AROMATIC RECOVERY COMPLEX WITH A HYDRODEARYLATION STEP TO PROCESS CLAY TOWER EFFLUENTS
20220033718 · 2022-02-03
Assignee
Inventors
Cpc classification
C10G67/06
CHEMISTRY; METALLURGY
C10G49/04
CHEMISTRY; METALLURGY
C10G25/003
CHEMISTRY; METALLURGY
C10G49/08
CHEMISTRY; METALLURGY
C10G47/20
CHEMISTRY; METALLURGY
International classification
Abstract
The disclosure provides a process to hydrodearylate the non-condensed alkyl-bridged multi-aromatics at the outlet of the clay tower where such multi-aromatics form rather than performing hydrodearylation on the reject stream of the aromatics complex. Hydrodearylation may feature combining a C.sub.8+ hydrocarbon stream from a clay treater with a hydrogen stream over a catalyst bed comprising a support and an acidic component optionally containing Group 8 and/or Group 6 metals.
Claims
1. A process for the recovery of alkyl mono-aromatic compounds, the process comprising (a) directing a C.sub.8+ feed stream from a clay treater of an aromatic recovery complex into a hydrodearylation unit, wherein the stream comprises C.sub.8+ compounds of one or more heavy alkyl aromatic compounds and alkyl-bridged multi-aromatic compounds; (b) hydrodearylating alkyl-bridged multi-aromatic compounds in the hydrodearylation unit by adding a hydrogen stream to the C.sub.8+ feed stream over a catalyst to produce an alkyl mono-aromatic compound containing stream; and (c) directing the alkyl mono-aromatic compound containing stream produced from (b) into a xylene re-run unit to split the alkyl mono-aromatic compound containing stream into a stream comprising C.sub.8 and another stream comprising C.sub.9.
2. The process of claim 1, wherein the at least one or more heavy alkyl aromatic compounds and alkyl-bridged alkyl multi-aromatic compounds in the feed stream comprise at least two benzene rings connected by an alkyl bridge group of at least two carbons, wherein the benzene rings are connected to different carbons of the alkyl bridge group.
3. The process of claim 1, wherein the clay treater is operated at a temperature between 160° C. and 220° C.
4. The process of claim 3, wherein the clay treater is operated at 1-20 bars pressure.
5. The process of claim 3, wherein the clay treater is operated at an liquid hourly space velocity (LHSV) of about 0.5 hr.sup.−1 to about 10 hr.sup.−1.
6. The process of claim 3, wherein the clay treater outlet effluent is substantially olefin free.
7. The process of claim 6, wherein the clay treater outlet effluent has a bromine index less than 200.
8. The process of claim 1, wherein the hydrogen stream is combined with the feed stream before being supplied to the hydrodearylation unit.
9. The process of claim 1, wherein the hydrogen stream is comprised of a recycled hydrogen stream and a makeup hydrogen stream.
10. The process of claim 1, wherein the hydrogen partial pressure is at least 15 bars.
11. The process of claim 1, wherein the catalyst is presented as a catalyst bed in the hydrodearylation unit.
12. The process of claim 11, wherein a portion of the hydrogen stream is fed to the catalyst bed in the hydrodearylation unit to quench the catalyst bed.
13. The process of claim 1, wherein the catalyst comprises a support being at least one member selected from the group consisting of silica, alumina, titania or combinations thereof, and an acidic component selected from the group consisting of amorphous silica-alumina, zeolite, or combinations thereof.
14. The process of claim 13, wherein the catalyst further comprises an IUPAC Group 8-10 metal selected from the group consisting of iron, cobalt, and nickel, or combinations thereof and an IUPAC Group 6 metal selected from the group consisting of molybdenum, tungsten, or combinations thereof.
15. The process of claim 14, wherein the IUPAC 8-10 metal is 2 to 20 percent by weight of the catalyst and the IUPAC Group 6 metal is 1 to 25 percent by weight of the catalyst.
