HIGHLY-DISPERSED HYDROGENATION CATALYST, PREPARATION METHOD THEREOF, AND USE THEREOF IN PREPARATION OF BIOFUEL FROM PALM OIL OR OTHER OIL

Abstract

A highly-dispersed hydrogenation catalyst, a preparation method thereof, and use thereof in the preparation of biofuel from palm oil or other oil are provided. The combination of maleic anhydride-grafted polypropylene (MA-PP) and a silane coupling agent (SCA) is introduced into an aluminum oxide composite carrier through organic amidation to obtain a uniformly-dispersed composite carrier with regular pores. Moreover, through a multi-stage impregnation and roasting process, a particle size of an active component is greatly reduced, and the dispersion of the active component and the number of active sites are improved. A hydrogenation catalyst with high hydrothermal stability, high hydrogenation activity, and long life is prepared based on the composite carrier with regular pores and used in the preparation of biofuel from vegetable oil or other oil through hydrodeoxygenation (HDO), which has great industrial application value.

Claims

1. An aluminum oxide composite carrier, wherein maleic anhydride-grafted polypropylene (MA-PP) and a silane coupling agent (SCA) undergo amidation to obtain a reaction product, then γ-Al.sub.2O.sub.3 and tetrabutyl titanate (TBT) are added into the reaction product to obtain a solid material, and the solid material is dried and roasted to form the aluminum oxide composite carrier, wherein the aluminum oxide composite carrier is an aluminum oxide-titanium dioxide carrier.

2. An aluminum oxide composite carrier, wherein MA-PP and an SCA undergo amidation to obtain a reaction product, then γ-Al.sub.2O.sub.3 and tetrabutyl zirconate (TBZ) are added into the reaction product to obtain a solid material, and the solid material is dried and roasted to form the aluminum oxide composite carrier, wherein the aluminum oxide composite carrier is an aluminum oxide-zirconium dioxide carrier.

3. The aluminum oxide composite carrier according to claim 1, wherein a mass percentage of the titanium dioxide in the aluminum oxide composite carrier is 5% to 20%.

4. The aluminum oxide composite carrier according to claim 2, wherein a mass percentage of the zirconium dioxide in the aluminum oxide composite carrier is 5% to 20%.

5. The aluminum oxide composite carrier according to claim 1, wherein the SCA is KH-550; and 1% to 5% MA-PP is added to an ethanol solution with 1% to 5% of KH-550 under hot water reflux to allow the amidation under stirring.

6. A highly-dispersed hydrogenation catalyst, wherein the highly-dispersed hydrogenation catalyst is obtained by loading an active component on an aluminum oxide composite carrier through limited times of impregnation and roasting, wherein MA-PP and an SCA undergo amidation to obtain a reaction product, then γ-Al.sub.2O.sub.3 and TBT or TBZ are added into the reaction product to obtain a solid material, and the solid material is dried and roasted to form the aluminum oxide composite carrier, wherein the aluminum oxide composite carrier is an aluminum oxide-titanium dioxide carrier or an aluminum oxide-zirconium dioxide carrier.

7. The highly-dispersed hydrogenation catalyst according to claim 6, wherein the impregnation and roasting is conducted 2 to 6 times, and loaded particles in the highly-dispersed hydrogenation catalyst have a particle size of 0.1 nm to 10 nm.

8. The highly-dispersed hydrogenation catalyst according to claim 6, wherein the impregnation and roasting is conducted once, and loaded particles in the highly-dispersed hydrogenation catalyst have a particle size of 20 nm to 30 nm.

9. The highly-dispersed hydrogenation catalyst according to claim 6, wherein the active component comprises a main active metal component and a synergistic component; the main active metal component is Ni; and the synergistic component is one or more selected from the group consisting of Co, Mo and W.

10. A method for preparing a highly-dispersed hydrogenation catalyst, comprising: loading an active component on an aluminum oxide composite carrier through one-stage or multi-stage impregnation, wherein MA-PP and an SCA undergo amidation to obtain a reaction product, then γ-Al.sub.2O.sub.3 and TBT or TBZ are added into the reaction product to obtain a solid material, and the solid material is dried and roasted to form the aluminum oxide composite carrier, wherein the aluminum oxide composite carrier is an aluminum oxide-titanium dioxide carrier or an aluminum oxide-zirconium dioxide carrier.

11. The method according to claim 10, wherein the impregnation is conducted n times; a staged impregnation solution has a concentration of Y.sub.n, and a sum of concentrations of impregnation solutions in all stages is X; Y.sub.n=X/n; and n is an integer selected from 1 to 6.

12. The method according to claim 10, wherein a staged impregnation is conducted specifically as follows: completely dissolving a metal salt of the active component in water to prepare a staged impregnation solution, adding the staged impregnation solution to the aluminum oxide composite carrier, and thoroughly stirring for impregnation to obtain an impregnated solid material; and drying and roasting the impregnated solid material to form a staged catalyst; wherein a product obtained after the last impregnation is the highly-dispersed hydrogenation catalyst.

13. A method of using the highly-dispersed hydrogenation catalyst of claim 6, comprising: preparing a biofuel from palm oil, methyl-esterified palm oil, a waste fatty acid, or genetically modified soybean oil through hydrodeoxygenation (HDO) with the highly-dispersed hydrogenation catalyst.

14. The aluminum oxide composite carrier according to claim 2, wherein the SCA is KH-550; and 1% to 5% MA-PP is added to an ethanol solution with 1% to 5% of KH-550 under hot water reflux to allow the amidation under stirring.

