A METHOD FOR CATALYTIC CRACKING OF HYDROCARBONS TO PRODUCE OLEFINS AND AROMATICS WITHOUT STEAM AS DILUENT
20220259505 · 2022-08-18
Assignee
Inventors
- Xie PENG (Dalian, CN)
- Mingzhi LI (Dalian, CN)
- Zhongmin Liu (Dalian, CN)
- Haitao LIU (Shanghai, CN)
- Jinzhe LI (Dalian, CN)
- Talal Khaled AL-SHAMMARI (Riyadh, SA)
Cpc classification
B01J29/80
PERFORMING OPERATIONS; TRANSPORTING
B01J2229/24
PERFORMING OPERATIONS; TRANSPORTING
C10G11/05
CHEMISTRY; METALLURGY
B01J29/405
PERFORMING OPERATIONS; TRANSPORTING
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
C10G11/05
CHEMISTRY; METALLURGY
B01J29/08
PERFORMING OPERATIONS; TRANSPORTING
B01J29/40
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method of producing olefins and/or aromatics is disclosed. The method includes catalyzing a hydrocarbon cracking reaction with a catalyst comprising a mixture of ZSM-5 zeolite and USY zeolite modified with lanthanum. The cracking process includes providing a diluent comprising primarily methane to the reactor, wherein steam is not provided to the reactor as a diluent.
Claims
1. A method of producing olefins and/or aromatics, the method comprising: providing a hydrocarbon feed to a reactor, wherein the reactor has, disposed therein, a catalyst comprising a mixture of ZSM-5 zeolite and USY zeolite modified with lanthanum; providing a diluent comprising primarily methane to the reactor, wherein steam is not provided to the reactor such that water in the reactor is 5 wt. % or less; and contacting a mixture of the hydrocarbon feed and the diluent with the catalyst under reaction conditions sufficient to cause cracking and/or aromatization of compounds in the hydrocarbon feed and thereby producing one or more olefins and/or one or more aromatics.
2. The method of claim 1, wherein the catalyst has a Si to Al ratio by weight of less than 100.
3. The method of claim 1, wherein the reaction conditions comprise a temperature of 550° C. to 750° C.
4. The method of claim 1, wherein the diluent further comprises one or more of H.sub.2, CH.sub.4, N.sub.2, CO.sub.2.
5. The method of claim 1, wherein the hydrocarbon feed comprises a selection from the list consisting of: C.sub.4 to C.sub.40 alkane, cyclanes, olefin, aromatic compounds, and combinations thereof.
6. The method of claim 1, wherein the hydrocarbon feed comprises naphtha.
7. The method of claim 1, wherein the reactor comprises a selection from the list consisting of: a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, and combinations thereof.
8. The method of claim 1, wherein the reaction conditions comprise a LHSV in a range of 0.5 to 5 .sup.−1.
9. The method of claim 1, wherein the reaction conditions comprise a ratio of dilution gas (m.sup.3) to feedstock (kg) of 0 to 10 m.sup.3/kg.
10. The method of claim 1, wherein the catalyst is in service for at least 300 to 400 hours before it is regenerated.
11. The method of claim 1, wherein the yield of olefins and aromatics is at least 60%.
12. The method of claim 1, wherein the yield of olefins and aromatics is at least 70%.
13. The method of claim 3, wherein the yield of olefins and aromatics is at least 70%.
14. The method of claim 4, wherein the yield of olefins and aromatics is at least 70%.
15. The method of claim 5, wherein the yield of olefins and aromatics is at least 70%.
16. The method of claim 6, wherein the yield of olefins and aromatics is at least 70%.
17. The method of claim 7, wherein the yield of olefins and aromatics is at least 70%.
18. The method of claim 8, wherein the yield of olefins and aromatics is at least 70%.
19. The method of claim 9, wherein the yield of olefins and aromatics is at least 70%.
20. The method of claim 10, wherein the yield of olefins and aromatics is at least 70%.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0019]
[0020]
DETAILED DESCRIPTION OF THE INVENTION
[0021] A discovery has been made that provides a solution to at least some of the problems associated with catalytic cracking of hydrocarbons over molecular sieve catalyst to produce olefins and/or aromatics. The solution is premised on using steam free dilution gas conditions for the cracking process in the reactor in order to prevent the dealumination of molecular sieve catalyst.
