PROCESS FOR CONVERTING MIXED HYDROCARBON STREAMS TO LPG AND BTX

Abstract

The present invention relates to a process for converting a feed comprising C5-C12 hydrocarbons to higher BTX, LPG and methane in the presence of hydrogen in n reaction zones operated in series, wherein m reaction zones are not participating in the conversion process and only (nm) reaction zones are operated under reaction conditions sufficient to convert at least a portion of said a feed comprising C5-C12 hydrocarbons to an effluent having said BTX. An object of the present invention is to provide a process for converting C5-C12 hydrocarbons to LPG, optionally BTX, and methane in the presence of hydrogen wherein coke formation on the catalyst is controlled and the physical movement of particulate catalyst is avoided.

Claims

1. A process for converting a mixed C5-C12 hydrocarbons stream to BTX, LPG and methane in the presence of hydrogen in n reaction zones operated in series, wherein m reaction zones are not participating in the conversion process and only (nm) reaction zones are operated under reaction conditions sufficient to convert at least a portion of said C5-C12 hydrocarbon stream to an effluent having said BTX, wherein each reaction zone is initially numbered serially with a designator from 1 to n, the process comprising: (a) providing a quantity of catalytic material within each reaction zone; (b) providing to the reaction zone designated as 1 a hydrocarbon feedstock containing C5-C12 hydrocarbons and hydrogen; (c) cooling at least a portion of the effluent of the said reaction zone designated as 1 to the inlet temperature of the reaction zone designated as 2, and more generally, cooling at least a portion of the effluent of each reaction zone with a designator equal or smaller than (nm1) to the inlet temperature of the reaction zone with a designator larger by one than that of the reaction zone from which said effluent originates; (d) transferring said at least portion of said effluent of the said reaction zone designated as 1 to said reaction zone designated as 2, and more generally, transferring said at least portion of said reaction zone with a designator equal or smaller than (nm1) to the reaction zone with a designator larger by one than that of the reaction zone from which said at least portion of said effluent originates; (e) maintaining said reaction zone designated as 2 at an average temperature higher than or equal as in reaction zone designated as 1, and more generally, maintaining each reaction zone with a designator equal or smaller than (nm) at an average temperature higher or equal as in the reaction zone with designator smaller by one than that of said reaction zone, feeding the effluent from the reaction zone with the designator (nm) to another process unit, and regenerating the reaction zones with a designator larger than (nm), followed by (f) terminating transferring effluent from the reaction zone with the designator (nm1) to the reaction zone with the designator (nm); (g) starting regenerating said reaction zone with the designator (nm) containing deactivated catalytic material; (h) raising the inlet temperature of each reaction zone with a designator equal or smaller than (nm1) to the former inlet temperature of the reaction zones with a designator larger by one than that of said reaction zone, respectively; (i) changing the value of each designator equal or smaller than (n1) to a number larger by one than its initial value, and changing the value of the designator with a value of n to 1, (j) repeating steps (b) to (i).

2. A process for converting a mixed C5-C12 hydrocarbons stream to BTX, LPG and methane in presence of hydrogen in n reaction zones operated in series, wherein m reaction zones are not participating in the conversion process and only (nm) reaction zones are operated under reaction conditions sufficient to convert at least a portion of said C5-C12 hydrocarbon stream to an effluent having said BTX, wherein each reaction zone is initially numbered serially with a designator from 1 to n, the process comprising: (a) providing a quantity of catalytic material within each reaction zone; (b) providing to the reaction zone designated as 1 a hydrocarbon feedstock containing C5-C12 hydrocarbons and hydrogen; (c) cooling at least a portion of the effluent of the said reaction zone designated as 1 to the inlet temperature of the reaction zone designated as 2, and more generally, cooling at least a portion of the effluent of each reaction zone with a designator equal or smaller than (nm1) to the inlet temperature of the reaction zone with a designator larger by one than that of the reaction zone from which said effluent originates; (d) transferring said at least portion of said effluent of the said reaction zone designated as 1 to said reaction zone designated as 2, and more generally, transferring said at least portion of said reaction zone with a designator equal or smaller than (nm1) to the reaction zone with a designator larger by one than that of the reaction zone from which said at least portion of said effluent originates; (e) maintaining said reaction zone designated as 2 at an average temperature higher than or equal as in reaction zone designated as 1, and more generally, maintaining each reaction zone with a designator equal or smaller than (nm) at an average temperature higher or equal as in the reaction zone with designator smaller by one than that of said reaction zone, feeding the effluent from the reaction zone with the designator (nm) to another process unit, and regenerating the reaction zones with a designator larger than (nm), followed by (f) terminating transferring effluent from the reaction zone designated as 1 to the reaction zone designated as 2; (g) starting regenerating the reaction zone designated as 1 containing deactivated catalytic material; (h) decreasing the inlet temperature of each reaction zone with a designator larger than 1 and equal or smaller than (nm) to the former inlet temperature of the reaction zones with a designator smaller by one than that of said reaction zone, respectively; (i) changing the value of each designator equal and larger than 2 to a number smaller by one than its initial value, and changing the value of the designator with value 1 to n, (j) repeating steps (b) to (i).