15. The aluminum oxide composite carrier according to claim 3, wherein the SCA is KH-550; and 1% to 5% MA-PP is added to an ethanol solution with 1% to 5% of KH-550 under hot water reflux to allow the amidation under stirring.

16. The aluminum oxide composite carrier according to claim 4, wherein the SCA is KH-550; and 1% to 5% MA-PP is added to an ethanol solution with 1% to 5% of KH-550 under hot water reflux to allow the amidation under stirring.

17. The highly-dispersed hydrogenation catalyst according to claim 6, wherein a mass percentage of the titanium dioxide in the aluminum oxide composite carrier is 5% to 20%.

18. The highly-dispersed hydrogenation catalyst according to claim 6, wherein a mass percentage of the zirconium dioxide in the aluminum oxide composite carrier is 5% to 20%.

19. The highly-dispersed hydrogenation catalyst according to claim 6, wherein the SCA is KH-550; and 1% to 5% MA-PP is added to an ethanol solution with 1% to 5% of KH-550 under hot water reflux to allow the amidation under stirring.

20. The highly-dispersed hydrogenation catalyst according to claim 7, wherein the active component comprises a main active metal component and a synergistic component; the main active metal component is Ni; and the synergistic component is one or more selected from the group consisting of Co, Mo and W.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 is a TEM image of NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 2;

[0038] FIG. 2 is a TEM image of 2-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 3;

[0039] FIG. 3 is a TEM image of 3-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 5; and

[0040] FIG. 4 is a TEM image of 6-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 6.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0041] The present disclosure relates to a highly-dispersed hydrogenation catalyst, a preparation method thereof, and use thereof in the preparation of a biofuel from palm oil or other oil. In the prepared hydrogenation catalyst, a metal active component is loaded on a carrier with extremely high dispersion and nano-scale particle size, which increases the number of active sites and improves the HDO activity of the catalyst. In the present disclosure, the traditional aluminum oxide carrier is modified, where MA-grafted PP (MA-PP) is introduced to prepare an aluminum oxide composite carrier with regular pores, which improves the binding of the active component and the carrier to a great extent, such that the hydrothermal stability of the catalyst is improved and the service life of the catalyst is increased. The catalyst with high HDO activity, high stability, and long life is of great significance in the preparation of a biofuel from a vegetable oil through HDO. In the catalyst, modified aluminum oxide is adopted as a carrier, Ni is adopted as a main active metal, and Mo and W are adopted as a synergistic component. The synergistic component is used as an additive to improve the dispersion of the active component, which also has corresponding hydrogenation activity.

[0042] The modified aluminum oxide is specifically an aluminum oxide-titanium dioxide carrier or an aluminum oxide-zirconium dioxide carrier. A preparation method is specifically as follows: 1% to 5% of KH-550 is added to ethanol, and a resulting mixture is stirred for 0.5 h; 1% to 5% of MA-PP is added under reflux at 80° C., and a resulting mixture is stirred for 12 h to allow amidation; γ-Al.sub.2O.sub.3 and TBT are added, and a resulting mixture is further stirred for 1 h to 3 h; and a resulting mixture is filtered to obtain a solid material, and the solid material is washed to neutrality, and then dried and roasted to form the aluminum oxide-titanium dioxide carrier, where a mass percentage of the titanium dioxide in the carrier is 5% to 20%. If the TBT is replaced by TBZ, the aluminum oxide-zirconium dioxide carrier is formed after the drying and roasting, where a mass percentage of the zirconium dioxide in the carrier is 5% to 20%. The composite carrier obtained after the roasting has regular pores and uniform binding, and thus can improve the hydrothermal stability of the catalyst, thereby increasing the life span. Through experiments, it is found that an aluminum oxide-titanium dioxide carrier with 10% of titanium dioxide has the optimal stability; and the aluminum oxide-zirconium dioxide carrier with 15% of zirconium dioxide has the optimal stability.

[0043] For example, the aluminum oxide-titanium dioxide carrier with 10% of titanium dioxide is prepared through the following specific steps: 100 ml of ethanol and 5 g of KH-550 are added to a three-necked flask and stirred for 0.5 h; then 5 g of MA-PP is added under reflux at 80° C., and a resulting mixture is stirred for 12 h to allow amidation; 20 g of γ-Al.sub.2O.sub.3 is added, and a resulting mixture is stirred for 1 h to form a uniform γ-Al.sub.2O.sub.3 suspension in which γ-Al.sub.2O.sub.3 is uniformly dispersed in the solvent; then 9.57 g of TBT is added dropwise to the γ-Al.sub.2O.sub.3 suspension, and a resulting mixture is further stirred for 2 h; and a resulting mixture is subjected to suction filtration to obtain a solid, and the solid is dried at 120° C. for 2 h and roasted at 500° C. for 2 h to obtain the aluminum oxide-titanium dioxide (10%) carrier. For example, an aluminum oxide-zirconium dioxide carrier with 20% of zirconium dioxide is prepared through the following specific steps: 100 ml of ethanol and 5 g of KH-550 are added to a three-necked flask and stirred for 0.5 h; then 5 g of MA-PP is added under reflux at 80° C., and a resulting mixture is stirred for 12 h to allow amidation; 20 g of γ-Al.sub.2O.sub.3 is added, and a resulting mixture is stirred for 1 h to form a uniform γ-Al.sub.2O.sub.3 suspension in which γ-Al.sub.2O.sub.3 is uniformly dispersed in the solvent; then 6.91 g of TBZ is added to the γ-Al.sub.2O.sub.3 suspension, and a resulting mixture is further stirred for 2 h; and a resulting mixture is subjected to suction filtration to obtain a solid, and the solid is dried at 120° C. for 2 h and roasted at 500° C. for 2 h to obtain the aluminum oxide-zirconium dioxide (20%) carrier.