[0022] According to embodiments of the invention, hydrogen (H.sub.2), (CH.sub.4), (N.sub.2), carbon dioxide (CO.sub.2) or combinations thereof can be used as dilution gas, instead of steam, for the catalytic cracking reaction of hydrocarbons over molecular sieve catalyst to produce olefins and aromatics. Alternatively, according to embodiments of the invention, the catalytic cracking reaction of hydrocarbons over molecular sieve catalyst to produce olefins and aromatics is carried out without dilution gas. By providing steam free conditions, or almost steam free conditions (recognizing although steam is not added as a diluent, steam may enter the catalytic cracking unit, for example, as minute portions of the hydrocarbon feed stream), the catalytic cracking process can maintain initial catalytic activity for a longer period than conventional processes that use steam as a diluent. The steam free conditions provided by embodiments of the invention avoid dealumination of the molecular sieve catalyst that would occur under conditions in which high temperature is combined with steam. As noted above, when steam and high temperatures exist in a process catalyzed by a molecular sieve catalyst, the molecular sieve catalyst can lose frame aluminum, which decreases the acid active sites of the molecular sieve catalyst and thereby the activity of the catalyst.
[0023] As catalyst activity decreases, reaction time increases, and increased coking leads to further catalyst activity decline. In embodiments of the invention, however, performance of the catalyst can completely recover after burning off coke from the catalyst. The method, according to embodiments of the invention, can keep a molecular sieve catalyst performing sufficiently well for at least 370 hours of reaction time. In embodiments of the invention, the catalyst remains in service for at least 300 to 400 hours before it is regenerated. This is an improvement when compared with conventional catalytic cracking processes that use steam as dilution gas because in such situations, the molecular sieve catalyst performs sufficiently well for a maximum of 24 hours. In embodiments of the invention, the target products: ethylene, propylene, butene, and BTX yield, collectively, is as high as 70%. In embodiments of the invention, the yield of olefins and aromatics, collectively, is at least 60%.
[0024]
[0025] Method 20, as implemented by system 10, can include flowing hydrocarbon stream 100 to catalytic cracker 101, at block 200. Hydrocarbon stream 100 may comprise naphtha, gasoline, diesel, and any distilled hydrocarbons or combinations thereof. The naphtha comprised in hydrocarbon stream 100, in embodiments of the invention, includes normal paraffins, iso-paraffins, naphthenes, and aromatics. In embodiments of the invention, hydrocarbon stream 100 comprises C.sub.4 to C.sub.40 of any of the following: alkanes, cyclanes, olefins, aromatic compounds, and combinations thereof. In embodiments of the invention, at block 201, diluent stream 102 may also be flowed to catalytic cracker 101. Diluent stream 102 may include a selection from H.sub.2, CH.sub.4, N.sub.2, CO.sub.2, and combinations thereof. As shown in
[0026] According to embodiments of the invention, catalytic cracker 101 comprises a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, or combinations thereof. According to embodiments of the invention, disposed in catalytic cracker 101 is molecular sieve catalyst 104 adapted to catalyze the cracking of hydrocarbon molecules of hydrocarbon stream 100 to produce olefins and/or aromatics. Molecular sieve catalyst 104, according to embodiments of the invention, includes Si/Al molecular sieve as an active phase, where the structure of frame silicon and aluminum is MFI, Beta, MWW, or MOR; more preferably MFI structure ZSM-5. Molecular sieve catalyst 104, according to embodiments of the invention, may include a mixture of ZSM-5 zeolite and USY zeolite modified with lanthanum, or combinations thereof. In embodiments of the invention the catalyst has a Si to Al ratio by weight of less than 100
