Method for Improving Oil Quality and Increasing Yield of Low-carbon Olefins by Utilizing Bio-Oil Catalytic Cracking

Abstract

The Invention discloses a method for improving the quality of oil products and increasing the yield of low-carbon olefins by catalytic cracking of bio-oil, which takes bio-oil or mixed oil of bio-oil and hydrocarbon oil as raw oil for catalytic cracking reaction. With this method, the octane number of the gasoline in product is obviously increased, simultaneously, the content of propylene and other low-carbon olefins in product is also improved.

Claims

1. A method for catalytic cracking of bio-oil, wherein the bio-oil or mixed oil of bio-oil and hydrocarbon oil is used as raw oil for catalytic cracking reaction; the bio-oil has hydrogen/carbon molar ratio 1.75-3:1 and carbon/oxygen molar ratio 8-12:1.

2. The method according to claim 1, wherein the bio-oil has hydrogen/carbon molar ratio 1.75-1.95:1 and carbon/oxygen molar ratio 8-9.5:1.

3. The method according to claim 1, wherein the biological oil includes palm oil, peanut oil, soybean oil and/or sewer oil; the hydrocarbon oil includes straight distillate oil, atmospheric residual oil and/or vacuum residual oil.

4. The method according to claim 3, wherein the hydrocarbon oil is coker gas oil, deasphalted oil, foot oil from raw paraffin and/or extract oil.

5. The method according to claim 1, wherein the catalytic cracking is comprised three parts of: reaction-regeneration system, fractionation system and absorption-stabilization system.

6. The method according to claim 1, wherein the catalytic cracking reaction is as follows: biological oil or mixed oil of biological oil and hydrocarbon oil is used as raw oil and undergoes catalytic cracking or cracking reaction in device, cracked product is obtained under the action of catalyst, the cracked product and catalyst are separated by cyclone, and then the products are further separated by fractionation system and absorption-stabilization system.

7. The method according to claim 1, wherein in the catalytic cracking reaction, the catalyst consists of zeolite, inorganic matrix, clay and binder, with 25%-40% content of zeolite.

8. The method according to claim 7, wherein the zeolite consists of Y-type zeolite and ZSM-5 zeolite.

9. The method according to claim 8, wherein the Y-type zeolite is USY zeolite, or Y-type zeolite and USY zeolite modified with one or more elements of rare earth, phosphorus and alkaline earth metal.

10. The method according to claim 8, wherein the ZSM-5 zeolite accounts by no less than 3% of the total zeolite; the mole ratio of SiO2/Al2O3 of ZSM-5 zeolite is 20-50:1.

11. The method according to claim 8, wherein the ZSM-5 zeolite is ZSM-5 zeolite modified with phosphorus and/or rare earth.

12. The method according to claim 1, wherein in the catalytic cracking reaction, the catalyst comprises 40%-60% of modified 10 MR zeolite, 20%-40% of clay, 10%-20% of alumina matrix and 1%-12% of binder on a dry basis.

13. The method according to claim 12, wherein the modified 10 MR zeolite is modified with IIIA group and phosphorus element through a post-modification method, with 10˜100:1 molar ratio of SiO2/Al2O3, 1-5% content of P2O5, and 0.1-3% oxide content of IIIA group element.

14. The method according to claim 12, wherein the 10 MR zeolite is one of the MFI zeolite, MEL zeolite, MFS zeolite, MWW zeolite and MTT zeolite.

15. The method according to claim 12, wherein the alumina matrix is built up of one or more of alumina, aluminum hydroxide monohydrate and aluminum hydroxide trihydrate.

16. The method according to claim 7, wherein the inorganic matrix is composed of alumina and/or modified alumina.

17. The method according to claim 7, wherein the binder is composed of one or more of alumina, silica, alumina-silica and phosphorus-alumina; the clay is selected from one or more of kaolinite, montmorillonite and attapulgite.

18. The method according to claim 1, wherein in the reaction, the mass ratio of catalyst to raw oil is 4-20.

19. The method according to claim 1, wherein the reaction outlet temperature is 490-650° C.; the weight hourly space velocity based on raw materials is 0.2-20h-1.

20. The method according to claim 1, wherein ethylene, propylene, gasoline and diesel oil are obtained, and the total yield of ethylene and propylene is more than 30%.