[0044] The active component in the catalyst may include a main active metal component and a synergistic component. A mass percentage of the main active metal component may be 5% to 30%. Through many experiments, it is found that, when the main active metal component is Ni, the catalyst has the optimal hydrogenation activity. A mass percentage of the synergistic component may be 1% to 5%, and the synergistic component can be one or more from the group consisting of Co, Mo, and W. Through many experiments, it is found that, when the synergistic component is Mo and W, the catalyst shows significantly-improved activity. Mo and W can synergistically serve as additives to improve the dispersion of the active component, which also have corresponding hydrogenation activity.

[0045] A catalyst is usually prepared through single impregnation, where an active component-containing impregnation solution with a customized concentration is prepared and thoroughly mixed with a carrier, and a resulting mixture is roasted to form the catalyst. For example, the catalyst NiMoW/γ-Al.sub.2O.sub.3 is prepared through ordinary physical impregnation: corresponding masses of a nickel salt, a molybdenum salt, and a tungsten salt are weighed and added to water with an equal volumetric water absorption ratio to a carrier, and a resulting mixture is fully stirred to form an impregnation solution; and the impregnation solution is then added to the corresponding carrier, and a resulting mixture is thoroughly mixed, allowed to stand, and then dried and roasted to form the catalyst.

[0046] In order to improve the uniformity of a mixture and the dispersion of the metal active component, a rotary evaporator is used to conduct the thorough mixing, and the impregnation and loading is conducted under vacuum reflux, which effectively improves the load dispersion of the active component. In a catalyst formed in this way, the metal active component is loaded at a metal particle loading level of 20 nm to 30 nm.

[0047] The present disclosure adopts a multi-stage impregnation and roasting process to prepare a catalyst. For example, the catalyst n-NiMoW/γ-Al.sub.2O.sub.3 is prepared through multi-stage physical impregnation and roasting as follows: when a proportion of a target metal component is X, the impregnation and roasting is conducted n times, and a metal salt solution prepared for each stage has a concentration of Y.sub.n, Y.sub.1+Y.sub.2+ . . . +Y.sub.n=X, where n is 2 to 6; a specified amount of a metal salt is weighed and dissolved in a corresponding amount of water to prepare a first-stage impregnation solution with a concentration of Y.sub.1, the first-stage impregnation solution is added to a carrier, and a resulting mixture is thoroughly mixed, dried, and roasted to obtain a first-stage catalyst; then a second-stage impregnation solution with a concentration of Y.sub.2 is prepared and added to the first-stage catalyst, and a resulting mixture is thoroughly mixed, dried, and roasted to obtain a second-stage catalyst; and the subsequent impregnation and roasting is conducted by the corresponding method, and a catalyst obtained after the last impregnation and roasting is the highly-dispersed hydrogenation catalyst.

[0048] The impregnation solutions in all stages can have the same concentration. When the impregnation solutions in all stages have the same concentration, the impregnation effect is prominent and the metal active component is evenly distributed. The impregnation can be conducted under vacuum reflux, for example, a rotary evaporator can be used, which can improve the loading efficiency and loading uniformity. Through multi-stage impregnation, the metal active component can be loaded on the carrier at a metal particle loading level of 1 nm to 10 nm, the dispersion of the active metal component is improved, and the particle size is at a nano-scale, thereby improving the number of active sites and the HDO activity.

[0049] The highly-dispersed hydrogenation catalyst is efficient when used in the preparation of a biofuel from a vegetable oil, exhibiting improved hydrothermal stability and long life. For example, the catalyst can be used in the preparation of a biofuel from palm oil or a waste fatty acid through hydrogenation.

Example 1: Catalyst NiMoW/γ-Al.SUB.2.O.SUB.3.Prepared Through One-Time Impregnation

[0050] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3 was used as a carrier.

[0051] 15 g of water with an equal volumetric water absorption ratio to 7.5 g of γ-Al.sub.2O.sub.3 was taken, 8.6 g of nickel acetate, 0.46 g of ammonium molybdate, and 0.37 g of ammonium metatungstate (AMT) were added to the water, and a resulting mixture was stirred for dissolution to prepare an impregnation solution; the impregnation solution was added dropwise to a petri dish with the 7.5 g of γ-Al.sub.2O.sub.3, and a resulting mixture was thoroughly mixed, allowed to stand for 12 h, dried at 120° C. for 3 h, and ground into a powder; and the powder was roasted at 500° C. for 2 h to obtain a powdery catalyst NiMoW/γ-Al.sub.2O.sub.3, and the powdery catalyst was tableted and sieved to obtain a 20 to 40-mesh tableted catalyst NiMoW/γ-Al.sub.2O.sub.3.

[0052] The catalyst NiMoW/γ-Al.sub.2O.sub.3 was used to prepare a biofuel from palm oil through hydrogenation, and specific steps were as follows:

[0053] (1) Pretreatment of the catalyst: The catalyst NiMoW/γ-Al.sub.2O.sub.3 was shaped and then placed in a fixed bed reactor, then the fixed bed reactor was purged at room temperature for 0.5 h with nitrogen at a volumetric space velocity of 500 h.sup.−1 and then purged with hydrogen at an equal volumetric space velocity, and the catalyst was heated to 200° C. at a rate of 5° C./min, and then heated to 350° C. at a rate of 10° C./min and kept at the temperature for at least 3 h.

[0054] (2) HDO of the palm oil: At 350° C., based on a hydrogen-palm oil volume ratio of 800, a mixed solution of palm oil and cyclohexane (in a ratio of 3:2) was fed at a feed space velocity of 1 h.sup.−1, during which a reaction solution was sampled every 1 h, and a liquid product was separated from water and subjected to a composition test.

