CA2374233A1 - Multi-stage reforming process using rhenium-containing catalyst in the final stage - Google Patents

Abstract

This is a process for upgrading a petroleum naphtha fraction. The naphtha is subjected to reforming and the reformate is cascaded to a benzene and toluen e synthesis zone over a benzene and toluene synthesis catalyst comprising a molecular sieve of low acid activity. The preferred molecular sieve is steam ed ZSM-5. The benzene and toluene synthesis zone is operated under conditions compatible with the conditions of the reformer such as temperatures of above about 800 ~F (427 ~C). In one aspect of the invention, the benzene and tolue ne synthesis catalyst includes a metal hydrogenation component from group VII(B ), specifically rhenium. In one mode of operation, the benzene and toluene synthesis catalyst replaces at least a portion of the catalyst in the reformer. The process produces a product containing an increased proportion of benzene, toluene, and/or xylenes, and a reduced portion of alkylated aromatics, as compared to reformate.

Description

Multi-Stage Reforming Process Using Rhenium-Containing Catalyst in the Final Stage Field of the Invention 1o This invention relates to a process for conversion of hydrocarbons.
More specifically, the invention relates to a process for upgrading a hydrocarbon feedstock by reforming followed by hydrodealkylation. A
multi-stage reforming process using a rhenium-containing catalyst in the final stage is disclosed. The final stage produces additional benzene, toluene and xylenes by dealkylating alkylated aromatics.
Background of the Invention The reformate upgrading process of this invention, and its 2o background, is more completely described in U.S. Pat. No. 5,865,986, which is incorporated by reference in this application. In the instant application, however, the catalyst of the final stage is loaded with rhenium rather than palladium or platinum, providing significant cost advantages.
Catalytic reforming of naphtha feedstocks is well known in the petroleum refining industry. Most naphtha feeds contain large quantities of naphthenes and paraffins and consequently they have low octane numbers. In catalytic reforming these components go through a variety of hydrocarbon conversions resulting in a gasoline product of improved octane number. Some of the more important conversion reactions 3o include dehydrogenation of naphthenes to aromatics and dehydrocyclization of normal paraffins to aromatics. Less desirable reactions which commonly occur include hydrocracking of paraffins and naphthenes to produce gaseous hydrocarbons such as methane and ethane. Because of these less desirable reactions, an important objective of catalytic reforming is to rearrange the structure of the hydrocarbon molecules to form higher octane products without any significant change in the carbon number distribution of the stock.

12-06-2001 ~ - - ~ US 00001368E
. CA 02374233 2001-11-16 The reforming reactions are, typically, catalyzed by catalysts comprising porous supports, such as alumina, that have dehydrogenation promoting metal components impregnated or admixed therewith. Platinurn on alumina and more recently bimetallics such as platinum and rhenium on alumina are examples of these catalysts. Such catalysts are described in U.S. Pat. Nos. 3,415,737 and 3,953,3$8.
U.S. Pat. No. 5,744,674 discloses the preparation of benzene, toluene and xylene from C9* heavy aromatics using ZSM-5 loaded with rhenium, tin and platinum or palladium. This reference is not concerned with naphtha upgrading, however. There is no teaching of a mufti-stage reforming p rocess.
U.S. Pat. No. 4,877,514 discloses the preparation of catalyst suitable for use in fluid catalytic cracking or reduced crude conversion hydrocarbon conversion operations. These catalysts may comprise zeolites and may further incorporate rhenium oxide.
U.S. Pat, No. 4,855,03fi discloses a process for fluid catalytic cracking which employs a catalyst comprising a large pore zeolite. The zeolite is prepared by contact with a fluoroanion. U.S. Pat. Nos. 4,642,408;
4,654,x57; and 4,499,321 disclose dealkyiation of 1,4 dialkylbenzene with use of a zeolite catalyst such as ZSM-5. This catalyst may be nlodifred with a Group Vllb element such as rhenium.
U.S. Pat. No. 4,467,129 discloses catalytic dealkylation of ethylbenzene, where the ethylbenzene is mixed with xyiene. The catalyst comprises mordenite and a zeolite such as ZSM-5. Rhenium may be added for hydrogenation purposes. .
None of these patents discloses the concept of increasing ttte yield of benzene,~toluene and xylene products from a mufti-stage naphtha reforming process by use of a molecular sieve loaded with a Group ViIB metal in the last bed, as in the instant invention.
'AMENDED SHEET ~~°'~~~~~~°~"~o'°'ph).aoc Emufiangsteit l2.Juni 21:0 12-06-2001 l~-'"' "- ~ .. .. US 00001368E

