PROCESS FOR THE PRODUCTION OF LIGHT OLEFINS AND AROMATICS FROM A HYDROCARBON FEEDSTOCK
20170009157 · 2017-01-12
Inventors
Cpc classification
C10G2300/1059
CHEMISTRY; METALLURGY
C10G2300/1044
CHEMISTRY; METALLURGY
C10G69/06
CHEMISTRY; METALLURGY
C10G69/00
CHEMISTRY; METALLURGY
Y02P30/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
The present invention relates to a process for increasing the production of a light olefin hydrocarbon compound from a hydrocarbon feedstock, comprising the following steps of: (a) feeding a hydrocarbon feedstock into a reaction area for ringopening (b) separating reaction products, which are generated from said reaction area, into an overhead stream and a side stream; (c) feeding the side stream from (b) to a gasoline hydrocracker (GHC) unit, (d) separating reaction products of said GHC of step (c) into an overhead stream, which contains hydrogen, methane, ethane, and liquefied petroleum gas, and a stream, which contains aromatic hydrocarbon compounds, and a small amount of hydrogen and non-aromatic hydrocarbon compounds, (e) feeding the overhead stream from the gasoline hydrocracker (GHC) unit into a steam cracker unit.
Claims
1. A process for increasing the production of a light olefin hydrocarbon compound from a hydrocarbon feedstock, comprising: (a) feeding a hydrocarbon feedstock into a reaction area for ring opening operating at a temperature range of 300-500 C. and a pressure range of 2-10 MPa, (b) separating reaction products, which are generated from said reaction area, into an overhead stream and a side stream; (c) feeding the side stream from (b) to a gasoline hydrocracker (GHC) unit operating at a temperature range of 300-580 C. and a pressure range of 0.3-5 MPa, wherein said gasoline hydrocracker (GHC) unit is operated at a temperature higher than said ring opening reaction area, and wherein said gasoline hydrocracker (GHC) unit is operated at a pressure lower than said ring opening reaction area, (d) separating reaction products of said GHC of step (c) into an overhead gas stream, comprising C2-C4 paraffins, hydrogen and methane and a stream comprising aromatic hydrocarbon compounds and non-aromatic hydrocarbon compounds, and (e) feeding the overhead gas stream from the gasoline hydrocracker (GHC) unit into a steam cracker unit.
2. The process as set forth in claim 1, further comprising pretreating the hydrocarbon feedstock in an aromatics extraction unit, from which aromatics extraction unit its bottom stream is fed into said reaction area for ring opening and its overhead stream is fed into said steam cracker unit.
3. The process as set forth in claim 2, wherein said aromatics extraction unit is of the type of a distillation unit, or wherein said aromatics extraction unit is of the type of a solvent extraction unit, or wherein said aromatics extraction unit is of the type of a molecular sieve.
4.-5. (canceled)
6. The process as set forth in claim 3, wherein in said solvent extraction unit its overhead stream is washed for removal of solvent, wherein the thus recovered solvent is returned into said solvent extraction unit and the overhead stream thus washed being fed into said steam cracker unit.
7. The process as set forth in claim 1, further comprising separating C2-C4 paraffins from said overhead gas stream, and feeding said C2-C4 paraffins thus separated to the furnace section of a steam cracker unit.
8. The process according to claim 7, further comprising separating C2-C4 paraffins in individual streams, each stream predominantly comprising C2 paraffins, C3 paraffins and C4 paraffins, respectively, and feeding each individual stream to a specific furnace section of said steam cracker unit.
9. (canceled)
10. The process as set forth in claim 1, further comprising separating reaction products of said steam cracking unit into an overhead stream, comprising C2-C6 alkanes, a middle stream comprising C2-olefins, C3-olefins and C4-olefins, and a first bottom stream, comprising C9+ hydrocarbons, and a second bottom stream comprising aromatic hydrocarbon compounds and non-aromatic hydrocarbon compounds.
11. The process as set forth in claim 10, further comprising returning said overhead stream to said steam cracking unit.
12. The process as set forth in claim 10, further comprising feeding said second bottom stream into said gasoline hydrocracker (GHC) unit and further comprising feeding said first bottom stream reaction area for ring opening.