[0055] The catalyst NiMoW/γ-Al.sub.2O.sub.3 was used to prepare a biofuel from a waste fatty acid through hydrogenation, and specific steps were as follows:

[0056] (1) Pretreatment of the catalyst: The catalyst NiMoW/γ-Al.sub.2O.sub.3 was shaped and then placed in a fixed bed reactor, then the fixed bed reactor was purged at room temperature for 0.5 h with nitrogen at a volumetric space velocity of 500 h.sup.−1 and then purged with hydrogen at an equal volumetric space velocity, and the catalyst was heated to 200° C. at a rate of 5° C./min, and then heated to 350° C. at a rate of 10° C./min and kept at the temperature for at least 3 h.

[0057] (2) HDO of the waste fatty acid: At 350° C., based on a hydrogen-waste fatty acid volume ratio per unit time of 1,000, the waste fatty acid was fed at a feed space velocity of 1 h-1 under a reaction pressure of 3 MPa, during which a reaction solution was sampled every 1 h, and a liquid product was separated from water and subjected to a composition test.

Example 2: Catalyst NiMoW/γ-Al.SUB.2.O.SUB.3.—TiO.SUB.2./ZrO.SUB.2 .Prepared Through One-Time Impregnation

[0058] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used as a carrier.

[0059] 15 g of water with an equal volumetric water absorption ratio to 7.5 g of γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was taken, 8.6 g of nickel acetate, 0.46 g of ammonium molybdate, and 0.37 g of AMT were added to the water, and a resulting mixture was stirred for dissolution to prepare an impregnation solution; the impregnation solution was added dropwise to a petri dish with the 7.5 g of γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2, and a resulting mixture was thoroughly mixed, allowed to stand for 12 h, dried at 120° C. for 3 h, and ground into a powder; and the powder was roasted at 500° C. for 2 h to obtain a powdery catalyst NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2, and the powdery catalyst was tableted and sieved to obtain a 20 to 40-mesh tableted catalyst NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2.

[0060] The catalyst NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used to prepare a biofuel from palm oil or a waste fatty acid through hydrogenation, and specific steps were as in Example 1.

Example 3: Catalyst 2-NiMoW/γ-Al.SUB.2.O.SUB.3.—TiO.SUB.2./ZrO.SUB.2 .Prepared Through Two-Stage Impregnation

[0061] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used as a carrier.

[0062] 4.3 g of nickel acetate, 0.23 g of ammonium molybdate, and 0.18 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a first-stage impregnation solution; the first-stage impregnation solution was added to a rotary evaporator with 10.41 g of the γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 carrier, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a first-stage catalyst.

[0063] 4.3 g of nickel acetate, 0.23 g of ammonium molybdate, and 0.19 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a second-stage impregnation solution; the second-stage impregnation solution was added to a rotary evaporator with the first-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a second-stage catalyst (namely, 2-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2); and the powdery catalyst was tableted and sieved to obtain 20 to 40-mesh tableted 2-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2.

[0064] The catalyst 2-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used to prepare a biofuel from palm oil or a waste fatty acid through hydrogenation, and specific steps were as in Example 1.

Example 4: Catalyst 3-NiMoW/γ-Al.SUB.2.O.SUB.3.Prepared Through Three-Stage Impregnation

[0065] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3 was used as a carrier.

[0066] 4 g of nickel acetate, 0.3 g of ammonium molybdate, and 0.2 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a first-stage impregnation solution; the first-stage impregnation solution was added to a rotary evaporator with 10.41 g of the γ-Al.sub.2O.sub.3 carrier, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a first-stage catalyst.

[0067] 2.3 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.08 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a second-stage impregnation solution; the second-stage impregnation solution was added to a rotary evaporator with the first-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a second-stage catalyst.

[0068] 2.3 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.09 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a third-stage impregnation solution; the third-stage impregnation solution was added to a rotary evaporator with the second-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a third-stage catalyst (namely, 3-NiMoW/γ-Al.sub.2O.sub.3); and the powdery catalyst was tableted and sieved to obtain 20 to 40-mesh tableted 3-NiMoW/γ-Al.sub.2O.sub.3.

[0069] The catalyst 3-NiMoW/γ-Al.sub.2O.sub.3 was used to prepare a biofuel from palm oil or a waste fatty acid through hydrogenation, and specific steps were as in Example 1.

Example 5: Catalyst 3-NiMoW/γ-Al.SUB.2.O.SUB.3.—TiO.SUB.2./ZrO.SUB.2 .Prepared Through Three-Stage Impregnation

[0070] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used as a carrier.

[0071] 2.9 g of nickel acetate, 0.16 g of ammonium molybdate, and 0.13 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a first-stage impregnation solution; the first-stage impregnation solution was added to a rotary evaporator with 10.41 g of the γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 carrier, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a first-stage catalyst.

[0072] 2.9 g of nickel acetate, 0.15 g of ammonium molybdate, and 0.12 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a second-stage impregnation solution; the second-stage impregnation solution was added to a rotary evaporator with the first-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a second-stage catalyst.

[0073] 2.8 g of nickel acetate, 0.15 g of ammonium molybdate, and 0.12 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a third-stage impregnation solution; the third-stage impregnation solution was added to a rotary evaporator with the second-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a third-stage catalyst (namely, 3-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2); and the powdery catalyst was tableted and sieved to obtain 20 to 40-mesh tableted 3-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2.