16. The process of claim 1, wherein the catalyst comprises nickel, molybdenum, ultrastable Y-type zeolite, and γ-alumina support.
17. The process of claim 1, wherein step (b) includes an operating temperature within the hydrodearylation unit of about 200 to about 450° C.
18. The process of claim 1, wherein step (b) includes a hydrogen partial pressure within the hydrodearylation unit of about 5 to about 50 bars.
19. The process of claim 1, wherein step (b) includes a feed rate of the hydrogen stream to the hydrodearylation unit of about 100 to about 1000 standard liters per liter of feedstock.
20. The process of claim 1, wherein the aromatic recovery complex receives a reformate stream from a catalytic reforming unit.
21. The process of claim 20, wherein a reformate splitter within the aromatic recovery complex splits the reformate stream into a C.sub.5+C.sub.6 stream that goes to a benzene extraction unit and a C.sub.7+ stream that feeds to a splitter.
22. The process of claim 21, wherein the splitter divides the C.sub.7+ stream to a C.sub.7 stream and a C.sub.8+ stream that passes through the clay treater and thereafter into the hydrodearylation unit.
23. The process of claim 1, wherein the C.sub.8 stream from the xylene re-run unit flows to a para-xylene extraction unit and a xylene isomerization unit that recycles back to the xylene re-run unit.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
[0017]
[0018]
[0019]
[0020] The embodiments set forth in the drawing are illustrative in nature and not intended to be limiting to the claims. Moreover, individual features of the drawings will be more fully apparent and understood in view of the detailed description.
DETAILED DESCRIPTION
[0021] This disclosure describes various processes and systems for feeding a C.sub.8+ stream in an aromatics recovery complex to a hydrodearylation unit for conversion of alkyl-bridged non-condensed alkyl aromatics to lighter mono-alkyl aromatics for improved para-xylene recovery in a refinery.
[0022] As used herein, the term “hydrodearylation” refers to a reaction or series of steps to cleave alkyl bridges of non-condensed alkyl-bridged multi-aromatics or heavy alkyl aromatic compounds to form alkyl mono-aromatics, in the presence a catalyst and hydrogen. “Alkyl bridged non-condensed alkyl aromatic” compounds refer at least two aromatic (or benzene) rings connected by an alkyl bridge group with at least two carbons bridging between the rings, where the aromatic or benzene rings are connected to different carbons of the alkyl bridge group.
[0023] As used herein, the term “stream” (and variations thereof) refers to a connected pathway flow of vapors, gases or liquids from one source or system or unit to a second. In many instances, a stream may feature one or more of various hydrocarbon compounds, such as straight chain, branched or cyclical alkanes, alkenes, alkadienes, alkynes, alkyl aromatics, alkenyl aromatics, condensed and non-condensed di-, tri- and tetra-aromatics, and gases such as hydrogen and methane, C.sub.2+ hydrocarbons and further may include various impurities.
[0024] Heavy aromatics are byproducts formed during various processing steps during refining of crude oil. Heavy aromatics include mono-aromatics with long attached alkyl groups, as well as multi-aromatics of two or more aromatic rings linked with alkyl bridges. U.S. Pat. No. 10,053,401, identified that aromatic bottoms of C.sub.9+ hydrocarbons can be subjected to hydrodearylation using a hydrogen stream and a catalyst to cleave or sever the alkyl bridges and recover lighter mono-aromatics. Recovered mono-aromatics can then be processed to increase the yield of BTX compounds from refineries.
[0025] The clay treater within an aromatics recovery complex is present to remove olefins prior to xylene purification and recycling. By way of example, the clay treater may be operated at a temperature between 160° C. and 220° C. and at a pressure range of 1-20 bars. In some instances, the connected unit is at an elevated height. The clay treater may be operated at a liquid hourly space velocity (LHSV) of between 0.5 hr.sup.−1 and 10 hr.sup.−1 and with an outlet effluent bromine index of 200 or less.