It is known that pollution can be reduced by lowering gasoline endpoint, resulting in a product endpoint where, in a standard ASTM
distillation, 90 volume percent of the gasoline distills below about 27a°F
(132°G) to 350°F (177°C) (T90). Based on this, there have been regulatory proposals, particularly in the State of California, to require gasoline to meet a maximum T90 specification of 300°F (149°G). Meeting this T90 permits only 10% of the hydrocarbons in gasoline to boil above 300°F
(149°C). A
signifcant boiling range conversion of heavy naphthas will be required to meet this goal.
Brief Description of the Invention A process has been discovered for producing benzene; toluene and xylenes while enhancing the octane value of the gasoline boiling range materials of a naphtha fraction of low octane value and high gasoline end boiling range.
The process of this invention can increase the benzene production of a reformer by more than 10% while producing fewer G9* hydrocarbons, through hydrodealkylation reactions.
The invention is directed to a multistage integrated process for upgrading a petroleum naphtha comprising the steps of:
(a) introducing the naphtha to a catalytic reforming stage comprising a plurality of operatively connected catalyst zones including a first catalyst zone and a last catalyst zone, the last catalyst zone being maintained under reforming conditions of temperature ranging from at least 800°F (427°C) to 1050°F
(565°C) and pressure of 50 psig (44fi kPa) to 500 psig (3,549 kPa) to provide an intermediate product comprising aromatics and paraffins;
(b) transferring at least a portion of the intermediate product of the last catalyst zone to a benzene and toluene synthesis zone comprising at least one benzene and toluene synthesis catalyst operatively connected to the last catalyst zone of the reforming stage of step (a), the benzene and toluene synthesis zone being maintained under Empfa~gsteit l2,Ju~i 21:07 AMENDED SHEET

12-06-2001 ~ -°' - US 00001368E

conditions of hydrogen-to-hydrocarbon mole ratio and pressure compatible with the fast catalyst zone of the reforming stage and temperature of greater than 8Q0°F (427°C), the benzene and toluene synthesis catalyst zone containing a catalyst, which comprises a hydrogenation component from Group VIIB and further comprises a molecular sieve of Ivw acid activity, as determined by an alpha value of less than 60, to provide a hydrocarbon product comprising more benzene, toluene, xylenes content than the intermediate product of the last catalyst zone of the reforming stage; wherein the intermediate product of step (a) that is fed to the benzene, toluene, and xylenes synthesis zone of step (by has not been subjected to intermediate separation.
The hydrogenation component of Group VIIB in step (b) is preferably rhenium.
The catalytic reforming zone and the benzene and toluene synthesis zone are in series flaw arrangement, preferably without intermediate separation of the reformer effluent so that the two zones are operated undeF
compatible conditions including hydrogen circulation rate and pressure.
In one embodiment of the invention, a low acidity molecular sieve can be provided by using a deactivated catalyst from another refinery process.
in this respect, the other refinery process provides the catalyst treatment conditions needed to reduce catalyst acidity.
Prior to the contacting with the reformate, the deactivated catalyst cart be regenerated by conventional techniques such as by burning in an oxygen-containing gas to remove at feast a major part of the accumulated coke from the catalyst or by hydrogen regeneration.
Brief Description of the Drawings FIG. 1 is a simpl~ed scherrvatic flow diagram of the process of the invention_ EmDfaoBSteit l2.Juei 21:O;AMENDEDSHEET