[0074] The catalyst 3-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used to prepare a biofuel from palm oil, methyl-esterified palm oil, a waste fatty acid, or genetically modified soybean oil through hydrogenation, and specific steps were as in Example 1. HDO steps of the methyl-esterified palm oil and the genetically modified soybean oil were the same as that of the palm oil.

Example 6: Catalyst 6-NiMoW/γ-Al.SUB.2.O.SUB.3.—TiO.SUB.2./ZrO.SUB.2 .Prepared Through Six-Stage Impregnation

[0075] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used as a carrier.

[0076] 1.45 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.07 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a first-stage impregnation solution; the first-stage impregnation solution was added to a rotary evaporator with 10.41 g of the γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 carrier, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a first-stage catalyst.

[0077] 1.43 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.06 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a second-stage impregnation solution; the second-stage impregnation solution was added to a rotary evaporator with the first-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a second-stage catalyst.

[0078] 1.43 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.06 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a third-stage impregnation solution; the third-stage impregnation solution was added to a rotary evaporator with the second-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a third-stage catalyst.

[0079] 1.43 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.06 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a fourth-stage impregnation solution; the fourth-stage impregnation solution was added to a rotary evaporator with the third-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a fourth-stage catalyst.

[0080] 1.43 g of nickel acetate, 0.08 g of ammonium molybdate, and 0.06 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a fifth-stage impregnation solution; the fifth-stage impregnation solution was added to a rotary evaporator with the fourth-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a fifth-stage catalyst.

[0081] 1.43 g of nickel acetate, 0.06 g of ammonium molybdate, and 0.06 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a sixth-stage impregnation solution; the sixth-stage impregnation solution was added to a rotary evaporator with the fifth-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; a resulting solution was dried at 120° C., and then roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was a sixth-stage catalyst (namely, 6-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2); and the powdery catalyst was tableted and sieved to obtain 20 to 40-mesh tableted 6-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2.

[0082] The catalyst 6-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used to prepare a biofuel from palm oil or a waste fatty acid through hydrogenation, and specific steps were as in Example 1.

Example 7: Catalyst 3-O—NiMoW/γ-Al.SUB.2.O.SUB.3.—TiO.SUB.2./ZrO.SUB.2 .Prepared Through Three-Stage Impregnation (without Roasting)

[0083] A catalyst in which a mass percentage of a metal component was 25% was prepared, where Ni accounted for 20%, Mo accounted for 2.5%, and W accounted for 2.5%; and γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used as a carrier.

[0084] 2.9 g of nickel acetate, 0.16 g of ammonium molybdate, and 0.13 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a first-stage impregnation solution; the first-stage impregnation solution was added to a rotary evaporator with 10.41 g of the γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 carrier, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C. to obtain a powder, which was a first-stage catalyst (without roasting).

[0085] 2.9 g of nickel acetate, 0.15 g of ammonium molybdate, and 0.12 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a second-stage impregnation solution; the second-stage impregnation solution was added to a rotary evaporator with the first-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; and a resulting solution was dried at 120° C. to obtain a powder, which was a second-stage catalyst (without roasting).

[0086] 2.8 g of nickel acetate, 0.15 g of ammonium molybdate, and 0.12 g of AMT were added to 200 ml of water, and a resulting mixture was stirred for dissolution to obtain a third-stage impregnation solution; the third-stage impregnation solution was added to a rotary evaporator with the second-stage catalyst, vacuum-pumping was conducted, and then stirring was conducted under reflux at 100° C. for 2 h; a resulting solution was dried at 120° C. to obtain a powder, which was a third-stage catalyst (without roasting); the third-stage catalyst (without roasting) was roasted at 500° C. for 2 h in a muffle furnace to obtain a powder, which was 3-O—NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2; and the powdery catalyst was tableted and sieved to obtain 20 to 40-mesh tableted 3-O—NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2.

[0087] The catalyst 3-O—NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2/ZrO.sub.2 was used to prepare a biodiesel from palm oil or a waste fatty acid through hydrogenation, and specific steps were as in Example 1.

[0088] FIG. 1 is a TEM image of NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 2; FIG. 2 is a TEM image of 2-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 3; FIG. 3 is a TEM image of 3-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 5; and FIG. 4 is a TEM image of 6-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 (10%) in Example 6. From the comparison of the four figures, it can be clearly seen that, for the titanium dioxide-modified catalysts obtained through different times of impregnation, the particle size of the loaded metal active component gradually decreases with the increase of the number of impregnation times, and is reduced to a nano-scale or smaller when the impregnation is conducted four times; and as the particle size decreases, both the dispersion of the active component and the number of active sites increase. As measured, when the impregnation is conducted once, a size of loaded metal particles is 20 nm to 30 nm; when the impregnation is conducted 2 times, a size of loaded metal particles is 5 nm to 10 nm; when the impregnation is conducted 3 times, a size of loaded metal particles can reach 3 nm to 5 nm; and when the impregnation is conducted 4 to 6 times, a size of loaded metal particles can reach 0.1 nm to 3 nm.

[0089] Catalytic results of the catalysts of the examples in the preparation of a biodiesel from palm oil or a waste fatty acid through hydrogenation are shown in Tables 1 to 6.

