# Patent

## Title
Methods and apparatuses for reforming of hydrocarbons including recovery of products using an absorption zone and a pressure swing adsorption zone

## Abstract

Embodiments of apparatuses and methods for reforming of hydrocarbons including recovery of products are provided. In one example, a method comprises separating a reforming-zone effluent to form a net gas phase stream and a liquid phase hydrocarbon stream. The net gas phase stream is compressed, partially condensed and cooled, and separated to form an intermediate gas phase stream. The intermediate gas phase stream is cooled to form a cooled intermediate gas phase stream. The liquid phase hydrocarbon stream is cooled to form a cooled liquid phase hydrocarbon stream. The cooled intermediate gas phase stream is contacted with the cooled liquid phase hydrocarbon stream to form an H2-rich stream and a cooled second intermediate liquid phase hydrocarbon stream that is enriched with C3/C4 hydrocarbons. The H2-rich stream is contacted with an adsorbent to form an H2-ultra rich stream.

## Background
TECHNICAL FIELD
The technical field relates generally to reforming of hydrocarbons, and more particularly relates to apparatuses and methods for reforming of hydrocarbons with improved recovery of products from a reforming-zone effluent.
BACKGROUND
High octane gasoline is needed for modern gasoline engines. Previously, octane numbers were often improved by incorporating various lead-containing additives into the gasoline. As lead-containing additives have been phased out of gasoline for environmental reasons, it has become increasingly necessary to rearrange the structure of the hydrocarbons used in gasoline blending to achieve higher octane ratings. Catalytic reforming of hydrocarbons is a process widely used by refiners for upgrading the octane ratings of gasoline as well as for other useful hydrocarbon conversion applications.
In catalytic reforming, a hydrocarbon feedstock of, for example, C5 hydrocarbons to about C11 hydrocarbons, is contacted with a reforming catalyst to convert at least a portion of the heavier hydrocarbons to aromatic hydrocarbons, for example, to increase the octane content of gasoline. The catalytic reforming of the heavier hydrocarbons to produce a reformate that includes aromatic hydrocarbons also produces significant quantities of valuable hydrogen and lighter hydrocarbons, such as liquefied petroleum gas (LPG) containing primarily C3 and C4 hydrocarbons. Refiners are looking for ways to maximize the recovery of reforming products, such as reformate, hydrogen and LPG, from the reforming reactor effluent.
Accordingly, it is desirable to provide apparatuses and methods for reforming of hydrocarbons with improved recovery of products from a reforming reactor effluent. Furthermore, other desirable features and characteristics will become apparent from the subsequent detailed description and the appended claims, taken in conjunction with the accompanying drawings and this background.
BRIEF SUMMARY
Apparatuses and methods for reforming of hydrocarbons including recovery of products are provided herein. In accordance with an exemplary embodiment, an apparatus for reforming of hydrocarbons including recovery of products comprises a separation zone. The separation zone is configured to receive and separate a reforming-zone effluent that comprises H2, C4− hydrocarbons, and C5+ hydrocarbons including aromatics to form a net gas phase stream that comprises H2 and C6− hydrocarbons and a liquid phase hydrocarbon stream that comprises C5+ hydrocarbons. A first compressor is configured to receive and compress the net gas phase stream to form a compressed net gas phase stream. A first cooler is configured to receive and partially condense and cool the compressed net gas phase stream to form a partially condensed, compressed net gas phase stream. A knockout drum is configured to receive and separate the partially condensed, compressed net gas phase stream into an intermediate gas phase stream and a first intermediate liquid phase hydrocarbon stream. An absorption zone is configured to receive and cool the intermediate gas phase stream and the liquid phase hydrocarbon stream to form a cooled intermediate gas phase stream and a cooled liquid phase hydrocarbon stream, respectively. The absorption zone comprises an absorber that is configured for contacting the cooled intermediate gas phase stream with the cooled liquid phase hydrocarbon stream to extract C3/C4 hydrocarbons from the cooled intermediate gas phase stream to the cooled liquid phase hydrocarbon stream and to form an H2-rich stream and a cooled second intermediate liquid phase hydrocarbon stream that is enriched with C3/C4 hydrocarbons and further comprises C5+ hydrocarbons. A pressure swing adsorption (PSA) zone contains an adsorbent for selectively separating H2 from hydrocarbons. The PSA zone is configured for receiving the H2-rich stream and for contacting the H2-rich stream with the adsorbent to form an H2-ultra rich stream.
In accordance with another exemplary embodiment, a method for reforming of hydrocarbons including recovery of products is provided. The method comprises the steps of separating a reforming-zone effluent that comprises H2, C4− hydrocarbons, and C5+ hydrocarbons including aromatics to form a net gas phase stream that comprises H2 and C6− hydrocarbons and a liquid phase hydrocarbon stream that comprises C5+ hydrocarbons. The net gas phase stream is compressed to form a compressed net gas phase stream. The compressed net gas phase stream is partially condensed and cooled to form a partially condensed, compressed net gas phase stream. The partially condensed, compressed net gas phase stream is separated into an intermediate gas phase stream and a first intermediate liquid phase hydrocarbon stream. The intermediate gas phase stream is cooled to form a cooled intermediate gas phase stream. The liquid phase hydrocarbon stream is cooled to form a cooled liquid phase hydrocarbon stream. The cooled intermediate gas phase stream is contacted with the cooled liquid phase hydrocarbon stream to extract C3/C4 hydrocarbons from the cooled intermediate gas phase stream to the cooled liquid phase hydrocarbon stream and to form an H2-rich stream and a cooled second intermediate liquid phase hydrocarbon stream that is enriched with C3/C4 hydrocarbons and further comprises C5+ hydrocarbons. The H2-rich stream is contacted with an adsorbent to selectively separate H2 from hydrocarbons and form an H2-ultra rich stream.
In accordance with another exemplary embodiment, a method for reforming of hydrocarbons including recovery of products is provided. The method comprises the steps of contacting a gas phase stream that comprises H2 and C6− hydrocarbons with a liquid phase hydrocarbon stream that comprises C5+ hydrocarbons in an absorber to extract C3/C4 hydrocarbons from the gas phase stream into the liquid phase hydrocarbon stream and to form an H2-rich stream and an intermediate liquid phase hydrocarbon stream. The H2-rich stream comprises primarily H2 and the intermediate liquid phase hydrocarbon stream is enriched with C3/C4 hydrocarbons and further comprises C5+ hydrocarbons. The H2-rich stream is contacted with an adsorbent in a pressure swing adsorption (PSA) zone to selectively separate H2 from hydrocarbons and form an H2-ultra rich stream. The intermediate liquid phase hydrocarbon stream is separated in a stabilizer to form a C5+ hydrocarbon-rich reformate stream that comprises primarily C5+ hydrocarbons and a stabilizer gas stream that comprises H2 and C4− hydrocarbons. At least a portion of the stabilizer gas stream is partially condensed and cooled to form a partially condensed stabilizer net gas stream. The partially condensed stabilizer net gas stream is separated in a separator to form a C3/C4 hydrocarbon-rich LPG stream that comprises primarily C3/C4 hydrocarbons and a light ends gas stream that comprises primarily H2 and C2− hydrocarbons.