Description

MOST PREFERRED EMBODIMENTS OF THE INVENTION

Embodiment 1

[0030] Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2 kg (dry-basis) pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 3.55 kg (dry basis) RE/USY (RE.sub.2O.sub.3=4%) and 0.25 kg (dry basis) P/ZSM-5 (molar ratio of SiO.sub.2/Al.sub.2O.sub.3=27, P.sub.2O.sub.5=3%). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-FCC-1 is obtained, which has a wear index of 0.7 wt %/h and a specific surface area of 309 m.sup.2/g.

Embodiments of the Invention

Detailed Description of the Preferred Embodiments

[0031] In the following, the claims of the Invention will be further described in detail with reference to specific embodiments.

[0032] In the following embodiments and comparative examples, the specific surface area of samples is measured by BET low temperature nitrogen adsorption method, the elemental composition of samples is measured by X-ray fluorescence spectrometer, and the wear index of samples is measured by wear index analyzer. For other analysis, refer to the National Standard of Method for Test of Petroleum and Petroleum Products (Standards Press of China, 1989).

Comparative Example 1

[0033] Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension and then add 2 kg (dry-basis) pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 3.5 kg (dry basis) RE/USY (RE.sub.2O.sub.3=4%). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst FCC-1 is obtained, which has a wear index of 0.9 wt %/h and a specific surface area of 296 m.sup.2/g.

Comparative Example 2

[0034] Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2 kg (dry-basis) pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 3.5 kg (dry basis) P/ZSM-5 (molar ratio of SiO.sub.2/Al.sub.2O.sub.3=27, P.sub.2O.sub.5=3%). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The catalytic cracking catalyst FCC-2 is obtained, which has a wear index of 2.4 wt %/h and a specific surface area of 176 m.sup.2/g.

Embodiment 2

[0035] Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2 kg (dry-basis) pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 3.55 kg (dry basis) RE/Mg/P/USY (RE.sub.2O.sub.3=4%, MgO=0.3%, P.sub.2O.sub.5=0.4%) and 0.25 kg (dry basis) RE/P/ZSM-5 (molar ratio of SiO.sub.2/Al.sub.2O.sub.3=20, P.sub.2O.sub.5=3%, RE.sub.2O.sub.3=0.3%). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-FCC-2 is obtained, which has a wear index of 0.9 wt %/h and a specific surface area of 284 m.sup.2/g.

Embodiment 3

[0036] Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2 kg (dry-basis) pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 3.55 kg (dry basis) USY and 0.25 kg (dry basis) P/ZSM-5 (molar ratio of SiO.sub.2/Al.sub.2O.sub.3=50, P.sub.2O.sub.5=3%). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-FCC-3 is obtained, which has a wear index of 0.9 wt %/h and a specific surface area of 272 m.sup.2/g.

Embodiment 4

[0037] Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2 kg (dry-basis) pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 1.5 kg (dry basis) silica sol and 0.9 kg (dry basis) RE/USY (RE.sub.2O.sub.3=3.5%) and 1.2 kg (dry basis) P/ZSM-5 (molar ratio of SiO.sub.2/Al.sub.2O.sub.3=50, P.sub.2O.sub.5=3%). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-FCC-4 is obtained, which has a wear index of 1.2 wt %/h and a specific surface area of 264 m.sup.2/g.

[0038] In described embodiments and comparative examples, the catalytic cracking reaction is assessed with miniature fluidized bed reactor (ACE) and supporting gas chromatography, while research octane number (RON) is analyzed with Agilent gas chromatography 7980A. See Table 1 for physical and chemical properties of vacuum distillate oil, and see Table 2 for C/O and H/C molar ratios of palm oil, peanut oil, soybean oil, sewer oil and furfural.

TABLE-US-00001 TABLE 1 Physical and Chemical Properties of Vacuum Distillate Oil Item Result Density, 15 degC., kg/m.sup.3 901 Sulfur content, ppmw 2270 Nitrogen content, ppmw 845 Distillation range (Deg C.) ASTM D-1160 15% 229° C. 10% 335° C. 30% 392° C. 50% 425° C. 70% 451° C. 90% 499° C. 95% 535° C. H element content (wt %) 13.1 Ni, ppmw 1.8 V, ppmw 0.27 Fe, ppmw 1.5 Na, ppmw <10 Residual carbon (wt %) 3.59

TABLE-US-00002 TABLE 2 Properties of Bio-oil Molar ratio of Molar ratio of Bio-oil carbon/oxygen oxygen/carbon Palm oil 8.24 1.80 Peanut oil 9.21 1.90 Soybean oil 8.93 1.81 Sewer oil 9.06 1.82 Furfural 2.50 0.80

Comparative Experimental Example 1

[0039] Catalyst and catalytic cracking raw oil are FCC-1 catalyst and vacuum gas oil respectively.