TABLE-US-00001 TABLE 1 Catalytic results of the catalysts prepared using 10% titanium dioxide-modified aluminum oxide as a carrier through different times of impregnation in HDO of palm oil Temp LHSV C5-C7 C8-C14 C15-C18 C17/ Catalyst (° C.) (hr.sup.−1) (%) (%) (%) C18 NiMoW/ 350 1 2.6 7.7 89.6 1.9 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 2.9 9.8 87.3 1.5 330 1 1.5 4.6 93.9 2.5 0.5 0.9 4.7 94.4 1.6 310 0.5 0.8 3.2 96.0 2.2 2-NiMoW/ 350 1 3.0 7.9 89.1 4.7 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 3.6 12.3 84.1 3.9 330 1 1.6 4.9 93.5 4.7 0.5 2.0 7.2 90.8 4.6 310 1 1.0 3.0 96.0 5.1 0.5 1.1 4.4 94.5 5.2 3-NiMoW/ 350 1 3.4 10.0 86.5 5.8 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 4.6 14.4 81.0 5.6 330 1 1.7 4.9 93.4 5.5 0.5 2.2 7.0 90.8 5.4 310 1 1.0 2.7 96.2 5.2 0.5 1.3 4.1 94.7 5.3 6-NiMoW/ 350 1 3.4 14.1 82.5 5.8 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 4.5 17.5 78.0 5.6 330 1 1.9 5.3 92.8 5.5 0.5 2.6 8.1 89.3 5.5 310 1 1.1 3.1 95.7 5.6 0.5 1.1 3.6 95.3 5.3

TABLE-US-00002 TABLE 2 Catalytic results of the catalysts prepared using 15% zirconium dioxide-modified aluminum oxide as a carrier through different times of impregnation in HDO of palm oil Temp LHSV C5-C7 C8-C14 C15-C18 C17/ Catalyst (° C.) (hr.sup.−1) (%) (%) (%) C18 NiMoW/ 350 1 2.9 8.1 89.0 4.3 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 1.9 5.3 92.8 3.1 310 1 1.0 2.5 96.5 2.7 2-NiMoW/ 350 1 2.2 4.6 93.2 5.6 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 2.1 4.3 93.6 4.1 310 1 4.7 3.5 91.8 3.7 3-NiMoW/ 350 1 3.4 3.6 93.0 6.8 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 4.2 3.3 92.5 5.1 310 1 5.5 3.2 91.3 4.7 6-NiMoW/ 350 1 0.8 4.6 94.6 7.2 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 2.3 4.3 93.0 5.8 310 1 4.6 3.8 91.6 5.0

TABLE-US-00003 TABLE 3 Catalytic results of the catalysts in HDO of palm oil Temp LHSV C5-C7 C8-C14 C15-C18 C17/ Catalyst (° C.) (hr.sup.−1) (%) (%) (%) C18 NiMoW/ 350 1 3 17.1 79.9 1.6 γ-Al.sub.2O.sub.3 330 1 1.4 7 91.6 1.7 310 1 There is a yellow precipitate in product, indicating incomplete conversion 3-NiMoW/ 350 1 3 19.8 77.2 2.3 γ-Al.sub.2O.sub.3 330 1 1.4 7.2 91.4 2.1 310 1 There is a yellow precipitate in product, indicating incomplete conversion 3-NiMoW/ 350 1 3.4 3.6 93.0 6.8 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 4.2 3.3 92.5 5.1 310 1 5.5 3.2 91.3 4.7 3-0-NiMoW/ 350 1 2.6 8.1 89.3 2.6 γ-Al.sub.2O.sub.3—TiO.sub.2 330 1 1.6 5.6 92.8 2.0 310 1 1.1 2.6 96.3 1.6 3-0-NiMoW/ 350 1 2.0 4.4 93.6 2.4 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 1.6 4.0 94.4 2.1 310 1 1.2 3.8 95.0 1.9

TABLE-US-00004 TABLE 4 Catalytic results of the catalysts prepared using 10% titanium dioxide-modified aluminum oxide as a carrier through different times of impregnation in HDO of a waste fatty acid Temp LHSV C5-C7 C8-C14 C15-C18 C17/ Catalyst (° C.) (hr.sup.−1) (%) (%) (%) C18 NiMoW/ 350 1 2.5 7.6 89.8 1.8 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 2.8 9.7 87.5 1.4 330 1 1.4 4.5 94.1 2.3 0.5 0.8 4.6 94.6 1.5 310 0.5 0.6 3.0 96.4 2.0 2-NiMoW/ 350 1 3.2 7.9 88.9 4.6 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 3.3 12.0 84.1 3.5 330 1 1.5 4.8 93.5 4.3 0.5 2.1 7.1 90.8 4.2 310 1 1.1 3.1 95.8 5.5 0.5 1.0 4.5 94.5 5.3 3-NiMoW/ 350 1 3.2 10.5 86.0 6.3 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 4.6 14.4 81.0 6.5 330 1 1.7 4.9 93.4 6.3 0.5 2.2 7.0 90.8 5.9 310 1 1.0 2.7 96.2 5.4 0.5 1.3 4.1 94.7 5.2 6-NiMoW/ 350 1 3.2 14.0 82.8 5.9 γ-Al.sub.2O.sub.3—TiO.sub.2 0.5 4.2 17.3 78.5 5.8 330 1 1.4 5.3 92.6 5.7 0.5 2.5 8.1 89.0 5.6 310 1 1.6 3.1 95.2 5.5 0.5 1.3 3.6 95.2 5.3

TABLE-US-00005 TABLE 5 Catalytic results of the catalysts prepared using 15% zirconium dioxide-modified aluminum oxide as a carrier through different times of impregnation in HDO of a waste fatty acid Temp LHSV C5-C7 C8-C14 C15-C18 C17/ Catalyst (° C.) (hr.sup.−1) (%) (%) (%) C18 NiMoW/ 350 1 2.8 8.1 89.0 4.2 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 1.6 5.3 92.8 3.0 310 1 1.0 2.4 96.5 2.5 2-NiMoW/ 350 1 2.5 4.6 93.2 5.6 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 2.1 4.5 93.6 4.1 310 1 4.7 3.3 91.8 3.7 3-NiMoW/ 350 1 3.4 3.6 93.0 6.7 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 4.2 3.4 92.5 5.2 310 1 5.5 3.2 91.0 4.3 6-NiMoW/ 350 1 0.4 4.2 94.6 7.0 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 2.3 4.6 93.0 5.6 310 1 4.6 3.8 91.5 5.1