5 FIG. 2 is a simplified schematic flow diagram of an alternative embodiment of the invention.
Detailed Description of the Invention o A more detailed discussion of reforming, reformate upgrading, and catalyst composition is provided in U.S. Pat. No. 5,865,986.
In the present invention a petroleum naphtha characterized by a boiling range of C5 to about 450°F (232°C), typically boiling up to about 400°F (204°C), is contacted with a reforming catalyst under reforming ~5 conditions selected to produce a reaction product comprising aromatics and paraffins. Typically, the hydrocarbon feed contains a percentage of components which boil above 300°F (149°C). The components boiling above 300°F (149°C) usually comprise at least 10% of the entire feed. In general, the feed can be further characterized by the presence of C9+
2o hydrocarbons which are usually present in an amount of less than about 40 wt. %, typically 25 wt. % to 40 wt. %, based on the entire weight of the feed. Yield advantages can be achieved by increasing the cut-point of the reformer feed to boost C9+ aromatics. Alternatively, a C9+ aromatic cofeed can be employed in which case the feed can contain over 40 wt.
25 % C9+ hydrocarbons, typically, up to 50 wt. % C9' hydrocarbons. Since Cs components are olefin precursors, yield loss is minimized by removing them from the feed. Thus, the feed can be substantially devoid of Cs hydrocarbons.
The reforming process can be continuous, cyclic or 3o serniregenerative. The process can be in a fixed bed, moving bed, tubular, radial flow or fluid bed. Typically, a hydrogen to hydrocarbon mole ratio of up to 8:1 is employed to maintain a reasonable catalyst cycle length.
The conditions of reforming typically include temperatures of at 35 least about 800°F (427°C) to about 1050°F
(565°C) and pressures from about 50 psig (446 kPa) to about 500 psig (3,549 kPa), more specifically from about 50 psig (446 kPa) up to and including 450 psig (3,204 kPa).
It may often be preferred to employ pressures in the lower ranges e.g.
50 psig (446 kPa) to about 125 psig (963 kPa) to encourage formation of aromatics which supply precursors for the preferred reactions of the o benzene and toluene synthesis zone and enhance yield of the preferred products. The hydrogen-to-hydrocarbon ratio ranges from about 0.5 to about 20 and the liquid hourly space velocity can be in the range of about 0.1 to 10, usually about 0.5 to 5.
It is contemplated that any molecular sieve having a pore size s appropriate to admit the bulky C9+ hydrocarbons and catalytically dealkylate the aromatics can be employed in this reformate upgrading process. More detailed information concerning appropriate molecular sieves for this invention is found in U.S. Pat. No. 5,865,986. The hydrogenation component which is preferred in this invention is rhenium, 2o which produces results comparable to those produced using platinum or palladium but at a lower cost.
The molecular sieve which catalyzes these reactions is usually an intermediate or large pore size zeolite having a silica-to-alumina mole ratio of at least about 12, specifically from about 12 to 2000. The zeolite 25 is usually characterized by a Constraint Index of about 0.5 to 12 specifically about 1 to 12 as described in U.S. Pat. No. 4,088,605.
Typically, the molecular sieve of choice is a zeolite. Zeolites contemplated include ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38, zeolite beta and other similar materials. U.S. Pat. No. 3,702,886 3o describing and claiming ZSM-5 is incorporated herein by reference.

Process Configuration In the multi-step integrated process the petroleum naphtha is catalytically reformed and the reformate is cascaded to the hydrodealkylation reaction zone.
o FIG. 1 is a simplified schematic flow diagram of one useful process configuration. Referring to FIG. 1, a petroleum naphtha supplied by line is charged to reformer heater 12 which elevates the temperature of the feed to a temperature suitable for reforming. The heated feed is charged to a plurality of reformer reaction zones 16a, 16b and 16c with ~5 interstage heaters 15a and 15b.
Although three reformer reaction zones are shown, there can be less than three or more than three reaction zones. The bottom portion of the last reformer reaction zone 18 is loaded with the hydrodealkylation catalyst. The feed passes over the hydrodealkylation catalyst just before 2o it exits the reformer to produce a product of increased benzene content as compared to the effluent of the last reforming catalyst zone 16c.
The hydrodealkylation catalyst of reaction zone 18 is typically isolated from the reforming catalyst to maximize its opportunity to work on the products of reforming as opposed to the reformer feed. This can 25 be accomplished by providing a separate reactor or by segregating the catalysts within the same reactor.
However, intermingling of the hydrodealkylation catalyst and the reforming catalyst will be difficult to avoid and will not be detrimental in the last part of the final reactor.
3o Usually when the hydrodealkylation catalyst is located within the reformer, regardless of where the hydrodealkylation catalyst is located, a radial flow reactor is particularly suitable to maintain a low pressure drop. The radial flow reactor, particularly in combination with smaller particle size hydrodealkylation catalyst, contributes to improved flow 35 distribution in the last bed of the reformer.