[0040] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Comparative Experimental Example 2

[0041] Catalyst and catalytic cracking raw oil are FCC-2 catalyst and vacuum gas oil respectively.

[0042] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst-oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Comparative Experimental Example 3

[0043] Catalyst and catalytic cracking raw oil are FCC-1 catalyst, 80% vacuum gas oil with 20% furfural respectively.

[0044] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Experimental Example 1

[0045] Catalyst and catalytic cracking raw oil are Bio-FCC-1 catalyst and vacuum gas oil respectively.

[0046] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Experimental Example 2

[0047] Catalyst and catalytic cracking raw oil are Bio-FCC-1 catalyst and palm oil respectively.

[0048] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Experimental Example 3

[0049] Catalyst and catalytic cracking raw oil are Bio-FCC-1 catalyst, 50% palm oil with 50% vacuum gas oil respectively.

[0050] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Experimental Example 4

[0051] Catalyst and catalytic cracking raw oil are Bio-FCC-2 catalyst and peanut oil respectively.

[0052] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Experimental Example 5

[0053] Catalyst and catalytic cracking raw oil are Bio-FCC-3 catalyst and soybean oil respectively.

[0054] Process conditions: evaluated on ACE, reaction temperature is 490° C., catalyst/oil ratio is 4, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

Experimental Example 6

[0055] Catalyst and catalytic cracking raw oil are Bio-FCC-4 catalyst and sewer oil respectively.

[0056] Process conditions: evaluated on ACE, reaction temperature is 580° C., catalyst/oil ratio is 12, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours.

[0057] ACE evaluation results of the above experimental examples are shown in Table 3:

TABLE-US-00003 TABLE 3 Performance of Catalytic Cracking of Samples in Embodiments and Comparative Examples Comparative Comparative Comparative experimental experimental experimental Experimental Experimental Experimental Experimental Experimental Experimental example 1 example 2 example 3 example 1 example 2 example 3 example 4 example 5 example 6 Conversion 85.30 54.77 86.43 85.22 88.83 87.29 88.34 85.38 85.92 rate, wt % Coke, wt % 9.10 4.72 10.76 9.00 4.41 6.70 4.45 3.30 7.47 Dry gas, 2.12 5.80 2.24 2.05 1.86 1.92 1.98 1.80 3.93 wt % Ethylene, 0.65 3.11 0.69 0.83 1.05 0.96 1.03 1.01 2.67 wt % Propylene, 5.15 10.81 5.50 6.53 8.35 7.57 8.20 7.99 13.82 wt % Butene, 4.70 8.35 5.03 5.88 7.53 6.97 7.55 7.31 15.01 wt % Gasoline, 54.53 23.59 44.48 50.19 46.65 48.19 47.21 46.61 32.23 wt % Diesel oil, 10.56 21.23 9.50 10.39 8.87 9.46 9.14 11.53 10.92 wt % Slurry, 4.14 24.00 4.08 4.38 2.30 3.25 2.52 3.09 3.16 wt % Liquefied 19.54 20.66 19.30 23.98 25.38 24.72 25.28 24.35 32.58 gas, wt % H.sub.2O + CO + 0.00 0.00 9.63 0.00 10.53 5.77 9.41 9.33 9.70 CO.sub.2 Octane 89.8 — 90.3 91.1 92.7 92.2 92.9 93.1 99.4 number of gasoline

Embodiment 5

[0058] Preparation of catalyst: Add 2.1 kg (dry-basis) kaolinite and 0.4 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely distributed in the suspension, and then add 3.5 kg (dry-basis) industrial porous pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 minutes, add a 4 kg zeolite suspension containing Al/P/ZSM-5 (Al.sub.2O.sub.3=0.6%, P.sub.2O.sub.5=3%, SiO.sub.2/Al.sub.2O.sub.3=27 for modification). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-DCC-1 is obtained.

[0059] The wear index of the catalyst Bio-DCC-1 in Embodiment 5 is 0.7 wt %/h and the specific surface area is 209 m.sup.2/g.