BRIEF DESCRIPTION OF THE DRAWINGS
The various embodiments will hereinafter be described in conjunction with the following drawing FIGURES, wherein like numerals denote like elements, and wherein:
FIG. 1 schematically illustrates an apparatus and a method for reforming of hydrocarbons including recovery of products in accordance with an exemplary embodiment.



DETAILED DESCRIPTION
The following Detailed Description is merely exemplary in nature and is not intended to limit the various embodiments or the application and uses thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.
Various embodiments contemplated herein relate to apparatuses and methods for reforming of hydrocarbons with improved recovery of products from a reforming-zone effluent. The exemplary embodiments taught herein provide a separation zone in fluid communication with a reforming zone to receive a reforming-zone effluent. As used herein, the term “zone” refers to an area including one or more equipment items and/or one or more sub-zones. Equipment items can include one or more reactors or reactor vessels, scrubbers, strippers, fractionators or distillation columns, absorbers or absorber vessels, regenerators, heaters, exchangers, coolers/chillers, pipes, pumps, compressors, controllers, and the like. Additionally, an equipment item can further include one or more zones or sub-zones. The reforming-zone effluent comprises hydrogen (H2), C4− hydrocarbons, and C5+ hydrocarbons including aromatics. As used herein, CX+ means hydrocarbon molecules that have “X” number of carbon atoms, CX+ means hydrocarbon molecules that have “X” and/or more than “X” number of carbon atoms, and CX− means hydrocarbon molecules that have “X” and/or less than “X” number of carbon atoms.
The separation zone separates the reforming-zone effluent to form a net gas phase stream and a liquid phase hydrocarbon stream. The net gas phase stream comprises H2 and C6− hydrocarbons and the liquid phase hydrocarbon stream comprises C5+ hydrocarbons. In an exemplary embodiment, the net gas phase stream is compressed and partially condensed and cooled to form a partially condensed, compressed net gas phase stream. In an exemplary embodiment, a knockout drum separates the partially condensed, compressed net gas phase stream into a first intermediate liquid phase hydrocarbon stream that is recycled back to the separation zone and an intermediate gas phase stream.
The intermediate gas phase stream and the liquid phase hydrocarbon stream are passed along to an absorption zone. In an exemplary embodiment, the absorption zone comprises an absorber and first and second chiller sections that are upstream from the absorber. In one embodiment, the first and second chiller sections are separate chiller sections in a dual-bundle chiller. In another embodiment, the first and second chiller sections are in two separate chillers. In either embodiment, the first chiller section receives and cools the intermediate gas phase stream to form a cooled intermediate gas phase stream. The second chiller section receives and cools the liquid phase hydrocarbon stream to form a cooled liquid phase hydrocarbon stream. In an exemplary embodiment, the cooled intermediate gas phase stream and the cooled liquid phase hydrocarbon stream are introduced to the absorber as separate streams. In the absorber, the cooled intermediate gas phase stream contacts the cooled liquid phase hydrocarbon stream, for example, in countercurrent flow, to extract C3/C4 hydrocarbons from the cooled intermediate gas phase stream to the cooled liquid phase hydrocarbon stream and to form an H2-rich stream and a cooled second intermediate liquid phase hydrocarbon stream. The cooled second intermediate liquid phase hydrocarbon stream is enriched with C3/C4 hydrocarbons and further comprises C5+ hydrocarbons including aromatics. As used herein, the term “rich” means the corresponding component(s) is present in an amount of about 70 mole % or greater, such as about 80 mole % or greater. As used herein, the term “enriched” means that the concentration of the corresponding component(s) has increased relative to its original or previous concentration.
In an exemplary embodiment, the H2-rich stream is passed along to a pressure swing adsorption (PSA) zone that contains an adsorbent for selectively separating H2 from hydrocarbons. In the PSA zone, the H2-rich stream is contacted with the adsorbent to form an H2-ultra rich stream. As used herein, the term “ultra rich” means about 90 mole percent (mole %) or greater.
In an exemplary embodiment, at least a portion of the cooled second intermediate liquid phase hydrocarbon stream is passed through at least one heater and/or heat exchanger(s) to form a heated second intermediate liquid phase hydrocarbon stream. The heated second intermediate liquid phase hydrocarbon stream is separated in a stabilizer to form a C5+ hydrocarbon-rich reformate stream that comprises primarily C5+ hydrocarbons including aromatics and a stabilizer gas stream that comprises H2 and C4− hydrocarbons. As used herein, the term “primarily” means about 50 mole percent (mole %) or greater. A stabilizer gas separation zone partially condenses, cools and further separates at least a portion of the stabilizer gas stream to form a C3/C4 hydrocarbon-rich LPG stream that comprises primarily C3/C4 hydrocarbons and a light ends gas stream that comprises H2 and C2− hydrocarbons.