13. (canceled)
14. The process as set forth in claim 12, further comprising separating said bottom stream from reaction products of said gasoline hydrocracker (GHC) unit in a BTX rich fraction and in heavy fraction.
15. The process as set forth in claim 1, further comprising feeding said overhead stream from the gasoline hydrocracker (GHC) unit to a dehydrogenation unit.
16. The process as set forth in claim 1, further comprising feeding said overhead stream from the reaction area for ring opening to a dehydrogenation unit.
17. The process as set forth in claim 1, further comprising recovering a stream rich in mono aromatics from said hydrocarbon feedstock of step (a) and feeding the stream thus recovered to said gasoline hydrocracker (GHC) unit.
18. The process as set forth in claim 1, further comprising recovering hydrogen from the reaction products of said steam cracking unit and feeding the hydrogen thus recovered to said gasoline hydrocracker (GHC) unit and/or said reaction area for ring opening.
19. The process as set forth in claim 16, further comprising recovering hydrogen from said dehydrogenation unit and feeding the hydrogen thus recovered to said gasoline hydrocracker (GHC) unit and/or said reaction area for ring opening.
20. The process as set forth in claim 1, wherein said hydrocarbon feedstock into said reaction area for ring opening is gasoil, vacuum gas oil (VGO), naphtha and pretreated naphtha, or a combination thereof.
20. (canceled)
21. The process as set forth in claim 1, wherein the process conditions prevailing in said gasoline hydrocracker (GHC) unit are a reaction temperature of 300-580 C., a pressure of 0.300-5000 kPa MPa gauge, a Weight Hourly Space Velocity (WHSV) of 0.1-10 h-1.
22. The process as set forth in claim 1, wherein the process conditions prevailing in said steam cracking unit include a reaction temperature of 750-900 C., a residence time of 50-1000 milliseconds and a pressure of atmospheric up to 175 kPa gauge.
23. (canceled)
24. The process as set forth in claim 1, wherein in step (e) the overhead gas stream from the gasoline hydrocracker (GHC) unit is directly fed into the furnace section of said steam cracker unit.
25. (canceled)
26. The process as set forth in claim 1, wherein the process conditions prevailing in said reaction area for ring opening are a temperature from 300 C. to 500 C. and a pressure from 2 to 10 MPa together with from 100 to 300 kg of hydrogen per 1,000 kg of feedstock over an aromatic hydrogenation catalyst and passing the resulting stream to a ring cleavage unit at a temperature from 200 C. to 600 C. and a pressure from 1 to 12 MPa together with from 50 to 200 kg of hydrogen per 1,000 kg of said resulting stream over a ring cleavage catalyst.
Description
[0074] The sole FIGURE provides a schematic flow sheet of an embodiment of the present invention.
EXAMPLE
[0075] The process scheme can be found in the sole FIGURE. A hydrocarbon feedstock 29 is fed into a reaction area for ringopening 4 and its reaction products, which are generated from said reaction area, are separated into an overhead stream 9 and a side stream 13. The side stream 13 is fed into a gasoline hydrocracker (GHC) unit 5, wherein the reaction products of said GHC unit 5 are separated into an overhead gas stream 33, comprising light components such C2-C4 paraffins, hydrogen and methane, and a stream 15 comprising predominantly aromatic hydrocarbon compounds and non-aromatic hydrocarbon compounds. The overhead gas stream 33 from the gasoline hydrocracker (GHC) unit 5 is fed as feedstock 8 to a steam cracker unit 1.
[0076] In a preferred embodiment hydrocarbon feedstock 7 can be divided in a feed 28 and a feed 12, wherein feed 28 is pretreated in an aromatics extraction unit 3. From aromatics extraction unit 3 its bottom stream 34 is fed into said reaction area for ringopening 4 and its overhead stream 26 is fed into said steam cracker unit 1. The aromatics extraction unit 3 is chosen from the group of the type of a distillation unit, a solvent extraction unit and a molecular sieve, or even a combination thereof. For example light Naphtha 6 is a feedstock directly sent to the steam cracker unit 1.