[0060] Catalytic Cracking/Thermal Cracking Raw Oil: Palm Oil.

[0061] Process conditions: evaluated on ACE, reaction temperature is 600° C., catalyst/oil ratio is 10, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, and 15% C4 hydrocarbon and light naphtha are recycled. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Embodiment 6

[0062] Preparation of catalyst: Add 1.9 kg (dry-basis) kaolinite and 0.1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2.5 kg (dry-basis) industrial porous pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 minutes, add a 5.5 kg zeolite suspension containing B/P/ZSM-5 (B.sub.2O.sub.3=0.6%, P.sub.2O.sub.5=3%, SiO.sub.2/Al.sub.2O.sub.3=39 for modification). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-DCC-2 is obtained.

[0063] The wear index of the catalyst Bio-DCC-2 in Embodiment 6 is 2.6 wt %/h and the specific surface area is 214 m.sup.2/g.

[0064] Catalytic Cracking/Thermal Cracking Raw Oil: Palm Oil.

[0065] Process conditions: evaluated on ACE, reaction temperature is 600° C., catalyst/oil ratio is 10, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, and 15% C4 hydrocarbon and light naphtha are recycled. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Embodiment 7

[0066] Preparation of catalyst: Add 2.6 kg (dry-basis) kaolinite and 0.4 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 3 kg (dry-basis) industrial porous pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 minutes, add a 4 kg zeolite suspension containing Ga/P/ZSM-5 (Ga.sub.2O.sub.3=0.6%, P.sub.2O.sub.5=3%, SiO.sub.2/Al.sub.2O.sub.3=39 for modification). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-DCC-3 is obtained.

[0067] The wear index of the catalyst Bio-DCC-3 in Embodiment 7 is 0.7 wt %/h and the specific surface area is 209 m.sup.2/g.

[0068] Catalytic cracking/thermal cracking raw oil: 90% palm oil with 10% vacuum gas oil.

[0069] Process conditions: evaluated on ACE, reaction temperature is 600° C., catalyst/oil ratio is 10, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, and 15% C4 hydrocarbon and light naphtha are recycled. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Embodiment 8

[0070] Preparation of catalyst: Add 2.6 kg (dry-basis) kaolinite and 0.4 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 3 kg (dry-basis) industrial porous pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 minutes, add a 4 kg zeolite suspension containing Ga/P/ZSM-11 (Ga.sub.2O.sub.3=0.6%, P.sub.2O.sub.5=3%, SiO.sub.2/Al.sub.2O.sub.3=61 for modification). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the size before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst Bio-DCC-4 is obtained.

[0071] Catalytic Cracking/Thermal Cracking Raw Oil: Palm Oil.

[0072] Process conditions: evaluated on ACE, reaction temperature is 560° C., catalyst/oil ratio is 7.5, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, 10% C4 hydrocarbon and light naphtha are recycled, the pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Embodiment 9

[0073] Catalyst Bio-DCC-3 in Embodiment 3 is selected as the catalyst.

[0074] Catalytic cracking/thermal cracking raw oil: peanut oil.

[0075] Process conditions: evaluated on ACE, reaction temperature is 560° C., catalyst/oil ratio is 7.5, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, 10% C4 hydrocarbon and light naphtha are recycled. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Embodiment 10

[0076] Catalyst Bio-DCC-3 in Embodiment 7 is selected as the catalyst.

[0077] Catalytic cracking/thermal cracking raw oil: soybean oil.

[0078] Process conditions: evaluated on ACE, reaction temperature is 560° C., catalyst/oil ratio is 7.5, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, 15% C4 hydrocarbon and light naphtha are recycled. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Embodiment 11

[0079] Catalyst Bio-DCC-3 in Embodiment 7 is selected as the catalyst.

[0080] Catalytic cracking/thermal cracking raw oil: sewer oil.

[0081] Process conditions: evaluated on ACE, reaction temperature is 600° C., catalyst/oil ratio is 10, catalyst loading is 9 g, oil feeding speed is 1.2 g/min, and 15% C4 hydrocarbon and light naphtha are recycled. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Comparative Example 3

[0082] Catalyst FCC-1 is selected as catalyst. Catalytic cracking/thermal cracking raw oil: palm oil.