Referring to FIG. 1, an apparatus 10 for reforming of hydrocarbons in accordance with an exemplary embodiment is provided. The apparatus 10 comprises a reforming zone 12, a separation zone 14, a knockout drum 16, an absorption zone 17 including an absorber 18 (e.g., multi-stage vessel or separation vessel that contains trays or packing), a pressure swing adsorption (PSA) zone 20, a stabilizer 22, and a stabilizer gas separation zone 23 that are in fluid communication.
In an exemplary embodiment, a reforming-zone feedstock 26 containing naphtha fraction hydrocarbons, such as from C5 to about C11 hydrocarbons with a boiling point range of, for example, from about 70 to about 205° C., is introduced to the apparatus 10. The reforming-zone feedstock 26 and a recycle net gas phase stream 28 (discussed in further detail below) are passed along to the reforming zone 12 that contains a reforming catalyst as is well-known in the art. The reforming zone 12 will typically comprise a plurality of stacked or side-by-side reactors with provisions for intermediate heating of the intermediate reactant stream (e.g., the reforming-zone feedstock 26 and the recycle net gas phase stream 28 including any conversion products formed therefrom) and one or more heat exchangers. In an exemplary embodiment, in the reforming zone 12, the recycle net gas phase stream 28 is combined with the reforming-zone feedstock 26 for contact with the reforming catalyst.
A reforming-zone effluent 32 is formed in the reforming zone 12 and contains H2, C5+ hydrocarbons including aromatics, and lighter hydrocarbons such as C4− hydrocarbons including C3 and C4 hydrocarbons. In an exemplary embodiment, the reforming-zone effluent 32 is a two-phase liquid-gas stream in which H2 and the lighter hydrocarbons (e.g., C4− hydrocarbons) are predominately in the gas phase and the heavier hydrocarbons (e.g., C5+ hydrocarbons including aromatics) are predominately in the liquid phase. In one embodiment, the reforming-zone effluent 32 has a temperature of from about 35 to about 50° C. and, independently, a pressure of from about 240 to about 830 kPa gauge.
The reforming-zone effluent 32 is introduced to the separation zone 14. The separation zone 14 separates the reforming-zone effluent 32 into net gas phase stream 34 and a liquid phase hydrocarbon stream 36. In an exemplary embodiment, the net gas phase stream 34 comprises H2 and C6− hydrocarbons and the liquid phase hydrocarbon stream 36 comprises C5+ hydrocarbons including aromatics. In one example, the net gas phase stream 34 comprises H2 present in an amount of from about 80 to about 90 mole %, C1 hydrocarbons present in an amount of about 2 to about 5 mole %, C2 hydrocarbons present in an amount of from about 2 to about 5 mole %, C3 hydrocarbons present in an amount of from about 2 to about 4 mole %, C4 hydrocarbons present in an amount of from about 1.5 to about 2.5 mole %, and some C5+ hydrocarbons. In another example, the liquid phase hydrocarbon stream 36 comprises C5+ hydrocarbons present in an amount of from about 90 to about 99.9 mole % and some C4− hydrocarbons and H2. In an exemplary embodiment, the separation zone 14 is operated at a temperature of from about 35 to about 50° C. and, independently, a pressure of from about 240 to about 830 kPa gauge.
A portion of the net gas phase stream 34 is passed back to the reforming zone 12 as the recycle net gas phase stream 28 as discussed above and a remaining portion of the net gas phase stream 34 is passed along to a compressor 40. As illustrated and will be discussed in further detail below, in an exemplary embodiment, a recycle portion 202 of a partially cooled, compressed PSA tail gas stream 204 that contains C2− hydrocarbons, H2, and some C3+ hydrocarbons is passed through a valve 206 and is introduced to the net gas phase stream 34 upstream from the compressor 40. Although not illustrated, alternatively the recycle portion 202 may be passed along to other locations, such as, for example, stream 46, which is discussed in further detail below. The compressor 40 compresses the net gas phase stream 34 including the recycle portion 202 to form a compressed net gas phase stream 42. In an exemplary embodiment, the compressed net gas phase stream 42 has a temperature of from about 120 to about 150° C. and, independently, a pressure of from about 720 to about 2,490 kPa gauge.
The compressed net gas phase stream 42 is passed along to a cooler 45. In the cooler 45, the compressed net gas phase stream 42 is partially condensed and cooled to form a partially condensed, compressed net gas phase stream 50. In an exemplary embodiment, the partially condensed, compressed net gas phase stream 50 has a temperature of from about 30 to about 65° C. and, independently, a pressure of from about 690 to about 2,460 kPa gauge.