3. The process according to claim 1, wherein said reaction zones are adiabatic catalytic fixed bed reaction zones.

4. The process according to claim 3, wherein said adiabatic catalytic fixed bed reaction zones are adiabatic radial flow fixed bed reactors.

5. The process according to claim 1, wherein said catalytic material comprises one or more transition metals or metal sulfides and a solid catalyst support.

6. The process according to claim 1, wherein said total number of reaction zones, n, is at least 4, wherein said total number of reaction zones not participating in the conversion process is at most 4.

7. The process according to any one or more of claim 1, wherein step (f) further comprises monitoring the temperature rise along said bed of catalytic material and terminating transferring effluent when said temperature rise comes below a threshold value.

8. The process according to any one or more of claim 1, wherein the inlet temperature of each reaction zone not in regeneration is continuously adjusted in small steps such that the temperature rise along the catalyst bed in said reaction zone deviates not more than 10% from a constant value.

9. The process according to any one of the claim 1, wherein in said step (g) of regenerating a regeneration gas is chosen from the group of steam, air, oxygen and hydrogen, or suitable mixtures thereof.

10. The process according to claim 9, wherein said regeneration gas comprises at least two different components, said different components are dosed together.

11. The process according to claim 9, wherein said regeneration gas comprises at least two different components, said different components are dosed in a sequence.

12. The process according to claim 1, wherein the exothermic heat originating from regenerating said bed of catalytic material is used for preheating of fresh feed to the first reactor on stream.

13. The process according to claim 1, wherein the mixed C5-C12 hydrocarbons is selected from the group consisting of pyrolysis gasoline, straight run naphtha, hydrocracked gasoline, light coker naphtha, coke oven light oil, FCC gasoline and reformate or a mixture thereof.

14. The process according to claim 2, wherein said reaction zones are adiabatic catalytic fixed bed reaction zones.

15. The process according to claim 2, wherein said catalytic material comprises one or more transition metals or metal sulfides and a solid catalyst support.

16. The process according to claim 2, wherein said total number of reaction zones, n, is at least 4, wherein said total number of reaction zones not participating in the conversion process is at most 4.

17. The process according to claim 2, wherein step (f) further comprises monitoring the temperature rise along said bed of catalytic material and terminating transferring effluent when said temperature rise comes below a threshold value.

18. The process according to claim 2, wherein the inlet temperature of each reaction zone not in regeneration is continuously adjusted in small steps such that the temperature rise along the catalyst bed in said reaction zone deviates not more than 10% from a constant value.

19. The process according to claim 2, wherein in said step (g) of regenerating a regeneration gas is chosen from the group of steam, air, oxygen and hydrogen, or suitable mixtures thereof.

20. The process according to claim 19, wherein said regeneration gas comprises at least two different components, said different components are dosed together.

Description

[0058] FIG. 1a shows an embodiment of a process for converting C5-C12 hydrocarbons to BTX, LPG and methane.

[0059] FIG. 1b shows another phase of the same process for converting C5-C12 hydrocarbons to BTX, LPG and methane.

[0060] FIG. 1c shows another phase of the same process for converting C5-C12 hydrocarbons to BTX, LPG and methane with simulated cocurrent flow of reactants, products and catalyst.