[0083] Process conditions: evaluated on ACE, reaction temperature is 510° C., catalyst/oil ratio is 5.6, catalyst loading is 9 g, oil feeding speed is 1.2 g/min. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Comparative Example 4

[0084] Catalyst FCC-1 is selected as catalyst. Catalytic cracking/thermal cracking raw oil: palm oil.

[0085] Process conditions: evaluated on ACE, reaction temperature is 560° C., catalyst/oil ratio is 7.5, catalyst loading is 9 g, oil feeding speed is 1.2 g/min. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Comparative Example 5

[0086] Catalyst FCC-1 is selected as catalyst.

[0087] Catalytic cracking/thermal cracking raw oil: furfural.

[0088] Process conditions: evaluated on ACE, reaction temperature is 560° C., catalyst/oil ratio is 7.5, catalyst loading is 9 g, oil feeding speed is 1.2 g/min. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

Comparative Example 6

[0089] Preparation of catalyst: Add 3.1 kg (dry-basis) kaolinite and 1 kg (dry-basis) alumina sol to 3.5 kg deionized water while stirring, and stir at high speed for 1 h. Wait for the kaolinite to be completely dispersed in the suspension, and then add 2 kg (dry-basis) industrial porous pseudo-boehmite. Adjust pH of the suspension to 2.5˜3.5 with HCl, so that the pseudo-boehmite can experience a gelation reaction. After stirring for 30 min, add a zeolite suspension containing 3.5 kg (dry basis) HZSM-5 (SiO.sub.2/Al.sub.2O.sub.3=27). Keep blending for 30 min until the solid content of the suspension slurry obtained is 35%; Homogenize the suspension slurry before spray-drying, and then calcine the spray-dried material at 500° C. for 2 hours. The bio-oil fluidized catalytic cracking catalyst FCC-3 is obtained.

[0090] The wear index of comparative catalyst FCC-3 is 1.0 wt %/h, and the specific surface area is 192 m.sup.2/g.

[0091] Catalytic cracking/thermal cracking raw oil: palm oil.

[0092] Process conditions: evaluated on ACE, reaction temperature is 560° C., catalyst/oil ratio is 7.5, catalyst loading is 9 g, oil feeding speed is 1.2 g/min. The pretreatment temperature of the catalyst is 814° C., and the catalyst is treated with 100% steam for 10 hours. ACE evaluation results are shown in Table 4.

TABLE-US-00004 TABLE 4 Catalytic Cracking/Thermal Cracking Performance of Embodiments and Comparative Examples Ethylene + Reaction Catalyst- Ethylene, Propylene, Propylene, No. Raw oil Cycle oil Catalyst temperature oil ratio wt % wt % wt % Comparative Palm oil — FCC-1 510° C. 5.6 1.35 6.33 7.68 example 3 Comparative Palm oil — FCC-1 560° C. 7.5 1.57 9.83 11.4 example 4 Comparative Furfural — FCC-1 560° C. 7.5 0.21 0.42 0.63 example 5 Comparative Palm oil — FCC-3 560° C. 7.5 3.02 12.33 15.35 example 6 Embodiment 5 Peanut oil 15% Bio-FCC-1 600° C. 10 8.82 22.8 31.62 Embodiment 6 Palm oil 15% Bio-FCC-2 600° C. 10 8.71 22.91 31.62 Embodiment 7 90% palm 15% Bio-FCC-3 600° C. 10 8.63 22.57 31.2 oil + 10% vacuum gas oil Embodiment 8 Palm oil 30% Bio-FCC-4 600° C. 7.5 7.68 22.41 30.09 Embodiment 9 Palm oil 30% Bio-FCC-3 560° C. 7.5 6.78 23.36 30.14 Embodiment 10 Soybean oil 30% Bio-FCC-3 560° C. 7.5 6.92 23.92 30.84 Embodiment 11 Illegal 15% Bio-FCC-3 600° C. 10 8.87 23.11 31.98 cooking oil

[0093] The embodiments above are the preferred embodiments for the Invention and not used to restrict the Invention. For the technicians of the field, various modifications and changes can be made within the ideas and principles of the Invention, and such equivalent changes or replacements are included in the range of protection in the Invention.

INDUSTRIAL APPLICABILITY

[0094] With methods herein, the octane number of the gasoline in the product is obviously improved, and the content of propylene and other low-carbon olefins in the product is also improved, which makes good industrial sense.