The partially condensed, compressed net gas phase stream 50 is introduced to the knockout drum 16. The knockout drum 16 separates the partially condensed, compressed net gas phase stream 50 into an intermediate gas phase stream 46 and an intermediate liquid phase hydrocarbon stream 48. In an exemplary embodiment, the intermediate gas phase stream 46 comprises H2 and C6− hydrocarbons and the intermediate liquid phase hydrocarbon stream 48 comprises C3+ hydrocarbons. In an exemplary embodiment, the intermediate liquid phase hydrocarbon stream 48 is passed through a valve 51 and recycled back to the separation zone 14 for further separation.
The intermediate gas phase stream 46 is introduced to the absorption zone 17. The liquid phase hydrocarbon stream 36 exits the separation zone 14, is passed through a pump 62 and introduced to the absorption zone 17. In an exemplary embodiment, the absorption zone 17 is configured as a countercurrent gas and liquid phase absorption zone for further separating H2, C3/C4 hydrocarbons, and/or C5+ hydrocarbons via extraction and/or absorption by contacting the liquid and gas phase fractions of the intermediate gas phase stream 46 and the liquid phase hydrocarbon stream 36. As illustrated, in an exemplary embodiment, the absorption zone 17 comprises a single absorber 18 as well as other types of equipment items as will be described in further detail below. Alternatively, the absorption zone 17 may have more than one absorber as well as other types of equipment items.
In the absorption zone 17, the intermediate gas phase stream 46 is passed along to a compressor 52. The compressor 52 compresses the intermediate gas phase stream 46 to form a compressed intermediate gas phase stream 54. In an exemplary embodiment, the compressed intermediate gas phase stream 54 has a temperature of from about 120 to about 160° C. and, independently, a pressure of from about 1,980 to about 5,580 kPa gauge.
The compressed intermediate gas phase stream 54 is passed along to a cooler 56. In the cooler 56, the compressed intermediate gas phase stream 54 is partially cooled to form a partially cooled, compressed intermediate gas phase stream 58. In an exemplary embodiment, the partially cooled, compressed intermediate gas phase stream 58 has a temperature of from about 30 to about 65° C. and, independently, a pressure of from about 1,950 to about 5,550 kPa gauge.
Optionally, in an exemplary embodiment, the absorption zone 17 includes a dryer 60 (e.g., vessel with adsorbent material or the like adsorbing water or otherwise removing water) for removing water from the partially cooled, compressed intermediate gas phase stream 58 to help avoid the formation of hydrates. In an exemplary embodiment, upstream from the dryer 60, the partially cooled, compressed intermediate gas phase stream 58 includes water present in an amount of about 15 ppm by weight or greater, and after being passed through the dryer 60, the partially cooled, compressed intermediate gas phase stream 58 includes water present in an amount of less than about 15 ppm by weight.
The partially cooled, compressed intermediate gas phase stream 58 is introduced to the absorption zone heat exchanger 230. In the absorption zone heat exchanger 230, heat is indirectly exchanged between the partially cooled, compressed intermediate gas phase stream 58 and an H2-rich stream 84, which is discussed in further detail below, to form a partially cooled, compressed intermediate gas phase stream 238 and a partially heated H2-rich stream 239. In an exemplary embodiment, the partially cooled, compressed intermediate gas phase stream 238 has a temperature of from about 10 to about 40° C. and, independently, a pressure of from about 1,920 to about 5,520 kPa gauge. In an exemplary embodiment, the partially heated H2-rich stream 239 has a temperature of from about 2 to about 60° C. and, independently, a pressure of from about 1,850 to about 5,450 kPa gauge.
The partially cooled, compressed intermediate gas phase stream 238 is introduced to a chiller 222 that includes a chiller section 226 to form a cooled, compressed intermediate gas phase stream 80. In an exemplary embodiment, the cooled, compressed intermediate gas phase stream 80 has a temperature of from about −28 to about 4° C., such as about −12 to about 0° C. and, independently, a pressure of from about 1,890 to about 5,490 kPa gauge.
As illustrated, the liquid phase hydrocarbon stream 36 is introduced to an absorption zone heat exchanger 228 for indirect heat exchange with a cooled intermediate liquid phase hydrocarbon stream 82, which is discussed in further detail below, to form a partially cooled liquid phase hydrocarbon stream 234 and a partially heated intermediate liquid phase hydrocarbon stream 236. In an exemplary embodiment, the partially cooled liquid phase hydrocarbon stream 234 has a temperature of from about −10 to about 40° C. and, independently, a pressure of from about 1,920 to about 5,520 kPa gauge. In an exemplary embodiment, the partially heated intermediate liquid phase hydrocarbon stream 236 has a temperature of from about 60 to about 150° C. and, independently, a pressure of from about 1,850 to about 5,450 kPa gauge.