[0061] FIG. 1d shows another phase of the same process for converting C5-C12 hydrocarbons to BTX, LPG and methane with simulated cocurrent flow of reactants, products and catalyst.

[0062] FIG. 1e shows another phase of the process for converting C5-C12 hydrocarbons to BTX, LPG and methane with simulated countercurrent flow of reactants, products and catalyst.

[0063] FIG. 1f shows another phase of the process for converting C5-C12 hydrocarbons to BTX, LPG and methane with simulated countercurrent flow of reactants, products and catalyst.

[0064] No valves are shown in FIGS. 1a-1f for better readability. Pipelines with fluid flow are marked by bold line and pipelines without fluid flow are marked by thin lines.

[0065] FIG. 2a illustrates the temperature profile during the first two cycles with simulated cocurrent flow of reactants, products and catalyst shown in FIGS. 1a-1d.

[0066] FIG. 2b illustrates the temperature profile during the first two cycles with simulated countercurrent flow of reactants, products and catalyst shown in FIGS. 1a-b, and 1e-1f.

[0067] Mixed C5-C12 hydrocarbon feedstock and hydrogen are fed to the first of a series of n adiabatic catalytic fixed bed reactors. The feed is brought to a preset temperature in a preheater and sent to the first reactor. Each reactor contains particulate catalyst, e.g. a catalyst comprising one or more transition metals or metal sulfides and a solid catalyst support. m reactors are being regenerated in order to remove coke from the catalyst while nm reactors are on stream, which means convert C5-C12 hydrocarbons into BTX, LPG and methane.

[0068] The mixture of hydrogen, reactant and nascent products passes through the first adiabatic reactor where it heats up due to the exothermic nature of the reaction.

[0069] Hence, an increasing temperature profile along the flow direction is established inside the catalytic fixed bed of the first reactor. After leaving the first reactor, the effluent is cooled down again and enters the second reactor. More C5-C12 hydrocarbons are converted into BTX, LPG and methane in the second reactor where the reactant/product mixture heats up and a rising temperature profile is again established. The outlet temperature of the second reactor is higher than the outlet temperature of the first reactor. The sequence of cooling the hydrogen/reactant/product mixture, the conversion of the cooled mixture inside each reactor accompanied by temperature increase, and the converted mixture leaving each reactor at a higher temperature than the outlet temperature of the previous reactor is repeated according to the total number (nm) of reactors on stream.

[0070] The detailed discussion of the FIGS. 1a-1f relates to the specific embodiment of the present invention in which the overall temperature profile increases.

EXAMPLE 1

[0071] A first example is given in FIG. 1a with n=4 reactors of which m=1 reactor is regenerated and which are operated to simulate a cocurrent flow pattern of reactant-feed mixture and solid catalyst. The effluent of the last (nm)th reactor on stream is quenched and fed to the product separation section of the process. As a result of the increasing profile of the inlet temperatures of each of the (nm) reactors on stream the catalytic fixed bed of the (nm)th reactor has the highest average temperature (FIG. 2a). This implies that the rate of coke formation, which is an undesired side reaction, is highest and therefore the catalyst deactivates most quickly in the (nm)th reactor.

[0072] When a preset minimum conversion is reached indicated by a minimum temperature rise along the catalytic bed of the (nm)th reactor as result of catalyst deactivation, the (nm)th reactor will be taken off stream and regenerated. The nth reactor was regenerated until now and is purged from regeneration gas, e.g. preheated diluted air (FIG. 1b). The catalytic bed of the (nm)th reactor is first cooled down by a purge gas, e.g. nitrogen (FIG. 1c), and then the catalyst is regenerated by converting coke with a regeneration gas. At the same time, all inlet temperature set points of the first to (nm1)th reactor are raised to the values of the second to (nm)th reactor before the (nm)th reactor was taken off stream for regeneration. Then the feed stream is not fed to the first reactor anymore but to the nth reactor (FIG. 1c). The inlet temperature set point of the nth reactor is now the same as for the first reactor before the (nm)th reactor was taken off stream for regeneration. According to FIG. 1d the effluent of the nth reactor is now routed to the first reactor (n=4 and m=1).