[0026] While the clay treater is effective for reducing olefin content, the acidity of the clay and the temperature of the clay treater provides an opportunity for alkenyl aromatics to react with alkyl aromatics to form non-condensed alkyl-bridged di-aromatics. Some di-aromatics can similarly react to form tri-aromatics and so on, providing a site for multi-aromatics production prior to being received at the xylene re-run column where mono-aromatic C.sub.8 compounds (e.g. xylenes) are to be isolated. As C.sub.8 compounds can be depleted during the clay treating, it is a function of this disclosure to recover light mono-aromatics prior to xylene purification to improve yields and reduce loss of valuable hydrocarbons. The recovery includes, therefore, not just alkyl aromatics that reacted with alkenyl aromatics, but the alkenyl aromatics now reduced to alkyl aromatics.
[0027] The disclosure therefore relates to introducing a hydrodearylation unit into an aromatics recovery complex within a refinery. In some instances, the hydrodearylation unit is introduced between a clay treater and a xylene re-run unit to increase the alkyl mon-aromatic compounds entering the xylene re-run unit. A hydrodearylation unit assists in the recovery of light alkylated mono-aromatics from streams that contain alkyl-bridged non-condensed alkylated multi-aromatic compounds and heavy alkyl-aromatic compounds. Alkyl-bridged non-condensed alkyl aromatic compounds may be referred to as multi-aromatics or poly-aromatics. A more in-depth description of the hydrodearylation process is found in U.S. Pat. No. 10,053,401, which is hereby incorporated by reference in its entirety.
[0028] Hydrodearylation refers to generating mono-aromatic or alkyl aromatic compounds from multi-aromatics, through a process of dearylation or cleaving of the alkyl bridge(s) between the aromatic rings. As set forth herein, a hydrodearylation unit receives a stream of C.sub.8+ hydrocarbon compounds that include multi- or poly-aromatic compounds. In some instances, the C.sub.8+ stream may be from a clay treater in an aromatics recovery complex. Clay treatment (or clay filtration; e.g. using a clay treater) refers to a process by which contaminants, such as olefins and alkenyl aromatics, may be removed in an aromatics recovery complex. Typically, a stream may be passed through or over a clay treater or clay tower, where it comes into contact with a surface of the clay. The olefinic species are composed primarily of alkenyl aromatics, such as styrene and methyl-styrene. Such molecules would be expected to react across clay-containing Lewis-acid sites at temperatures around 200° C. with the alkyl aromatics via a Friedel-Crafts reaction to form molecules with two aromatic rings connected with an alkyl bridge. Analysis of spent clay from a commercial unit found polar solvent (i.e., toluene and tetrahydrofuran) soluble hydrocarbons and solvent insoluble hydrogen deficient hydrocarbons on the clay surface. Solvent soluble hydrocarbons are leftovers from the reformate stream and solvent insoluble hydrogen deficient hydrocarbons are basically coke and removed at temperature 400° C. and above.
[0029] The C.sub.8+ stream from the day treater is contacted or combined with a further stream of hydrogen as an initial step in hydrodearylation. The two may be contacted wither before or following entry into the unit, but prior to collectively flowing over any catalyst therein.
[0030] The combined flow of the C.sub.8+ hydrocarbon stream and hydrogen may then contact a catalyst. Collectively, the combination of hydrogen and the catalyst allows for hydrodearylation to occur. The product stream leaves the unit containing newly generated mono-aromatic compounds. The processes for conversion of multi-aromatics into alkyl aromatics may allow for the use of the alkyl aromatics as feedstock to a benzene, toluene, and xylenes (BTX) petrochemicals processing unit.