The partially cooled liquid phase hydrocarbon stream 234 is introduced to a chiller 220 and is passed through the chiller section 224 to form a cooled liquid phase hydrocarbon stream 83. Although the chiller sections 224 and 226 are shown as being incorporated in separate chillers 220 and 222, respectively, alternatively both of the chiller sections 224 and 226 may be incorporated into a single chiller such as in a dual-bundle chiller (shown with dashed lines 78). In an exemplary embodiment, the cooled liquid phase hydrocarbon stream 83 has a temperature of from about −28 to about 4° C., such as about −12 to about 0° C. and, independently, a pressure of from about 1,890 to about 5,490 kPa gauge.
The cooled, compressed intermediate gas phase stream 80 and the cooled liquid phase hydrocarbon stream 83 are introduced to the absorber 18. In an exemplary embodiment, the cooled, compressed intermediate gas phase stream 80 is introduced to a lower portion of the absorber 18 and rises upwardly while the cooled liquid phase hydrocarbon stream 83 is introduced to an upper portion of the absorber 18 and descends downwardly for countercurrent contact with the rising cooled, compressed intermediate gas phase stream 80. During contact in the absorber 18, C3/C4 hydrocarbons from the cooled, compressed intermediate gas phase stream 80 are extracted and/or absorbed to the cooled liquid phase hydrocarbon stream 83 to form an H2-rich stream 84 and a cooled intermediate liquid phase hydrocarbon stream 82 that is enriched with C3/C4 hydrocarbons and further comprises C5+ hydrocarbons including aromatics. In an exemplary embodiment, the H2-rich stream 84 comprises H2 present in an amount of from about 80 to about 95 mole % with possibly some C4− hydrocarbons. In an exemplary embodiment, the cooled intermediate liquid phase hydrocarbon stream 82 has a temperature of from about −28 to about 4° C., such as about −12 to about 0° C., and, independently, a pressure of from about 1,890 to about 5,490 kPa gauge.
As discussed above, the H2-rich stream 84 is passed through the absorption zone heat exchanger 230 to form the partially heated H2-rich stream 239. The partially heated H2-rich stream 239 is introduced to the PSA zone 20 for further purifying the stream 239 by removing hydrocarbons to form an H2-ultra rich stream 250.
In an exemplary embodiment, the PSA zone 20 contains an adsorbent (e.g., adsorbent material(s)) and is configured for contacting the partially heated H2-rich stream 239 with the adsorbent for selectively separating H2 from hydrocarbons (e.g., C4− hydrocarbons) to form the H2-ultra rich stream 250. The exemplary PSA zone 20 operates on the principle of selectively adsorbing hydrocarbons and/or other impurities onto the adsorbent at a relatively high pressure (e.g., 1,850 to 5,450 kPa gauge) to form the H2-ultra rich stream 250, and desorbing the hydrocarbons from the adsorbent at relatively low pressure (e.g., 10 to 500 kPa gauge) to regenerate the adsorbent and to form a tail gas stream 252 that contains the hydrocarbons and/or other impurities.
In an exemplary embodiment, the PSA zone 20 includes a plurality of fixed-bed adsorption units each containing layers of different adsorbent materials where the lower layer or layers are filled with weaker adsorbent materials, e.g., relatively low affinity for adsorbing gaseous hydrocarbons, and the upper layer or layers are filled with stronger adsorbent materials, e.g., relatively high affinity for adsorbing gaseous hydrocarbons. For example, the lower layer(s) can contain weakly adsorbent materials, such as activated alumina and/or silica gel, while the intermediate layer(s) can contain intermediate strength adsorbent materials, such as activated carbon, and the upper layer(s) can contain strong adsorbent materials, such as zeolite and/or molecular sieve materials. In an exemplary embodiment, the multiple fixed-bed adsorption units cooperatively operate in a staggered sequence to produce constant feed (e.g., the partially heated H2-rich stream 239), product (e.g., the H2-ultra rich stream 250), and tail gas (e.g., the tail gas stream 252) flows. In an exemplary embodiment, the PSA zone 20 operates following a five-step pressure-swing cycle including an adsorption step, a co-current depressurization step, a counter-current depressurization step, a purge step, and a repressurization step. During the adsorption step, the partially heated H2-rich stream 239 enters a lower portion of the fixed-bed adsorption unit at a relatively high pressure, and as the feed gas rises in the unit, the hydrocarbons are adsorbed in the various layers of the adsorbent materials depending upon their respective adsorption selectivity to form the H2-ultra rich stream 250. The co-current depressurization, counter-current depressurization and purge steps decrease the pressure in the fixed-bed adsorption unit and purge the unit with high purity gas from the product (e.g., the H2-ultra rich stream 250) or co-current depressurization steps, respectively, to remove the hydrocarbons and regenerate the adsorption materials. The repressurization step increases the pressure in the fixed-bed adsorption unit with either feed gas (e.g., the partially heated H2-rich stream 239) or product gas (e.g., the H2-ultra rich stream 250) in preparation for the next adsorption step. Other pressure swing adsorption configurations for forming an H2-ultra rich stream known to those skilled in the art may also be used.
