Method for preparing transportation fuel from hydrothermal liquefaction produced bio-crude oil

Abstract

Provided is a method for preparing a transportation fuel from a hydrothermal liquefaction produced bio-crude oil. A hydrothermal liquefaction produced bio-crude oil is subjected to distillation to obtain a purified bio-oil and a distillation residue; the purified bio-oil is subjected to hydrocracking to obtain a cracked bio-oil; the cracked bio-oil is subjected to catalytic hydrogenation to obtain a refined bio-oil; and the refined bio-oil is subjected to fractionation to obtain a transportation fuel.

Description

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This patent application claims the benefit and priority of Chinese Patent Application No. 202411593435.1 filed with the China National Intellectual Property Administration on Nov. 8, 2024, the disclosure of which is incorporated by reference herein in its entirety as part of the present disclosure.TECHNICAL FIELD

[0002] The present disclosure relates to the technical field of bio-crude oil treatment, in particular to a method for preparing a transportation fuel from a hydrothermal liquefaction produced bio-crude oil.BACKGROUND

[0003] With the continuous exploitation of resources, the reserve of conventional fossil energy such as coal, oil, natural gas, is gradually decreasing, leading to an increase of the pressure of energy supply. Under such circumstances, the bio-crude oil, as a renewable energy fuel, has gradually attracted widespread attention. Compared with conventional fossil fuels, bio-crude oil has the advantages of being renewable and few pollutants from burning, which is of great significance for solving the energy crisis and environmental pollution problems. It is worth noting that compared with conventional fuels, bio-crude oil has a low carbon and hydrogen content, a high oxygen content and a low heating value, and thus cannot provide sufficient power. Furthermore, factors such as a high acid value and a high viscosity also limit the use of bio-crude oil. Therefore, it has become the current research focus that optimization and improvement of the preparation process, and processing the bio-crude oil for hydrogenation and upgrading to improve the stability of bio-crude oil and improve related parameters.

[0004] At present, bio-crude oil is mainly prepared by two methods: pyrolysis and hydrothermal liquefaction. Pyrolysis is performed by a process of transforming biomass into bio-crude oil, charcoal and gas products through thermal decomposition reaction under the condition of isolating air or supplying a small amount of air. At present, bio-crude oil fuel conversion is performed mostly with pyrolysis produced bio-crude oil as raw material, by processes such as hydrogenation refining and catalytic reforming to obtain a single transportation fuel, such as diesel, gasoline, jet fuel, that can partially replace transportation fuel / directly applied. However, pyrolysis has high requirements for biomass raw materials, treatment processes, reaction conditions, application scenes, which is not conducive to the popularization of bio-crude oil fuel conversion technology. In contrast, hydrothermal liquefaction can obtain bio-crude oil by thermochemical conversion of biomass under a high temperature and a high pressure in water phase, and does not need to dry biomass, such that a wider variety of biomass raw materials could be used as raw materials. In addition, compared with pyrolysis produced bio-crude oil, hydrothermal liquefaction produced bio-crude oil has the advantages of a low water content, a low oxygen content and a high heating value, and thereby is more suitable for upgrading to realize fuel conversion. Therefore, it has become an urgent technical problem in this field that how to provide a hydrothermal liquefaction produced bio-crude oil fuel conversion technology.SUMMARY

[0005] An object of the present disclosure is to provide a method for preparing a transportation fuel from a hydrothermal liquefaction produced bio-crude oil, which successfully converts hydrothermal liquefaction produced bio-crude oil to transportation fuel to apply to diesel engines, gasoline engines and jet fuel engines. Moreover, after metal recovery, distillation residue obtained by distillation can be used to prepare high-quality biochar for subsequent returning to farmland, so as to realize full resource utilization and energy utilization of raw materials.

[0006] In order to achieve the above object, the present disclosure provides the following technical solutions:

[0007] The present disclosure provides a method for preparing a transportation fuel from a hydrothermal liquefaction produced bio-crude oil, which comprises the following steps:

[0008] 1) subjecting a hydrothermal liquefaction produced bio-crude oil to distillation to obtain a purified bio-oil and a distillation residue,

[0009] 2) subjecting the purified bio-oil to hydrocracking to obtain a cracked bio-oil,

[0010] 3) subjecting the cracked bio-oil to catalytic hydrogenation to obtain a refined bio-oil, and

[0011] 4) subjecting the refined bio-oil to fractionation to obtain a transportation fuel.