In some operations it will be useful to employ a small particle size catalyst, typically when reactor volume is small or to alleviate pressure drop. A self bound zeolite such as self-bound ZSM-5 is specifically contemplated.
FIG. 2 shows an embodiment of the invention in which the o hydrodealkylation catalyst is located in a separate reactor 19 associated with switching valves 17a and 17b which, optionally, enable the catalyst zone to be removed from on-line contact during at least a portion of regeneration of the reformer catalyst. Optionally, heater 15c is located between the last reactor of the reformer and the hydrodealkylation ~ 5 catalyst reactor 19.
Referring to both FIGS. 1 and 2, after cooling, the aromatics rich product is passed to vapor/liquid separator 22 which separates a hydrogen-rich gas via hydrogen compressor 25 for recycling to the reformer via line 21. Via line 24, the liquid product is conveyed from 2o separator 22 to fractionator 26 typically a series of fractionators that separate the product into C4 , C5, C6 Ce and C9+ hydrocarbon streams.
The C9+ aromatics can be separated and recycled to the reformer or the hydrodealkylation reactor to increase yield.
The Cs to CB stream of fractionator 26 is transferred by line 28 to a 25 paraffin separator 34 which separates the paraffins from the aromatics, typically, by solvent extraction. The aromatics extract can then be conveyed via line 35 to separation zone 36 which separates the extract into benzene, toluene and xylenes streams. An important advantage of the invention is a low consumption of hydrogen. Typically, hydrogen 3o consumption is less than about 200 SCFB (35.6n.1.1.< - 1 > ), more typically, ranging from about 0 SCFB (0 n.1.1< - 1 > ) to about 100 S.C.F.B. (17.8 n.1.1.< - 1 > ), more typically less than about 50 SCFB (8.9 n.1.1.< - 1 > ). This low hydrogen consumption can be particularly advantageous when there is a need to balance a high hydrogen consumption in the reformer.
The hydrodealkylation catalyst can be exposed to the conditions of the reformer during rejuvenative treatment of the reformer catalyst.
Typically, the reformer catalyst is rejuvenated by oxychlorination but any o rejuvenating method is contemplated.
The hydrodealkylation catalyst may be reactivated by the rejuvenative treatment of the reformer catalyst. However, other methods known for reactivating the catalyst may be employed such as burning with oxygen, regeneration with hydrogen or an inert gas such as nitrogen.
Examples Example 1 A reformate was obtained which had the following composition.
Example 2 The catalyst used in this study was prepared by steaming an alumina bound ZSM-5 base (65/35) at 1200°F for 15 hours. The alpha activity of this catalyst after steaming is 2.6. This steamed catalyst was then impregnated (incipient wetness impregnation) 3o with an aqueous solution of ammonium perrhenate to yield a 5 catalyst which contains 0.3% rhenium by weight (measured as the metal). This catalyst was then dried and calcined for one hour at 975°F in a rotary calciner. This dried catalyst is herein referred to as 0.3% Re/ZSM-5.
1o Example 3 The hydrocarbon mixture of Example 1 was used as feed in a fixed-bed, laboratory reactor filled with the catalyst of Example 2.
The catalyst was first oxychlorided with a mixture of 1300 ppmv chlorine and 7% oxygen in nitrogen at 990°F, followed by reduction with hydrogen at 700°F in a glass-lined, fixed bed reactor to simulate commercial reformer catalyst reactivation conditions.
Five grams of the oxychlorided and reduced catalyst were then transferred to a 0.68" ID, stainless steel tube, fixed-bed reactor operated in an adiabatic fashion. The catalyst was sulfided with 400 ppmv hydrogen sulfide in Hydrogen at 750°F prior to feeding the hydrocarbon mixture to the reactor to simulate commercial reformer catalyst preparation.
The conditions for the experiment were 24 WHSV, ca. 6:1 2s H2:HC, 940°F WABT, and ca. 300 psig. The hydrocarbon feed mixture was combined with makeup hydrogen and recycle gas to simulate the conditions present in the last reactor of a commercial catalytic reformer. The reactor product is cooled and flashed in a separator. A portion of the flash separator overhead gas is 3o recycled to the inlet of the reactor by a compressor. On-line, gas chromatography is used to analyze the gaseous and liquid products from the flash separator and calculate yields of the various hydrocarbon molecules.