In an exemplary embodiment, the H2-ultra rich stream 250 comprises H2 present in an amount of from about 90 to less than 100 mole %, such as from about 90 to about 99.999 mole %, such as from about 95 to about 99.999 mole %, such as from about 98 to about 99.999 mole %, such as from about 99 to about 99.999 mole %, for example about 99.99 mole %, and possibly some C2− hydrocarbons. In an exemplary embodiment, the H2-ultra rich stream 250 has a temperature of from about 2 to about 60° C. and, independently, a pressure of from about 1,850 to about 5,450 kPa gauge, for example about 2,000 to about 2,800 kPa gauge. In an exemplary embodiment, the tail gas stream 252 comprises C4-hydrocarbons present in an amount of from about 25 to about 80 mole %, H2 present in an amount of from about 25 to about 75 mole %, and possibly some C3+ hydrocarbons. In an exemplary embodiment, the tail gas stream 252 has a temperature of from about 2 to about 60° C. and, independently, a pressure of from about 10 to about 500 kPa gauge, for example about 20 to about 50 kPa gauge.
The H2-ultra rich stream 250 is removed from the apparatus 10, for example, to be used as a hydrogen product stream. The tail gas stream 252 is passed through a compressor 254 to form a compressed PSA tail gas stream 255 that is further advanced through a cooler 256 to partially cool the stream 255 and form the partially cooled, compressed PSA tail gas stream 204. In an exemplary embodiment, the partially cooled, compressed PSA tail gas stream 204 has a temperature of from about 35 to about 150° C. and, independently, a pressure of from about 200 to about 1,400 kPa gauge, for example of from about 300 to about 500 kPa gauge.
As discussed above, the recycle portion 202 of the partially cooled, compressed PSA tail gas stream 204 is recycled back and combined with the net gas phase stream 34 just upstream of the compressor 40. The remaining portion of the partially cooled, compressed PSA tail gas stream 204 is passed through a compressor 258 to form a partially cooled, further compressed PSA tail gas stream 259 that is further advanced through a cooler 260 to partially cool the stream 259 and form a further partially cooled, further compressed PSA tail gas stream 262. In an exemplary embodiment, the further partially cooled, further compressed PSA tail gas stream 262 has a temperature of from about 30 to about 60° C. and, independently, a pressure of from about 700 to about 1,400 kPa gauge. The further partially cooled, further compressed PSA tail gas stream 262 is removed from the apparatus 10, for example, to be used as fuel gas.
As discussed above, the cooled intermediate liquid phase hydrocarbon stream 82 exits the absorber 18 and is passed through the absorption zone heat exchanger 228 to form the partially heated intermediate liquid phase hydrocarbon stream 236. The partially heated intermediate liquid phase hydrocarbon stream 236 is passed through a valve 94 to reduce the pressure of the stream 236 and to form a partially heated intermediate liquid phase hydrocarbon stream 98. In an exemplary embodiment, the partially heated intermediate liquid phase hydrocarbon stream 98 has a temperature of from about 60 to about 150° C. and, independently, a pressure of from about 1,000 to about 1,500 kPa gauge.
The partially heated intermediate liquid phase hydrocarbon stream 98 is passed through a stabilizer heat exchanger 100 for indirect heat exchange with a C5+ hydrocarbon-rich reformate stream 102, which is discussed in further detail below, to form a heated intermediate liquid phase hydrocarbon stream 104. Optionally, the partially heated intermediate liquid phase hydrocarbon stream 98 may also include a portion from the liquid phase hydrocarbon stream 36 via line 300. In an exemplary embodiment, the heated intermediate liquid phase hydrocarbon stream 104 has a temperature of from about 150 to about 200° C. and, independently, a pressure of from about 900 to about 1,400 kPa gauge.
The heated intermediate liquid phase hydrocarbon stream 104 is passed along to the stabilizer 22. The stabilizer 22 separates the heated intermediate liquid phase hydrocarbon stream 104 into a stabilizer gas stream 106 that comprises H2 and C4− hydrocarbons enriched with C3/C4 hydrocarbons and the C5+ hydrocarbon-rich reformate stream 102. In an exemplary embodiment, the C5+ hydrocarbon-rich reformate stream 102 comprises C5+ hydrocarbons including aromatics present in an amount of about 90 to about 99.9 mole %. As discussed above, the C5+ hydrocarbon-rich reformate stream 102 is passed through the stabilizer heat exchanger 100 and is removed from the apparatus 10 as a reformate product 107.