[0027] Method 20, according to embodiments of the invention, includes, at block 202, subjecting hydrocarbon stream 100 (e.g., as a part of combined feed stream 103) to reaction conditions, in the presence of molecular sieve catalyst 104, sufficient to crack hydrocarbon molecules of hydrocarbon stream 100 to produce olefins such as ethylene, propylene, and butene and/or aromatics such as benzene, xylene, and toluene. According to embodiments of the invention, the reaction conditions for the catalytic cracking reaction include a temperature in a range of 550 to 750° C. and all ranges and values there between including ranges of 550 to 575° C., 575 to 600° C., 600 to 625° C., 625 to 650° C., 650 to 675° C., 675 to 700° C., 700 to 725° C., and 725 to 750° C. According to embodiments of the invention, the reaction conditions for the catalytic cracking reaction include a pressure in a range of 0.5 to 1.5 atm. According to embodiments of the invention, the reaction conditions for the catalytic cracking reaction include a LHSV in a range of 0.5 to 5 h.sup.−1 and all ranges and values there between including ranges of 0.5 to 1.0 h.sup.−1, 1.0 to 1.5 h.sup.−1, 1.5 to 2.0 h.sup.−1, 2.0 to 2.5 h.sup.−1, 2.5 to 3.0 h.sup.−1, 3.0 to 3.5 h.sup.−1, 3.5 to 4.0 h.sup.−1, 4.0 to 4.5 h.sup.−1, and 4.5 to 5.0 h.sup.−1. According to embodiments of the invention, the reaction conditions for the catalytic cracking reaction include a ratio of dilution gas (m.sup.3) to feedstock (kg) of 0 to 10 m.sup.3/kg and all ranges and values there between including ranges of 0 to 1 m.sup.3/kg, 1 to 2 m.sup.3/kg/2 to 3 m.sup.3/kg, 3 to 4 m.sup.3/kg, 4 to 5 m.sup.3/kg, 5 to 6 m.sup.3/kg, 6 to 7 m.sup.3/kg, 7 to 8 m.sup.3/kg, 8 to 9 m.sup.3/kg and 9 to 10 m.sup.3/kg.
[0028] Method 20, according to embodiments of the invention, includes, at block 203, flowing catalytic cracker effluent 105 from catalytic cracker 101. According to embodiments of the invention, catalytic cracker effluent 105 comprises 10 to 25 wt. % ethylene, 20 to 30 wt. % propylene, 5 to 10 wt. % butene, 4 to 15 wt. % benzene, 5 to 20 wt. % toluene, and 5 to 12 wt. % xylene.
[0029] In embodiments of the invention, catalytic cracker effluent 105 may be separated in separation unit 106 to recover the olefins and aromatics desired in streams 107, at block 204. Additionally or alternatively, catalytic cracker effluent 105 may be processed further to produce additional olefins and/or aromatics, at block 205. Streams 107 may comprise a first stream having primarily C.sub.2 to C.sub.5 olefins and aromatics, a second stream having primarily C.sub.2 to C.sub.4 olefins, third stream having primarily C.sub.2 and C.sub.3. For example, catalytic cracker effluent 105 may be fed to steam cracker 108 to undergo steam cracking to produce steam cracker effluent 109. Reaction conditions for the steam cracking include a temperature in a range of 780 to 870° C. and all ranges and values there between including ranges of 780 to 790° C., 790 to 800° C., 800 to 810° C., 810 to 820° C., 820 to 830° C., 830 to 840° C., 840 to 850° C., 850 to 860° C. and 860 to 870° C. According to embodiments of the invention, the reaction conditions for the steam cracking include a pressure in a range of 0.5 bars to 1.5 bars. According to embodiments of the invention, the reaction conditions for the steam cracking reaction include a LHSV in a range of 0.5 to 2.5 h.sup.−1. According to embodiments of the invention, the reaction conditions for the steam cracking reaction include a ratio of dilution gas (m.sup.3) to feedstock of (kg) 0 to 10 m.sup.3/kg and all ranges and values there between including ranges of 0 to 1 m.sup.3/kg, 1 to 2 m.sup.3/kg/2 to 3 m.sup.3/kg, 3 to 4 m.sup.3/kg, 4 to 5 m.sup.3/kg, 5 to 6 m.sup.3/kg, 6 to 7 m.sup.3/kg, 7 to 8 m.sup.3/kg, 8 to 9 m.sup.3/kg and 9 to 10 m.sup.3/kg.