[0073] The (nm1)th reactor has the highest average temperature now (FIG. 2a) and will be the next one to be regenerated. Once the temperature rise inside the (nm1)th reaches a preset minimum value the same switching sequence is triggered like described above. After the new switching event, the feed will be routed to the (n2)th reactor, the average temperature level in the (nm2)th reactor will be the highest and the effluent of the (nm2)th reactor is fed to the product separation section (n=4 and m=1).

[0074] The process as discussed above has been disclosed in Table 1 and FIG. 2a.

TABLE-US-00001 TABLE 1 Schematic overview of status of reaction zones in the process according to the invention (example 1, cocurrent flow of hydrogen reactant, products and catalyst) Reaction zone (number) 1 2 3 4 Cycle 1 R R R X 2 R R X R 3 R X R R 4 X R R R 5 R X X X

[0075] From Table 1 one can deduce that in the first cycle only reaction zones 1-3 are participating in the conversion process whereas reaction zone 4 is not participating in the conversion process. The sequence in the first cycle is thus 1-2-3 (on stream) and 4 (off stream). In the second cycle reaction zone 4 is taken on stream and the first reaction zone will now be reaction zone 4. The effluent from reaction zone 4 is fed to the inlet of first reaction zone, now being reaction zone 1. The sequence in the second cycle is thus 4-1-2 (on stream) and 3 (off stream), wherein the highest temperature is in reaction zone 2. The sequence in the third cycle is thus 3-4-1 (on stream) and 2 (off stream), wherein the highest temperature is in reaction zone 1. This table 1 shows a number of five cycles wherein the situation of cycle 1 is similar to cycle 5. As mentioned before, the present invention is not restricted to any specific number of reaction zones.

[0076] In the FIGS. 1a-1g the reference numbers used refer to the following: [0077] 1 Intercooler 1 to n (4) [0078] 2 Reaction zone 1 to n (4) [0079] 3 Hydrogen and C5-C12 hydrocarbon feed [0080] 4 Product mixture [0081] 5 Oxygen-containing regeneration gas feed [0082] 6 Regeneration gas effluent [0083] 7 Purge gas feed [0084] 8 Purge gas effluent

EXAMPLE 2

[0085] A second example is given in FIGS. 1a-1b and-1e-1f with n=4 reactors of which m=1 reactor is regenerated with oxygen-containing gas, and which are operated to simulate a countercurrent flow pattern of reactant-feed mixture and solid catalyst.

[0086] The effluent of the last (third) reactor on stream is quenched and fed to the product separation section of the process. The catalyst in the first reactor has accumulated more coke and is more deactivated than that in the second and third reactor because it has been on stream for longer.

[0087] When a preset minimum conversion is reached indicated by a minimum temperature rise along the catalytic bed of the first reactor as result of catalyst deactivation, the first reactor will be taken off stream and regenerated. For this, the catalyst is regenerated by combusting coke with an oxygen-containing regeneration gas. At the same time, the inlet temperature set point of the second reactor is adjusted to the value of the first reactor before it was taken off stream for regeneration. The feed stream is not fed to the first reactor anymore but to the second reactor (FIG. 1f). The inlet temperature set point of the second reactor is now the same as for the first reactor before it was taken off stream for regeneration. According to FIG. 1f the effluent of the second reactor is now routed to the third reactor.

[0088] The catalyst bed of the second reactor has been on stream for the longest time now and will be the next one to be regenerated. Once the temperature drop inside the second reactor reaches a preset minimum value the same switching sequence is triggered like described above.

[0089] FIG. 1b shows how the fourth reactor is purged from oxygen-containing regeneration gas before it is coming on stream in FIG. 1e, and FIG. 1e shows how the first reactor taken off-stream is purged from hydrocarbons before taken into regeneration in FIG. 1f.

[0090] Table 2 gives an overview of a complete repetition of switching events (cycles #1 to 4),

TABLE-US-00002 TABLE 2 Schematic overview of status of reaction zones in the process according to the invention (example 1, countercurrent flow of reactant, products and catalyst) Reaction zone (number) 1 2 3 4 Cycle 1 R R R X 2 X R R R 3 R X R R 4 R R X R 5 R R R X