The stabilizer gas stream 106 is introduced to the stabilizer gas separation zone 23 and is passed through a first cooler 108 (e.g., an air cooler) and a second cooler 110 (e.g., a water cooler) to partially condense and cool the stream 106 and form a partially condensed stabilizer gas stream 112. In an exemplary embodiment, the partially condensed stabilizer gas stream 112 has a temperature of from about 30 to about 65° C. and, independently, a pressure of from about 800 to about 1,300 kPa gauge.
The partially condensed stabilizer gas stream 112 is passed along to a receiver 114 to remove condensed/liquid hydrocarbons from the stream 112 and to form a stabilizer net gas stream 90 and a C3+ hydrocarbon-containing liquid phase stream 116. The C3+ hydrocarbon-containing liquid phase stream 116 exits the receiver 114 and is passed along through a pump 118 and a valve 119 back to the stabilizer 22 as a recycle stream.
The stabilizer net gas stream 90 is passed towards a condenser 88 (e.g., chiller that uses a refrigerant). Optionally, in an exemplary embodiment, the stabilizer gas separation zone 23 includes a dryer 120 upstream from the condenser 88 for removing water from the stabilizer net gas stream 90 to help avoid the formation of hydrates. In an exemplary embodiment, upstream from the condenser 88, the stabilizer net gas stream 90 includes water present in an amount of about 15 ppm by weight or greater, and after being passed through the dryer 120, the stabilizer net gas stream 90 includes water present in an amount of less than about 15 ppm by weight.
The stabilizer net gas stream 90 is passed through the condenser 88 to partially condense and cool the stream 90 and form a partially condensed stabilizer net gas stream 122. Although the stabilizer net gas stream 90 is shown as being passed through only a single condenser 88, the stream 90 may be partially condensed and cooled by being advanced through one or more heat exchangers, chillers, coolers, or combination thereof. In an exemplary embodiment, the partially condensed stabilizer net gas stream 122 has a temperature of from about −28 to about 4° C., for example, from about −12 to about 0° C. and, independently, a pressure of from about 700 to about 1,200 kPa gauge.
The partially condensed stabilizer net gas stream 122 is introduced to a separator 124. The separator 124 may be configured as a flash drum, or alternatively, may be configured as a multi-stage fractionation tower. The separator 124 separates C3/C4 hydrocarbons and any remaining H2 and C2− hydrocarbons from the partially condensed stabilizer net gas stream 122 to form a light ends gas stream 126 and a C3/C4 hydrocarbon-rich LPG stream 128. In an exemplary embodiment, the C3/C4 hydrocarbon-rich LPG stream 128 comprises C3/C4 hydrocarbons present in an amount of about 70 to about 99.9 mole % and the light ends gas stream 126 comprises H2 present in an amount of from about 1 to about 50 mole %, C2− hydrocarbons present in an amount of from about 20 to about 60 mole %, and possibly some C3+ hydrocarbons. As illustrated, the C3/C4 hydrocarbon-rich LPG stream 128 is passed through a pump 130 and is optionally combined with a side stream 132 of the C3+ hydrocarbon-containing liquid phase stream 116 and is removed from the apparatus 10 as an LPG product stream. The light ends gas stream 126 is removed from the apparatus 10 to be used, for example, as fuel gas.
Accordingly, apparatuses and methods for reforming of hydrocarbons with improved recovery of products from a reforming-zone effluent have been described. The exemplary embodiments taught herein separate a reforming-zone effluent in a separation zone to form a net gas phase stream and a liquid phase hydrocarbon stream. The net gas phase stream is compressed, partially condensed and cooled to form a partially condensed, compressed net gas phase stream. The partially condensed, compressed net gas phase stream is separated in a knockout drum to form an intermediate gas phase stream. In an exemplary embodiment, in an absorption zone, the intermediate gas phase stream is cooled to form a cooled intermediate gas phase stream. The liquid phase hydrocarbon stream is cooled to form a cooled liquid phase hydrocarbon stream. The cooled intermediate gas phase stream is contacted with the cooled liquid phase hydrocarbon stream in an absorber to form an H2-rich stream and a cooled second intermediate liquid phase hydrocarbon stream that is enriched with C3/C4 hydrocarbons. In an exemplary embodiment, the H2-rich stream is passed along to a pressure swing adsorption (PSA) zone that contains an adsorbent for selectively separating H2 from hydrocarbons. In the PSA zone, the H2-rich stream is contacted with the adsorbent to form an H2-ultra rich stream. The cooled second intermediate liquid phase hydrocarbon stream is further separated to form a C5+ hydrocarbon-rich reformate stream, a light ends gas stream, and a C3/C4 hydrocarbon-rich LPG stream.
While at least one exemplary embodiment has been presented in the foregoing detailed description of the disclosure, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the disclosure in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the disclosure. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the disclosure as set forth in the appended claims.