[0030] In embodiments of the invention, steam cracker effluent 109 comprises 20 to 30 wt. % ethylene, 30 to 40 wt. % propylene, 5 to 10 wt. % butene, and 5 to 10 wt. % BTX (benzene, toluene, and xylene). At block 206, embodiments of the invention may include separating steam cracker effluent 109 by separation unit 110 to form product streams 111.
[0031] Although embodiments of the present invention have been described with reference to blocks of
EXAMPLES
[0032] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the invention. Those of ordinary skill in the art will readily recognize parameters that can be changed or modified to yield essentially the same results.
[0033] In the examples of this application, the yield and selectivity are calculated based on mass. The fixed bed uses molecular sieve catalyst having lanthanum and phosphorus-modified ZSM-5 zeolite in hydrogen form, and the fluidized bed uses molecular sieve catalyst having
[0034] LaZSM-5 mixed with USY. The reaction of olefin and aromatic hydrocarbons is catalyzed by hydrocarbon compounds in a steam-free atmosphere.
TABLE-US-00001 TABLE 1 Classified Feedstock-Naphtha Normal Naphthenic Aromatic Paraffin Iso-paraffin species Species content content content content Feedstock (wt. %) (wt. %) (wt. %) (wt. %) Naphtha 41.04 24.23 15.26 14.49
Example 1
The Catalytic Cracking of Naphtha Using H.SUB.2 .as Diluted Gas
[0035] Reaction conditions for Example 1 include a reaction temperature of 630 to 670° C., a raw material space velocity of 1.2 h.sup.−1, and a gas oil ratio is 0.6 m.sup.3/kg.
[0036] The results obtained for Example 1 are shown in Table 2. In each recycle period, with the increase of reaction time, the coking amount increases and the activity decreases. The initial activity can be restored after regeneration (burnt in air under 700° C. for 2 hours). In the initial stage, the yield of the target product can reach 70%. The way of controlling the reaction temperature affects the yield and the length of time of the single operation period.
TABLE-US-00002 TABLE 2 Yield of Products in 8 Recycle Period Using H.sub.2 as Diluted Gas Recycle No. 1 2 3 4 5 6 7 8 Reaction time, hour 30.5 34.6 35 21.7 23.2 30.5 109.9 76.9 Products Average yield (wt. %) CH.sub.4 6.29 5.58 5.54 6.59 6.44 4.65 3.78 4.45 C.sub.2H.sub.6 5.04 4.41 4.24 5.02 4.80 3.94 3.22 3.30 C.sub.2H.sub.4 14.18 13.85 13.79 14.74 14.93 13.07 10.54 12.54 C.sub.3H.sub.8 4.43 4.42 4.15 4.37 4.27 4.98 4.23 4.52 C.sub.3H.sub.6 15.83 18.07 18.18 17.10 18.27 17.96 17.81 18.90 C.sub.4H.sub.10 1.90 2.31 2.16 1.78 1.88 2.65 2.65 2.70 C.sub.4H.sub.8 4.09 5.13 5.21 4.39 4.85 5.62 6.28 5.84 C.sub.5 1.05 1.21 1.20 1.03 1.11 1.38 1.61 1.37 C.sub.6+ 21.70 20.72 21.64 18.01 17.57 21.89 29.09 22.94 Benzene 8.24 7.62 7.55 9.38 8.97 7.19 5.91 7.14 Toluene 10.30 9.74 9.42 10.76 10.26 9.74 8.11 9.20 Xylene 6.95 6.93 6.92 6.83 6.66 6.93 6.76 7.11 C.sub.2H.sub.4 + C.sub.3H.sub.6 30.01 31.92 31.97 31.84 33.20 31.03 28.35 31.44 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 34.10 37.05 37.19 36.23 38.05 36.65 34.64 37.27 BTX 25.49 24.29 23.89 26.97 25.88 23.86 20.78 23.45 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 + BTX 59.59 61.35 61.08 63.20 63.93 60.51 55.42 60.72
Example 2
The catalytic Cracking of Naphtha Using H.SUB.2.+CH.SUB.4 .as Diluted Gas
[0037] Reaction conditions for Example 2 include a reaction temperature of 630 to 660° C., a raw material space velocity is 1.2 h.sup.−1, a gas oil ratio of 0.83 m.sup.3/kg, and H.sub.2:CH.sub.4=1:1. The results for Example 2 are shown in Table 3.