TABLE-US-00006 TABLE 6 Catalytic results of the catalysts in HDO of a waste fatty acid Temp LHSV C5-C7 C8-C14 C15-C18 C17/ Catalyst (° C.) (hr.sup.−1) (%) (%) (%) C18 NiMoW/ 350 1 3.2 17.1 79.9 1.4 γ-Al.sub.2O.sub.3 330 1 1.5 7 91.6 1.5 310 1 There is a yellow precipitate in product, indicating incomplete conversion 3-NiMoW/ 350 1 3 19.6 77.2 2.0 γ-Al.sub.2O.sub.3 330 1 1.2 7.2 91.4 1.9 310 1 There is a yellow precipitate in product, indicating incomplete conversion 3 -NiMoW/ 350 1 3.4 3.6 93.0 6.5 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 4.2 3.2 92.5 5.0 310 1 5.5 3.2 91.3 4.4 3-0-NiMoW/ 350 1 2.6 8.0 89.3 2.4 γ-Al.sub.2O.sub.3—TiO.sub.2 330 1 1.6 5.4 92.8 2.1 310 1 1.1 2.6 96.2 2.0 3-0-NiMoW/ 350 1 2.1 4.4 93.5 2.5 γ-Al.sub.2O.sub.3—ZrO.sub.2 330 1 1.6 4.5 94.4 2.2 310 1 1.2 3.8 95.1 2.2

TABLE-US-00007 TABLE 7 Catalytic results of the catalyst 3-NiMoW/γ-Al.sub.2O.sub.3—TiO.sub.2 in HDO of palm oil, methyl-esterified palm oil, a waste fatty acid, and genetically modified soybean oil Oil Temp LHSV C5-C7 C8-C14 C15-C18 C17/ category (° C.) (hr.sup.−1) (%) (%) (%) C18 Palm oil 350 1 3.4 10.0 86.5 5.8 330 1 1.7 4.9 93.4 5.5 310 1 1.0 2.7 96.2 5.2 Methyl- 350 1 5.2 20.5 74.3 5.2 esterified 330 1 4.3 19.6 76.1 5.3 palm oil 310 1 3.2 18.9 77.9 5.0 Waste 350 1 3.2 10.5 86.0 6.3 fatty acid 330 1 1.7 4.9 93.4 6.3 310 1 1.0 2.7 96.2 5.4 Genetically 350 1 6.2 15.6 78.2 6.0 modified 330 1 5.3 18.4 76.3 5.6 soybean oil 310 1 4.8 16.2 79.0 5.2

[0090] From the catalytic results of the catalysts prepared using titanium dioxide-modified carrier through different times of impregnation in HDO of palm oil, it can be seen that, based on the composite carrier with regular pores, the particle size of the loaded metal active component gradually decreases with the increase of the number of impregnation times, and is reduced to a nano-scale or smaller when the impregnation is conducted six times; and as the particle size decreases, both the dispersion of the active component and the number of active sites increase. From the perspective of reaction, with the increase of the number of impregnation times, a ratio of C17 to C18 increases, indicating that the hydrodecarboxylation route has gradually become dominant, which increases the HDO activity, and reduces hydrogen consumption, hydrogen source loss, and energy consumption. A high C17 content indicates that the reaction is prone to the hydrodecarboxylation route and C is removed in the form of CO or CO.sub.2; and a high C18 content indicates that the reaction is prone to the hydrodehydration route and H.sub.2O is removed, which increases the corrosion of water vapor to the catalyst and reduces a life of the catalyst. It can be seen from Tables 1 and 4 that, with the increase of the number of impregnation times, a C17/C18 ratio increases and a proportion of C17 in the biodiesel product increases, which also proves that the multi-stage impregnation can increase active sites of the catalyst, reduce the production of water, and improve a life of the catalyst.

[0091] The multi-stage impregnation for the zirconium dioxide-modified carrier results in a similar effect to the multi-stage impregnation for the titanium dioxide-modified carrier, and the reaction data in Tables 2 and 5 also show similar laws, indicating that the catalysts prepared using the zirconium dioxide-modified carrier through multi-stage impregnation also have improved HDO activity.

[0092] As shown in Tables 3 and 6, conventional carrier-based catalysts and modified carrier-based catalysts prepared through the same number of impregnation times are compared, it can be known that the HDO activity drops sharply at a low temperature and thus the raw material cannot be converted into liquid alkane fuel components, resulting in yellow flocculent precipitates to block a reactor; the modified carrier with high hydrothermal stability can change the adaptability of the catalyst; and the decrease of the temperature among the reaction conditions can reduce the reaction risk factor and the production cost. In addition, the multi-stage impregnation process without roasting has the same effect as the ordinary one-time impregnation, and cannot achieve the physical and chemical parameters of the highly-dispersed hydrogenation catalyst; a catalyst prepared by the multi-stage impregnation process without roasting shows similar hydrogenation activity to a catalyst prepared by the ordinary one-time impregnation process; and in contrast, the catalyst prepared through the multi-stage impregnation and roasting process has more active sites, stronger hydrogenation activity, and longer lasting stability.