After nine days on stream, the following yields were obtained:
Note that there are increases in benzene, toluene, and xylenes 1 o versus the feed composition.

Claims

What is claimed is:
1. A multistage integrated process for upgrading a petroleum naphtha comprising the steps of:
(a) introducing the naphtha to a catalytic reforming stage comprising a plurality of operatively connected catalyst zones including a first catalyst zone and a last catalyst zone, the last catalyst zone being maintained under reforming conditions of temperature ranging from at least 800°F (427°C) to 1050°F (565°C) and pressure of 50 psig (446 kPa) to 500 psig (3,549 kPa) to provide an intermediate product comprising aromatics and paraffins;
(b) transferring at least a portion of the intermediate product of the last catalyst zone to a benzene and toluene synthesis zone comprising at least one benzene and toluene synthesis catalyst operatively connected to the last catalyst zone of the reforming stage of step (a), the benzene and toluene synthesis zone being maintained under conditions of hydrogen-to-hydrocarbon mole ratio and pressure compatible with the last catalyst zone of the reforming stage and temperature of greater than 800°F (427°C), the benzene and toluene synthesis catalyst zone containing a catalyst, which comprises a hydrogenation component from Group VIIB and further comprises a molecular sieve of low acid activity, as determined by an alpha value of less than 60, to provide a hydrocarbon product comprising more benzene, toluene, xylenes content than the intermediate product of the last catalyst zone of the reforming stage;
wherein the intermediate product of step (a) that is fed to the benzene, toluene, and xylenes synthesis zone of step (b) has not been subjected to intermediate separation.

2. The process as described in claim 1 in which the catalyst of step (b) comprises a molecular sieve selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38, MCM-22, MCM-36, MCM-48, MCM-56, and zeolite beta.

3. The process as described in claim 2 in which the catalyst of step (b) comprises ZSM-5 having an alpha value less than 50.

4. The process as described in claim 1 in which the benzene, toluene, or xylenes content of the intermediate product of step (a) is increased by at least 10% in step (b).

5. The process as described in claim 1 in which the hydrogenation component of step (b) is Re.

6. The process as described in claim 1 in which the catalyst of step (b) comprises a catalyst deactivated in another refinery oxygenate or hydrocarbon conversion process.

7. The process as described in claim 1 in which the hydrocarbon product of step (b) further comprises branched C6* paraffins, the process further comprising step (c) of contacting the hydrocarbon product of step (b) over a catalyst zone comprising another catalytic reforming stage which isomerizes the branched C6+ paraffins.

8. The process as described in claim 1 in which the catalyst of step (b) further comprises sulfur.

9. The process as described in claim 8 in which a source of sulfur is a cofeed introduced in step (b).

10. The process of claim 1 in which at least the catalyst zone of step (a) is a radial flow reactor zone.

11. The process of claim 1 in which at least the zone of step (b) is a radial flow reactor zone.

12. The process of claim 3 in which the catalyst of step (b) is self-bound ZSM-5.

13. The process of claim 12 in which the zone of step (b) is a fixed bed zone.

14. The process of claim 1 in which the hydrocarbon product of step (b) comprise C9+ hydrocarbons, the process further comprising separating the C9+ hydrocarbons from the product of step (b) and recycling the C9+ hydrocarbons to step (a) or step (b).

15. The process of claim 1 which further comprises a C9+ aromatic cofeed in step (a) or step (b).
16. The process of claim 1 in which the petroleum naphtha is free of C6- hydrocarbons.
17. The process of claim 2 in which the catalyst of step (b) is subjected to steaming.
20. The process of claim 1 in which the product of step (b) further comprises a xylenes content which is higher than the intermediate product of the last catalyst zone of the reforming stage.