 61 is traversed by a plurality of tubes 62 which allow grains of catalyst to flow from the oxychlorination section O to the calcining section CA. The tubes 62 extend below the plate 61 over a height H. The number, position, section and/or height H of the tubes 62 are determined so as to ensure that the catalyst can flow between the oxychlorination section O and the calcining section CA. The mixing section 60 is also divided into two spaces or compartments 64 and 64 by a separation means 63, for example a plate 63, which is impermeable to gas and which extends over the height H of said mixing section 60. As indicated in
(28) The plate 61 associated with the tubes 62 and with the plate 63 can be used to define two mixing spaces 64 and 64. The mixing spaces 64 and 64 extend over the height H of the tubes 62. In fact, the plate 61 associated with the tubes 62 can be used to prevent catalyst from getting into the mixing spaces 64 and 64 below the plate 61 over the height H. The tubes 62 may be substantially vertical. As an example, the axes of the tubes 62 form an angle in the range 0 to 15 with respect to the vertical direction. The conduits 24 and 24 pass through the vessel 2 and open into the compartments 64 and 64 of the mixing section 60 in order to introduce the oxychlorination gas into said compartments 64 and 64. The lower portion of the compartments 64 and 64 allow gas to pass through. As an example, the lower portion is open. Thus, the calcining gas moving in an upwardly vertical direction in the compartments 26 and 26 of the calcining section CA moves into the mixing section 60 so as to mix the calcining gas with the oxychlorination gas in the mixing section 60 which is free of grains of catalyst, which means that good mixing of the gases is obtained. In addition, the conduits 24 and 24 can be used to constitute a side inlet for gas into the mixing section 60, i.e. the conduits 24 and 24 may be horizontal and pass through the vessel 2. The fact of injecting the oxychlorination gas laterally via the horizontal conduits 24 and 24 further improves mixing with the calcining gas moving as a cross-current with respect to the oxychlorination gas injected horizontally via the conduits 24 and 24. Alternatively, a plate 66 may be provided which is permeable to gas over the lower surface of the mixing section 60. The plate 66, for example a screen or a perforated plate, allows the calcining gas to pass from the calcining section into the mixing section 60. In this particular case, the tubes 62 pass through the plate 66 to create a passage for grains of catalyst communicating between the oxychlorination sections O and the calcining sections CA. The perforated screen or plate can be used to introduce calcining gas at high speed without causing particles of solid to move from the bed of catalyst in the calcining section into the mixing section. In addition, the plate 66 may reinforce the mechanical strength of the plate 61 by fixing the tubes 62 on the one hand to the plate 66 and on the other hand to the plate 61.
(29) As can be seen in
(30) Alternatively, it is possible to use a mixing box type solution from document FR 2 993 794.
(31) In the context of the invention, the regenerator may clearly comprise more than two regeneration zones so that a catalyst can be separately regenerated in each of said zones under different operating conditions selected as a function of the degree of deactivation of the catalyst, and in particular as a function of the degree of coking.
(32) Still within the context of the invention, the catalysts which are respectively regenerated in each regeneration zone may be of a different composition in terms of the nature of the support and of the active metallic phase.
(33) A catalytic reforming process using a regenerator of the invention is described below with reference to
(34) The reforming unit 40 comprises at least a first and a second reaction section 41 and 42. In
(35) Similarly, the second reaction section 42 comprises two moving bed reforming reactors 44 and 44, means (not shown in
(36) In accordance with the invention, the first reaction section 41 may be used to employ a specific catalyst with a different composition from that of the catalyst used in the second reaction section 42.
(37) Each of the reaction sections 41 and 42 also comprises means 49 and 51 for transferring the catalyst collected at the outlet from the last reactor of each of the reaction sections to a regenerator 1 in accordance with the invention which is capable of regenerating the catalysts used in the reaction sections at the same time and separately.
(38) In the first reaction section 41, the reaction of dehydrogenation of naphthenic compounds to aromatic compounds principally takes place, while in the second reaction section, the principal reactions of dehydrocyclisation of n-paraffins to aromatics, hydrocracking of paraffins and naphthenic compounds to form saturated short chain (C3, C4) hydrocarbons and coke formation (the principal factor in catalyst deactivation) take place. It will thus be clearly understood that the catalysts which are extracted from the first reaction zone 41 will have a lower degree of deactivation than those from the second reaction zone 42. As a consequence, it is advantageous to use less severe regeneration operating conditions in order to restore the activity of the catalysts in the first reaction zone 41 than for the catalysts obtained from the second reaction zone 42.
(39) As indicated in
(40) The second effluent obtained from the second reactor 43 of the first reaction section 41 is sent to the head of the first reactor 44 of the second reaction section 42 in which it is brought into contact with catalyst contained in a moving bed flowing under gravity in order to produce a third effluent. The third effluent withdrawn from the bottom of reactor 44 is sent to the head of the second reactor 44 of the second reaction section 42 via the transfer means (not indicated in
(41) In an alternative embodiment, the process of the invention uses, in each reaction section, a reactor in which the moving catalytic beds are stacked vertically.
(42) In another alternative embodiment, it is also possible to dispose the first and second reaction zones in a vertical configuration in a reactor with the first reaction zone 41 which is located above the second reaction zone 42.
(43) Preferably, the moving bed or beds of the reaction zones are of the radial moving bed type in which the hydrocarbon feed moves through the catalytic bed in a radial flow path from the outer periphery of the bed towards the centre of the reactor which comprises a central effluent collector.
(44) By way of example, the reaction sections are operated under the following operating conditions: a mean inlet temperature in the reaction section in the range 470 C. to 570 C.; a pressure in the range 0.3 to 1.5 MPa; a (mass flow rate of feed/quantity by weight of catalyst) ratio in the range 1 to 10 h.sup.1; a H.sub.2/hydrocarbons molar ratio in the range 0.8 to 8.
(45) In the context of the invention, the process may comprise more than two reaction sections which each operate with catalysts with identical compositions or different compositions. As an example, the process may employ three or four reaction sections in series.
(46) The process exemplified in
(47) The hydrocarbon feed is generally a hydrocarbon cut of the naphtha type, rich in paraffinic and naphthenic compounds and relatively low in aromatic hydrocarbon compounds. The feed preferably has a distillation range in the range 50 C. to 250 C. A naphtha feed which may be treated by the process is, for example, obtained from atmospheric distillation of crude oil or a natural gas condensate. The process of the invention is also applicable to heavy naphthas produced by a catalytic cracking (FCC), cokefaction or hydrocracking unit, or indeed to steam cracked gasoline.
(48) Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
(49) The entire disclosures of all applications, patents and publications, cited herein and of corresponding application No. FR 1458504, filed Sep. 10, 2014 are incorporated by reference herein.
(50) From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.