[0031] In the hydrodearylation unit, the catalyst may be provided as an exposed bed in a reactor. In some instances, a portion of the hydrogen stream may be fed to the catalyst bed in the reactor to provide quenching to the catalyst bed. In some aspects, the catalyst bed may include two or more catalyst beds. The catalyst may further include a support, such as a support selected from silica, alumina, titania and/or combinations thereof. The catalyst may also include an acidic component(s) selected from amorphous silica-alumina, zeolite, and/or combinations thereof. The catalyst may include a Group 8-10 (per IUPAC grading) metal and/or a Group 6 (IUPAC) metal. The catalyst may be a metal selected from iron, cobalt, nickel, and/or combinations thereof. The catalyst may further include a metal selected from the group consisting of molybdenum, tungsten, and/or combinations thereof. The catalyst, in some instances, may contain an IUPAC Group 8-10 metal at about 2 to 20 percent by weight of the total weight of the catalyst (including 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19%) and an IUPAC Group 6 metal at about 1 to 25 percent by weight of the total weight of the catalyst (including 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24%). The catalyst may include one or more of nickel, molybdenum, ultrastable Y-type zeolite, and γ-alumina support.
[0032] The hydrodearylation unit can be operated at a temperature of about 250° C. to about 400° C. and at a pressure from about 5 bar to about 50 bar. In some instances, the hydrodearylation unit is operated at about 350° C. and at a pressure of 15 bar.
[0033] A typical refinery with an aromatic recovery complex (ARC) is presented in
[0034]
[0035] As outlined above, aromatic bottoms can be added to the gasoline pool or hydrodearylated per U.S. Pat. No. 10,053,401. The aromatics bottoms fraction from the xylene re-run splitter may then be either: i) fractionated with the 180−° C. fraction sent directly to a gasoline pool as blending components and the 180+° C. fraction sent to a hydrodearylation unit; or ii) fractionated such that the C.sub.9 and C.sub.10 components are sent directly to a transalkylation unit and the C.sub.11+ components are sent to a hydrodearylation unit or iii) sent directly to a hydrodearylation unit to recover light alkyl mono-aromatic compounds from heavy alkyl aromatic and alkyl-bridged non-condensed alkyl aromatic compounds (see, e.g.
[0036] The present invention, conversely, concerns introducing a hydrodearylation within the ARC itself, particularly at the point of receiving a C.sub.8+ stream at the outlet of the clay treater. Alkyl-bridged non-condensed di-aromatics (or multi-aromatics) may form in the clay treater or tower as described herein. Typically, the effluent at the outlet of the clay treater is fractionated through the xylene re-run splitter and the resulting C.sub.9+ feed is sent as aromatic bottoms and potentially either hydrodearylated or the C.sub.9 and C.sub.10 components are removed and the C.sub.11+ stream can be hydrodearylated, since the heavy alkyl-bridged non-condensed di-aromatics (or multi-aromatics) are now in these heavier streams.
[0037] It is therefore a distinguishing facet of the present disclosure to introduce the hydrodearylation prior to fractionation at the xylene re-run splitter. Placement of a hydrodearylation unit at this point provides an opportunity to reduce multi-aromatics from being fractioned with C.sub.9+ hydrocarbons from the xylene re-run and increase the C.sub.8 fraction for para-xylene extraction and isomerization. Hence, the embodiments of this disclosure offer an alternative process configuration for hydrodearylation by expanding hydrodearylation to process to the C.sub.8+ stream.