[0077] In a preferred embodiment the C2-C4 paraffins are separated from said overhead gas stream 33, and the C2-C4 paraffins thus separated are sent to the furnace section of steam cracker unit 1. In another preferred embodiment the C2-C4 paraffins are separated in individual streams, each stream predominantly comprising C2 paraffins, C3 paraffins and C4 paraffins, respectively, and each individual stream is fed to a specific furnace section of steam cracker unit 1. Such a separation of C2-C4 paraffins from said overhead gas stream 33 is carried out by cryogenic distillation or solvent extraction.
[0078] The reaction products 18 of said steam cracking unit 1 are separated in separator 2 into an overhead stream 17, comprising C2-C6 alkanes, a middle stream 14, which contains C2-olefins, C3-olefins and C4-olefins, and a first bottom stream 19 comprising C9+ hydrocarbons, and a second bottom stream 10 comprising aromatic hydrocarbon compounds and non-aromatic hydrocarbon compounds. Second bottom stream 10 comprises pygas. Hydrogen and methane can be recovered from separator 2 as well and re-used elsewhere. The overhead stream 17 is returned to said steam cracking unit 1. Second bottom stream 10 is fed into said gasoline hydrocracker (GHC) unit 5. First bottom stream 19 predominantly containing carbon black oil (CBO) and cracked distillates (CD) is fed into said reaction area for ringopening 4.
[0079] In a preferred embodiment stream 15 from said gasoline hydrocracker (GHC) unit 5 is further separated in a BTX rich fraction and in heavy fraction (not shown). Overhead stream 33 from the gasoline hydrocracker (GHC) unit 5 is divided into a stream 8 and a stream 20, wherein stream 20 is fed to a dehydrogenation unit 23. As mentioned before, it is preferred to send only the C3-C4 fraction of overhead stream 33 to the dehydrogenation unit 23. Overhead stream 9 from the reaction area for ring opening 4 can also be fed into dehydrogenation unit 23 and/or into steam cracker unit 1. And for this stream 9 it is also preferred to send only the C3-C4 fraction of stream 9 to the dehydrogenation unit 23. According to a preferred embodiment the C3-C4 fractions are recovered from both stream 9 and stream 33 in a single process unit and these C3-C4 fractions are sent to the dehydrogenation unit 23. This means that after suitable processing hydrogen and methane are removed from stream 9 and stream 33 before sending stream 20 to the dehydrogenation unit 23.
[0080] In a preferred embodiment a stream 25 rich in mono aromatics is recovered from said hydrocarbon feedstock 24 and stream 25 thus recovered is directly fed into said gasoline hydrocracker (GHC) unit 5. The remaining part 32 of feedstock 24 is sent to a reaction area for ringopening 4.
[0081] Hydrogen 27 can be recovered from the reaction products 18 of said steam cracking unit 1 and the hydrogen 27 thus recovered can be sent to said gasoline hydrocracker (GHC) unit 5 and/or said reaction area for ring opening 4 via line 22 and line 31, respectively. In another embodiment it is also possible to recover hydrogen 21 from said dehydrogenation unit 23 and the hydrogen 21 thus recovered can be fed into said gasoline hydrocracker (GHC) unit 5 and/or said reaction area for ring opening 4.
[0082] According to the process scheme of FIGURE feedstock 7 can be divided in a feedstock 28 and a feedstock 12, wherein feedstock 12 does not undergo an extraction in the aromatics extraction unit 3. Feedstock 12 can be mixed with other types of feedstock 29, if appropriate, and the combined feedstock 16, after being mixed, if necessary, with the bottom stream 34 of unit 3, is now indicated as reference number 24. In a preferred embodiment mono aromatics 25 are separated from feedstock 24 in unit 30 and the stream 32 thus obtained is fed into unit 4.
[0083] The Example disclosed herein makes a distinction between several cases.
[0084] According to case 1 kerosine as feedstock is sent directly to steam cracker unit (comparative example).