TABLE-US-00003 TABLE 3 Yield of Products Using H.sub.2 + CH.sub.4 as Diluted Gas Reaction time (hour) 0.5 2.1 3.7 5.3 6.9 Temperature (° C.) 630 630 640 650 660 CH.sub.4 7.23 7.56 7.66 8.09 8.47 C.sub.2H.sub.6 4.54 3.88 3.91 3.99 4.05 C.sub.2H.sub.4 18.65 16.46 16.84 17.19 17.45 C.sub.3H.sub.8 5.02 4.89 4.62 4.34 4.05 C.sub.3H.sub.6 18.61 18.91 19.16 19.15 18.90 C.sub.4H.sub.10 2.18 2.77 2.42 2.08 1.74 C.sub.4H.sub.8 5.08 5.60 5.37 5.02 4.57 C.sub.5 1.82 2.42 2.09 1.79 1.52 C.sub.6+ 14.58 14.50 13.40 12.64 12.07 Benzene 7.50 8.05 9.00 9.81 10.75 Toluene 9.41 9.47 9.89 10.21 10.64 Xylene 5.37 5.51 5.64 5.70 5.78 C.sub.2H.sub.4 + C.sub.3H.sub.6 37.26 35.37 36.00 36.35 36.35 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 42.34 40.96 41.37 41.37 40.92 BTX 22.28 23.02 24.53 25.71 27.17 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 + BTX 64.62 63.98 65.90 67.09 68.09
Example 3
The Catalytic Cracking of Naphtha Using CH.SUB.4 .as Diluted Gas
[0038] Reaction conditions for Example 3 includes a reaction temperature 630 to 660° C., a raw material space velocity is 1.2 h.sup.−1, and a gas oil ratio of 0.6 m.sup.3/kg.
[0039] The reaction results for Example 3 are shown in Table 4.
TABLE-US-00004 TABLE 4 Yield of Products Using CH.sub.4 as Diluted Gas Reaction time (hour) 0.5 2.1 3.7 5.3 6.9 Temperature (° C.) 630 630 640 650 660 CH.sub.4 2.22 5.93 7.43 8.41 8.67 C.sub.2H.sub.6 3.44 3.46 3.54 3.66 3.72 C.sub.2H.sub.4 14.80 15.16 15.84 16.59 16.94 C.sub.3H.sub.8 4.87 4.88 4.65 4.45 4.19 C.sub.3H.sub.6 15.93 17.10 17.69 18.23 18.33 C.sub.4H.sub.10 2.25 2.44 2.21 1.97 1.73 C.sub.4H.sub.8 4.63 5.05 4.95 4.81 4.56 C.sub.5 2.04 2.31 2.09 1.88 1.70 C.sub.6+ 23.13 19.06 16.24 13.24 12.70 Benzene 7.71 7.99 8.74 9.62 10.21 Toluene 11.48 10.48 10.61 11.01 11.14 Xylene 7.52 6.12 6.01 6.13 6.10 C.sub.2H.sub.4 + C.sub.3H.sub.6 30.72 32.26 33.53 34.82 35.27 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 35.35 37.31 38.48 39.62 39.83 BTX 26.70 24.60 25.36 26.76 27.46 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 + BTX 62.06 61.91 63.84 66.39 67.28
Example 4
The Catalytic Cracking of Naphtha Using CO.SUB.2 .as Diluted Gas
[0040] Reaction conditions for Example 4 include a reaction temperature 630 to 660° C., a raw material space velocity of 1.2 h.sup.−1, and a gas oil ratio is 0.6 m.sup.3/kg.