[0038] Referring now to
[0039] Referring to
[0040] The C.sub.8+ stream 420 is run through a clay treater 4 and then streamed 430 to a xylene re-run unit 5 to split C.sub.8+ hydrocarbons into a C.sub.8 hydrocarbon stream 431 and C.sub.9+ (heavy aromatic MoGas) hydrocarbon stream (aromatic bottoms) 60. The xylene-re-run unit 5 is a distillation column including trays and/or structured packing and/or random packing to fractionate mixed xylenes from heavier aromatics. The C.sub.8 hydrocarbon stream 431 proceeds to a para-xylene extraction unit 6 to recover para-xylene in a para-xylene product stream 433. The para-xylene extraction unit 6 also produces a C.sub.7 cut MoGas stream 432, which combines with the C.sub.7 cut MoGas stream 411 from the earlier splitter 3 to produce a combined C.sub.7 cut MoGas stream 412. Other xylenes are recovered from the para-xylene extraction unit 6 and sent to xylene isomerization unit 7 by stream 434 to convert them to para-xylene. The isomerization unit 7 includes a catalyst, such as a zeolite, that assists in transforming ortho- and meta-xylenes to para-xylene. The isomerized xylenes are sent to a further splitter column 8 by stream 450. The converted fraction is recycled back to para-xylene extraction unit 6 from splitter column 8 by way of streams 452 (C.sub.8+) and 431 (C.sub.8) and further re-passage through the xylene re-run unit 5. A top stream of lighter compounds 451 from the further splitter column 8 is recycled back to reformate splitter 1 for possible further benzene extraction. The heavy fraction from the xylene rerun unit 5 is recovered as aromatic bottoms (shown as C.sub.9+ and Hvy Aro MoGas in
[0041] Turning to
[0042] Turing to
[0043] According to an aspect, either alone or in combination with any other aspect, a process for the recovery of alkyl mono-aromatic compounds, the process including: (a) directing a feed stream from a clay treater of an aromatic recovery complex to a hydrodearylation unit, wherein the stream comprises C.sub.8+ compounds of one or more heavy alkyl aromatic compounds and alkyl-bridged multi-aromatic compounds; (b) hydrodearylating alkyl-bridged multi-aromatic compounds in the hydrodearylation unit by adding a hydrogen stream to the feed stream over a catalyst to produce an alkyl mono-aromatic compound containing stream; and (c) directing the alkyl mono-aromatic compound containing stream from (b) to a xylene re-run unit.
[0044] According to a second aspect, either alone or in combination with any other aspect, the alkyl-bridged alkyl multi-aromatic compounds in the feed stream include at least two benzene rings connected by an alkyl bridge group of at least two carbons, wherein the benzene rings are connected to different carbons of the alkyl bridge group,
[0045] According to a third aspect, either alone or in combination with any other aspect, the clay treater is operated at a temperature between 160° C. and 220° C.
[0046] According to a fourth aspect, either alone or in combination with any other aspect, the clay treater is operated at 1-20 bars pressure.
[0047] According to a fifth aspect, either alone or in combination with any other aspect, the clay treater is operated at a liquid hourly space velocity (LHSV) of about 0.5 hr.sup.−1 to about 10 hr.sup.−1.
[0048] According to a sixth aspect, either alone or in combination with any other aspect, the clay treater outlet effluent is substantially olefin free.
[0049] According to a seventh aspect, either alone or in combination with any other aspect, the clay treater outlet effluent has a bromine index less than 200.
[0050] According to an eighth aspect, either alone or in combination with any other aspect, the hydrogen stream is combined with the feed stream before being supplied to the hydrodearylation unit.
[0051] According to a ninth aspect, either alone or in combination with any other aspect, the hydrogen stream is comprised of a recycled hydrogen stream and a makeup hydrogen stream.
[0052] According to a tenth aspect, either alone or in combination with any other aspect, the hydrogen partial pressure is at least 15 bars
[0053] According to an eleventh aspect, either alone or in combination with any other aspect, the catalyst is presented as a catalyst bed in the hydrodearylation unit.
[0054] According to a twelfth aspect, either alone or in combination with any other aspect, a portion of the hydrogen stream is fed to the catalyst bed in the hydrodearylation unit to quench the catalyst bed.
[0055] According to a thirteenth aspect, either alone or in combination with any other aspect, the catalyst includes a support being at least one member selected from silica, alumina, titania or combinations thereof, and an acidic component selected from the group consisting of amorphous silica-alumina, zeolite, or combinations thereof.