[0093] Table 7 shows the HDO reaction data of different oils under the catalyst prepared through three times of impregnation. Different oils have different compositions, and thus the selectivities for alkanes obtained through HDO, hydrodecarboxylation, and hydrodecarbonylation are different, but the overall HDO activities are all very high and stable. In addition to the long-chain alkane-based components, some medium and long-chain alkane components and short-chain alkane components can also be obtained, and thus the product can be used as a bio-jet fuel and a bio-aviation gasoline, resulting in high utilization.

[0094] The biofuel products were further verified below. With the diesel component as an example, an alkane product obtained after HDO (an HDO product of palm oil or a waste fatty acid) was subjected to rectification, and a distillate at 170° C. to 300° C. was recovered as the biodiesel component, and tested for various physical and chemical properties using diesel No. 0 according to the 20% volume fraction blending standard. Results are shown in Tables 8 to 9, and it can be seen that all items meet the standards, indicating that the prepared biofuels fully comply with the existing diesel standards.

TABLE-US-00008 TABLE 8 Test results of physical and chemical properties of palm oil biodiesel Quality Test result 20% blended standard Diesel palm oil Item No. 0 No. 0 biodiesel Test method Oxidative stability (calculated based on total insoluble 2.5 0.3 0.4 SH/T 0175 matters)/(mg/100 ml) No more than Sulfur content, mg/kg 10 3.4 2.9 SH/T 0689 No more than Acidity (calculated based on KOH)/(mg/100 ml) 7 4.13 4.13 GB/T 258 No more than Carbon residue based on a 10% distillation residue 0.3 0.03 0.02 GB/T 17144 (mass fraction)/% No more than Ash content (mass fraction)/% 0.01 0.006 0.005 GB/T 508 No more than Copper sheet corrosion (50° C., 3 h)/level 1 1a 1a GB/T 5096 No more than Water content (volume fraction)/% Trace No water No water GB/T 260 No more than Lubricity 460 391 376 SH/T 0765 Corrected wear scar diameter (60° C.)/μm, no more than Polycyclic aromatic hydrocarbon (PAH) content (mass 7 4.9 3.9 SH/T 0806 fraction)/% No more than Total contaminant content/(mg/kg) 24 2.5 3.0 GB/T 33400 Kinematic viscosity (20° C.)/(mm.sup.2/s) 3.0-8.0 4.371 4.388 GB/T 265 Condensation point/° C. 0 −14 −8 GB/T 510 Not higher than Cold filter plugging point (CFPP)/° C. −5 −13 −10 SH/T 0248 Not higher than Flash point (closed)/° C. 60 76.0 76.0 GB/T 261 Not lower than Cetane number 51 55.4 55.2 GB/T 386 No less than Cetane index 46 54.0 59.9 SH/T 0694 No less than Distillation range 50% recovery temperature/° C. 300 269.5 271.5 GB/T 6536 not higher than 90% recovery temperature/° C. 355 323.5 316.5 not higher than 95% recovery temperature/° C. 365 340.5 334.5 not higher than Density (20° C.), kg/m.sup.3 810-845 832.9 821.5 GB/T 1884 GB/T 1885 Fatty acid methyl ester (FAME) content (volume 1.0 <0.1 <0.1 NB/SH/T 0916 fraction)/% No more than

TABLE-US-00009 TABLE 9 Test results of physical and chemical properties of waste fatty acid biodiesel Quality Test result 20% blended standard Diesel waste fatty Item No. 0 No. 0 acid biodiesel Test method Oxidative stability (calculated based on total insoluble 2.5 0.3 0.3 SH/T 0175 matters)/(mg/100 ml) No more than Sulfur content, mg/kg 10 3.4 2.8 SH/T 0689 No more than Acidity (calculated based on KOH)/(mg/100 ml) 7 4.13 4.0 GB/T 258 No more than Carbon residue based on a 10% distillation residue 0.3 0.03 0.01 GB/T 17144 (mass fraction)/% No more than Ash content (mass fraction)/% 0.01 0.006 0.004 GB/T 508 No more than Copper sheet corrosion (50° C., 3 h)/level 1 1a 1a GB/T 5096 No more than Water content (volume fraction)/% Trace No water No water GB/T 260 No more than Lubricity 460 391 374 SH/T 0765 Corrected wear scar diameter (60.sup.° C.)/μm, no more than PAH content (mass fraction)/% 7 4.9 3.5 SH/T 0806 No more than Total contaminant content/(mg/kg) 24 2.5 3.2 GB/T 33400 Kinematic viscosity (20° C.)/(mm.sup.2/s) 3.0-8.0 4.371 4.288 GB/T 265 Condensation point/° C. 0 −14 −6 GB/T 510 Not higher than CFPP/° C. −5 −13 −11 SH/T 0248 Not higher than Flash point (closed)/° C. 60 76.0 75.0 GB/T 261 Not lower than Cetane number 51 55.4 55.6 GB/T 386 No less than Cetane index 46 54.0 59.8 SH/T 0694 No less than Distillation range 50% recovery temperature/° C. 300 269.5 270.5 GB/T 6536 not higher than 90% recovery temperature/° C. 355 323.5 315.5 not higher than 95% recovery temperature/° C. 365 340.5 332.3 not higher than Density (20° C.), kg/m.sup.3 810-845 832.9 822.5 GB/T 1884 GB/T 1885 FAME content (volume fraction)/% 1.0 <0.1 <0.1 NB/SH/T 0916 No more than

[0095] Some examples of the present disclosure are described above in detail, which are merely preferred examples of the present disclosure and cannot be construed as limiting the scope of implementation of the present disclosure. Any equivalent modifications, improvements, and the like made within the application scope of the present disclosure should fall within the protection scope of the present disclosure.