## Claims

1. An apparatus for reforming of hydrocarbons including recovery of products, the apparatus comprising:
a separation zone configured to receive and separate a reforming-zone effluent that comprises H2, C4− hydrocarbons, and C5+ hydrocarbons including aromatics to form a net gas phase stream that comprises H2 and C6− hydrocarbons and a liquid phase hydrocarbon stream that comprises C5+ hydrocarbons;
a first compressor configured to receive and compress the net gas phase stream to form a compressed net gas phase stream;
a first cooler configured to receive and partially condense and cool the compressed net gas phase stream to form a partially condensed, compressed net gas phase stream;
a knockout drum configured to receive and separate the partially condensed, compressed net gas phase stream into an intermediate gas phase stream and a first intermediate liquid phase hydrocarbon stream;
an absorption zone configured to receive and cool the intermediate gas phase stream and the liquid phase hydrocarbon stream to form a cooled intermediate gas phase stream and a cooled liquid phase hydrocarbon stream, respectively, wherein the absorption zone comprises an absorber that is configured for contacting the cooled intermediate gas phase stream with the cooled liquid phase hydrocarbon stream to extract C3/C4 hydrocarbons from the cooled intermediate gas phase stream to the cooled liquid phase hydrocarbon stream and to form an H2-rich stream and a cooled second intermediate liquid phase hydrocarbon stream that is enriched with C3/C4 hydrocarbons and further comprises C5+ hydrocarbons; and
a pressure swing adsorption (PSA) zone containing an adsorbent for selectively separating H2 from hydrocarbons, wherein the PSA zone is configured for receiving the H2-rich stream and for contacting the H2-rich stream with the adsorbent to form an H2-ultra rich stream.

2. The apparatus of claim 1, wherein the separation zone is configured to receive the first intermediate liquid phase hydrocarbon stream as a recycle stream for further separation.

3. The apparatus of claim 1, wherein the absorption zone further comprises a chiller section configured to receive and cool the intermediate gas phase stream to form the cooled intermediate gas phase stream, and wherein the absorber is configured to receive the cooled intermediate gas phase stream to form the H2-rich stream and the cooled second intermediate liquid phase hydrocarbon stream.

4. The apparatus of claim 3, further comprising a dryer that is upstream from the chiller section and is configured to remove water from the intermediate gas phase stream before the intermediate gas phase stream is introduced to the chiller section.

5. The apparatus of claim 3, wherein the absorption zone further comprises an absorption zone heat exchanger that is configured for indirect heat exchange between the intermediate gas phase stream and the H2-rich stream to form a partially cooled intermediate gas phase stream and a partially heated H2-rich stream, respectively, wherein the chiller section is configured to receive and cool the partially cooled intermediate gas phase stream to form the cooled intermediate gas phase stream and the PSA zone is configured to receive the partially heated H2-rich stream to form the H2-ultra rich stream.

6. The apparatus of claim 5, wherein the absorption zone further comprises:
a second compressor configured to receive and compress the intermediate gas phase stream to form a compressed intermediate gas phase stream; and
a second cooler configured to receive and partially cool the compressed intermediate gas phase stream to form a partially cooled, compressed intermediate gas phase stream, wherein the absorption zone heat exchanger is configured for indirect heat exchange between the partially cooled, compressed intermediate gas phase stream and the H2-rich stream to form a further partially cooled, compressed intermediate gas phase stream and the partially heated H2-rich stream, respectively, wherein the chiller section is configured to receive and cool the further partially cooled, compressed intermediate gas phase stream to form a cooled, compressed intermediate gas phase stream as the cooled intermediate gas phase stream.

7. The apparatus of claim 5, wherein the PSA zone is configured to form a PSA tail gas stream that comprises H2, C2− hydrocarbons, and some C3+ hydrocarbons, and wherein the apparatus further comprises:
a first PSA tail gas compressor configured to receive and compress the PSA tail gas stream to form a compressed PSA tail gas stream; and
a first PSA cooler configured to receive and partially cool the compressed PSA tail gas stream to form a partially cooled, compressed PSA tail gas stream, and wherein the first compressor is configured to receive a recycle portion of the partially cooled, compressed PSA tail gas stream to form a portion of the compressed net gas phase stream.

8. The apparatus of claim 7, further comprising:
a second PSA tail gas compressor configured to receive and compress a remaining portion of the partially cooled, compressed PSA tail gas stream to form a partially cooled, further compressed PSA tail gas stream; and
a second PSA cooler configured to receive and partially cool the partially cooled, further compressed PSA tail gas stream to form a further partially cooled, further compressed PSA tail gas stream.

9. The apparatus of claim 1, further comprising:
at least one heater, heat exchanger, or combinations thereof configured to receive and heat the cooled second intermediate liquid phase hydrocarbon stream to form a heated second intermediate liquid phase hydrocarbon stream;
a stabilizer configured to receive and separate the heated second intermediate liquid phase hydrocarbon stream to form a C5+ hydrocarbon-rich reformate stream that comprises primarily C5+ hydrocarbons and a stabilizer gas stream that comprises H2 and C4− hydrocarbons; and
a stabilizer gas separation zone configured to receive and partially condense and cool at least a portion of the stabilizer gas stream to form a partially condensed stabilizer net gas stream, wherein the stabilizer gas separation zone comprises:
a separator configured to receive and separate the partially condensed stabilizer net gas stream to form a C3/C4 hydrocarbon-rich LPG stream that comprises primarily C3/C4 hydrocarbons and a light ends gas stream that comprises H2 and C2− hydrocarbons.

10. The apparatus of claim 9, wherein the stabilizer gas separation zone comprises at least one heat exchanger, chiller, cooler, or combination thereof configured to receive and partially condense and cool the at least the portion of the stabilizer gas stream to form the partially condensed stabilizer net gas stream.