[0056] According to a fourteenth aspect, either alone or in combination with any other aspect, the catalyst includes an IUPAC Group 8-10 metal selected from iron, cobalt, and nickel, or combinations thereof and an IUPAC Group 6 metal selected from the group consisting of molybdenum, tungsten, or combinations thereof.
[0057] According to a fifteenth aspect, either alone or in combination with any other aspect, the IUPAC 8-10 metal is 2 to 20 percent by weight of the catalyst and the IUPAC Group 6 metal is 1 to 25 percent by weight of the catalyst.
[0058] According to a sixteenth aspect, either alone or in combination with any other aspect, the catalyst is of a nickel, molybdenum, ultrastable Y-type zeolite, and γ-alumina support.
[0059] According to a seventeenth aspect, either alone or in combination with any other aspect, the hydrodearylation unit has an operating temperature of about 200 to about 450° C.
[0060] According to an eighteenth aspect, either alone or in combination with any other aspect, the hydrodearylation unit has a hydrogen partial pressure of about 5 to about 50 bars
[0061] According to a nineteenth aspect, either alone or in combination with any other aspect, the hydrodearylation unit has a feed rate of the hydrogen stream of about 100 to about 1000 standard liters per liter of feedstock.
[0062] According to a twentieth aspect, either alone or in combination with any other aspect, the aromatic recovery complex receives a reformate stream from a catalytic reforming unit.
[0063] According to a twenty-first aspect, either alone or in combination with any other aspect, a reformate splitter within the aromatic recovery complex splits the reformate stream into a C.sub.5+C.sub.6 stream that goes to a benzene extraction unit and a C.sub.7+ stream that feeds to a splitter.
[0064] According to a twenty-second aspect, either alone or in combination with any other aspect, the splitter divides the C.sub.7+ stream to a C.sub.7 stream and a C.sub.8+ stream that passes through the clay treater and thereafter into the hydrodearylation unit.
[0065] According to a twenty-third aspect, either alone or in combination with any other aspect, the xylene re-run splits the alkyl mono-aromatic compound stream to a C.sub.9+ stream and a C.sub.8 stream that flows to a para-xylene extraction unit and a xylene isomerization unit that recycles back to the xylene re-run unit.
EXAMPLES
[0066] One or more of the previously described features will be further illustrated in the following example simulations.
Example 1
[0067] Properties and composition of the C.sub.8+ stream at the outlet of the clay treater tower are shown in Table 1.
TABLE-US-00001 TABLE 1 Feedstock/Product properties and composition Property/Composition Units Feedstock Product Density g/cc 0.743 0.740 Paraffins 0.57 0.57 C7-MonoAromatics wt. % 0.22 0.22 C8-MonoAromatics wt. % 52.59 54.59 C9-MonoAromatics wt. % 23.68 23.68 C10-MonoAromatics wt. % 20.08 20.08 C11+ wt. % 2.86 0.86 Total wt. % 100.00 100.00
[0068] The C.sub.8+ stream was contacted with a catalyst subjected to hydrodearylation conditions as follows: Pressure: 15-30 bars, temperature: 280-350° C., liquid hourly space velocity (“LHSV”) 1.7 hr.sup.−1 (Equivalent LHSV based on di-aromatics in the stream: 140 hr.sup.−1).
[0069] The problematic di-aromatics in the hydrodearylated product after being subjected to hydrodearylation (at 350° C. and 15 bar) dropped by 70%. The absolute wt. % difference in di-aromatic content between the feed to the hydrodearylation reactor and the hydrodearylated products is almost entirely at the benefit of mono-aromatic formation. The increased % of high-value mono-aromatics can then be processed upstream for benzene and para-xylene formation as shown in Table 1.
[0070] Throughout this disclosure, ranges are provided. It is envisioned that each discrete value encompassed by the ranges are also included. Additionally, the ranges which may be formed by each discrete value encompassed by the explicitly disclosed ranges are equally envisioned.