[0041] The reaction results for Example 4 are shown in Table 5.
TABLE-US-00005 TABLE 5 Yield of Products Using CO.sub.2 as Diluted Gas Reaction time (hour) 0.5 2.1 3.7 5.3 6.9 Temperature (° C.) 630 630 640 650 660 CH.sub.4 3.83 3.66 4.00 4.40 4.81 C.sub.2H.sub.6 4.81 4.63 4.67 4.70 4.64 C.sub.2H.sub.4 18.70 17.48 17.52 17.48 17.30 C.sub.3H.sub.8 5.45 5.25 4.85 4.48 4.08 C.sub.3H.sub.6 18.82 19.38 19.85 20.15 20.52 C.sub.4H.sub.10 2.31 2.56 2.39 2.21 2.08 C.sub.4H.sub.8 5.40 5.78 5.72 5.58 5.49 C.sub.5 2.93 3.57 3.40 3.18 3.16 C.sub.6+ 19.16 20.17 19.60 19.00 18.55 Benzene 4.88 4.57 5.01 5.63 6.21 Toluene 8.57 8.03 8.17 8.41 8.43 Xylene 5.15 4.94 4.81 4.80 4.72 C.sub.2H.sub.4 + C.sub.3H.sub.6 37.53 36.85 37.37 37.63 37.82 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 42.93 42.63 43.08 43.21 43.31 BTX 18.60 17.54 18.00 18.83 19.37 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 + BTX 61.53 60.17 61.08 62.04 62.68
Example 5
The Catalytic Cracking of Naphtha Using N.SUB.2 .as Diluted Gas
[0042] Reaction conditions for Example 5 include a reaction temperature 630 to 660° C., a raw material space velocity of 1.2 h.sup.−1, and a gas oil ratio of 0.5 m.sup.3/kg.
[0043] The reaction results for Example 5 are shown in Table 6.
TABLE-US-00006 TABLE 6 Yield of Products Using N.sub.2 as Diluted Gas Reaction time (hour) 0.50 2.10 3.70 5.30 6.90 Temperature (° C.) 650 650 650 650 650 CH.sub.4 4.44 6.01 5.87 5.65 5.30 C.sub.2H.sub.6 3.93 4.62 4.36 4.19 4.08 C.sub.2H.sub.4 15.05 17.87 16.63 15.81 14.97 C.sub.3H.sub.8 4.28 5.13 4.78 4.52 4.30 C.sub.3H.sub.6 14.05 19.04 19.30 19.64 19.88 C.sub.4H.sub.10 1.35 2.08 2.22 2.30 2.51 C.sub.4H.sub.8 3.96 5.44 5.79 5.89 6.19 C.sub.5 1.33 2.00 2.35 2.70 3.28 C.sub.6+ 16.93 11.96 13.50 15.66 18.10 Benzene 6.30 7.86 7.79 7.39 6.65 Toluene 14.13 11.39 10.92 10.11 9.07 Xylene 14.25 6.61 6.50 6.14 5.67 C.sub.2H.sub.4 + C.sub.3H.sub.6 29.10 36.90 35.94 35.44 34.84 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 33.06 42.34 41.72 41.34 41.03 BTX 34.68 25.85 25.21 23.63 21.39 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 + BTX 67.74 68.19 66.93 64.97 62.42
Example 6
The Catalytic Cracking of Naphtha Using H.SUB.2 .as Diluted Gas in Fluidized Bed
[0044] Reaction conditions for Example 6 includes a reaction temperature 660° C., a raw material space velocity of 1.2 h .sup.−1, a gas oil ratio of 0.42 m.sup.3/kg.
[0045] The reaction results are shown in Table 7.