[0085] According to case 2 (example according to the invention) kerosine as feedstock is sent to a reaction area for ringopening and the side stream thereof is sent to a gasoline hydrocracker (GHC) unit, the LPG fraction from GHC being steam cracked.
[0086] According to case 3 (example according to the invention) kerosine as feedstock is first pretreated in an aromatics extraction unit, wherein the paraffins fraction is sent to a steam cracker unit and the naphthenes and aromatics fraction is sent to a reaction area for ringopening and the side stream thereof is sent to a gasoline hydrocracker (GHC) unit, the LPG fraction from GHC being steam cracked.
[0087] Case 4 (example according to the present invention) is similar to case 2 but the feedstock in case 4 is now LVGO.
[0088] The characteristics of kerosine and LVGO can be found in Table 1.
TABLE-US-00001 TABLE 1 characteristics of kerosine and LVGO Kerosine LVGO n-Paraffins wt-% 23.7 18.3 i-Paraffins wt-% 17.9 13.8 Naphthenes wt-% 37.4 35.8 Aromatics wt-% 21.0 32.0 Density 60 F. kg/L 0.810 0.913 IBP C. 174 306 BP10 C. 196 345 BP30 C. 206 367 BP50 C. 216 384 BP70 C. 226 404 BP90 C. 242 441 FBP C. 266 493
[0089] The conditions of the steam cracker unit are as follows: ethane and propane furnaces:coil outlet temperature=845 C., steam-to-oil-ratio=0.37, C4-furnaces: coil outlet temperature=820 C., Steam-to-oil-ratio=0.37, liquid furnaces: coil outlet temperature=820 C., steam-to-oil-ratio=0.37.
[0090] Table 2 shows the battery limit product slate (wt. % of feedstock).
TABLE-US-00002 TABLE 2 the battery limit product slate (wt. % of feedstock) CASE 2 CASE 3 KEROSINE TO KEROSINE TO CASE 4 PARTIAL DEARO, paraffins to LVGO TO PARTIAL CASE 1 RINGOPENING + SC, arom + naphthenes RINGOPENING + BATTERY LIMIT PRODUCT SLATE KEROSINE to SC GHC + SC to PARO GHC GHC + SC H2 production (SC) 0.6 2.5 1.6 2.5 H2 consumption (P-ARO + GHC) 0 3.5 2.1 4.5 CH4 14.4 18.6 15.8 18.9 ETHYLENE 29.0 47.7 42.6 48.6 PROPYLENE 15.1 12.4 15.4 12.6 BUTADIENE 4.9 2.4 4.1 2.5 ISO-BUTENE 2.0 0.5 0.9 0.5 BENZENE 7.9 5.4 7.2 5.0 TX CUT 4.0 6.4 7.1 5.6 STYRENE 1.6 3.0 3.2 2.6 OTHER C7-C8 2.3 0.3 0.6 0.3 C9 RESIN FEED 4.8 0.1 0.2 0.1 CD 1.6 0.0 0.2 0.0 CBO 11.6 0.5 1.0 0.6 % HIGH VALUE CHEMICALS 66.8 78.1 81.1 77.7
[0091] For each case the hydrogen balance was calculated. For case 1 the H2 balance is +0.6%, for case 2 the H2 balance is 1.0%, for case 3 the H2 balance is 0.5%, and for case 4 the H2 balance is 2.0%, respectively.
[0092] The data presented above show that the presence of a reaction area for ringopening and gasoline hydrocracking (GHC) of the diesel converts aromatics into BTX and LPG and converts naphthenes into LPG. The steam cracker product from this LPG contains increased olefins yields (ethylene and propylene), increased CH4 yield and decreased C9+ yield (compared to steam cracking diesel straight away as in case 1). The present inventors found that this effect also applies to LVGO and HVGO. It is to be noted that a reaction area for ringopening requires additional H.sub.2, i.e. a negative hydrogen balance for cases 2, 3, and 4. Moreover, when applying the propane dehydrogenation (PDH)/butane dehydrogenation (BDH) options a positive hydrogen balance can be achieved. Furthermore, the rise in ethylene is also highly remarkable in the method according to the present invention.