TABLE-US-00007 TABLE 7 Yield of Products Using H.sub.2 as Diluted Gas in Fluidized Bed Reactor Gas oil ratio (M.sup.3/Kg) 0.42 0.42 0.42 0.42 Space velocity (h.sup.−1) 1.2 1.2 1.2 1.2 Linear velocity (cm/s) 2.72 2.72 2.72 2.72 Temperature (° C.) 660 660 660 660 Reaction time (hour) 0.25 1.85 3.45 5.05 CH.sub.4 7.55 6.86 6.42 6.27 C.sub.2H.sub.6 5.32 4.98 4.53 4.26 C.sub.2H.sub.4 10.45 9.82 9.55 9.38 C.sub.3H.sub.8 3.08 3.25 2.98 2.79 C.sub.3H.sub.6 8.78 11.82 13.30 14.19 C.sub.4H.sub.10 0.73 1.26 1.58 1.77 C.sub.4H.sub.8 1.85 2.44 3.99 4.81 C.sub.5 0.92 1.90 3.03 4.00 C.sub.6+ 14.42 16.61 19.81 21.53 Benzene 19.41 15.76 13.47 11.95 Toluene 19.91 17.62 14.79 13.00 Xylene 7.58 7.67 6.55 6.05 C.sub.2H.sub.4 + C.sub.3H.sub.6 19.23 21.64 22.85 23.57 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 21.08 24.08 26.84 28.38 BTX 46.90 41.06 34.81 31.00 C.sub.2H.sub.4 + C.sub.3H.sub.6 + C.sub.4H.sub.8 + BTX 67.97 65.13 61.65 59.38
[0046] In the context of the present invention, at least the following 12 embodiments are described. Embodiment 1 is a method of producing olefins and/or aromatics. The method includes providing a hydrocarbon feed to a reactor, wherein the reactor has, disposed therein, a catalyst containing a mixture of ZSM-5 zeolite and USY zeolite modified with lanthanum. The method also includes providing a diluent containing primarily methane to the reactor, wherein steam is not provided to the reactor such that water in the reactor is 5 wt. % or less. The method further includes contacting a mixture of the hydrocarbon feed and the diluent with the catalyst under reaction conditions sufficient to cause cracking and/or aromatization of compounds in the hydrocarbon feed and thereby producing one or more olefins and/or one or more aromatics. Embodiment 2 is the method of embodiment 1, wherein the catalyst has a Si to Al ratio by weight of less than 100. Embodiment 3 is the method of either of embodiments 1 or 2, wherein the reaction conditions include a temperature of 550° C. to 750° C. Embodiment 4 is the method of any of embodiments 1 to 3, wherein the diluent further contains one or more of H.sub.2, CH.sub.4, N.sub.2, CO.sub.2. Embodiment 5 is the method of any of embodiments 1 to 4, wherein the hydrocarbon feed includes a selection from the list consisting of: C.sub.4 to C.sub.40 alkane, cyclanes, olefin, aromatic compounds, and combinations thereof. Embodiment 6 is the method of any of embodiments 1 to 5, wherein the hydrocarbon feed contains naphtha. Embodiment 7 is the method of any of embodiments 1 to 6, wherein the reactor includes a selection from the list consisting of: a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, and combinations thereof. Embodiment 8 is the method of any of embodiments 1 to 7, wherein the reaction conditions include a LHSV in a range of 0.5 to 5 h.sup.−1. Embodiment 9 is the method of any of embodiments 1 to 8, wherein the reaction conditions include a ratio of dilution gas (m.sup.3) to feedstock (kg) of 0 to 10 m.sup.3/kg. Embodiment 10 is the method of any of embodiments 1 to 9, wherein the catalyst is in service for at least 300 to 400 hours before it is regenerated. Embodiment 11 is the method of any of embodiments 1 to 10, wherein the yield of olefins and aromatics is at least 60%. Embodiment 12 is the method of any of embodiments 1 to 10, wherein the yield of olefins and aromatics is at least 70%.
[0047] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.