[0012] Optionally, the distillation is performed at a temperature of 150-350° C.

[0013] Optionally, the hydrocracking is performed at a temperature of 300-550° C., a hydrogen pressure of 5-20 MPa, and a hydrogen-oil ratio of 0.005-0.03 for 0.5-6 h.

[0014] Optionally, the hydrocracking is performed in the presence of a hydrocracking catalyst, the hydrocracking catalyst being a bifunctional catalyst consisting of a metal hydrogenation component and an acidic carrier;

[0015] the metal hydrogenation component comprises at least one selected from the group consisting of oxides of metal elements in groups VIB and VIII, sulfides of metal elements in groups VIB and VIII, and precious metals; and

[0016] the acidic carrier comprises at least one selected from the group consisting of an aluminosilicate ore, an artificial zeolite and a molecular sieve.

[0017] Optionally, the hydrocracking catalyst is presulfurized before use; a mass ratio of the purified bio-oil to the hydrocracking catalyst is in a range of 1.6-20:1.

[0018] Optionally, the catalytic hydrogenation is performed at a temperature of 200-400° C., a hydrogen pressure of 2-10 MPa, and a hydrogen-oil ratio of 0.01-0.04 for 1-6 h.

[0019] Optionally, the catalytic hydrogenation is performed in the presence of a hydrogenation catalyst, and the hydrogenation catalyst comprising at least one selected from the group consisting of an NiMo / Al2O3 catalyst and a Pt / Al2O3 catalyst.

[0020] Optionally, a mass ratio of the cracked bio-oil to the hydrogenation catalyst is 2:1.

[0021] Optionally, the transportation fuel comprises a gasoline, a jet fuel and a diesel fuel, and the gasoline is collected when the fractionation is performed at a temperature of 30-150° C., the jet fuel is collected when the fractionation is performed at a temperature of 150-250° C., and the diesel fuel is collected when the fractionation is performed at a temperature of 250-350° C.

[0022] Optionally, the method further comprises subjecting the distillation residue to metal recovery, and then preparing into a biochar.

[0023] Compared with the prior art, the present disclosure has the following beneficial effects:

[0024] 1. In the present disclosure, hydrothermal liquefaction produced bio-crude oil is converted to transportation fuel oil which can be applied in diesel engines, gasoline engines and jet fuel engines, through the process of purification by distillation, hydrocracking, catalytic hydrogenation and product fractionation.

[0025] 2. In the present disclosure, hydrothermal liquefaction produced bio-crude oil is preliminarily purified by distillation to remove impurities such as metals, salts, and micro carbon particles, thus avoiding the problems of catalyst metal poisoning, and difficult removal of solid impurities in the subsequent treatment process. The distillation residue, another product obtained in the distillation process, can be subjected to metal recovery, and then prepared as biochar for biological return to farmland to realize the resource utilization of raw materials.

[0026] 3. In the present disclosure, the purified bio-oil is hydrocracked to converted heavy oil in the bio-oil into light oil, and then subjected to catalytic hydrogenation to further remove harmful substances such as sulfur, oxygen and nitrogen in the bio-oil, so as to improve the quality of the bio-oil, and finally, transportation fuel, which can be directly applied to diesel, gasoline and aero-engines, is obtained through fractionation.

[0027] 4. Hydrogen involved in the hydrogenation of the present disclosure can be directly derived from wastewater treatment of hydrothermal liquefaction, and can also be obtained by combining the processes of dark fermentation hydrogen production of biomass waste, microbial electrochemical hydrogen production, so as to realize the full utilization of front-end hydrothermal liquefaction wastewater and biomass waste.

[0028] 5. The present disclosure provides a solution which breaks through the limitations of the prior art on the types of biomass raw materials for preparing hydrothermal liquefaction produced bio-crude oil, application scenes for upgrading bio-oil, and provides a feasible technical solution for the application and popularization of the technical route of hydrothermal liquefaction of biomass-bio-crude oil fuel conversion.DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] A number of exemplary embodiments of the present disclosure will now be described in detail, and this detailed description should not be considered as a limitation of the present disclosure, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present disclosure.

[0030] It should be understood that the terminology described in the present disclosure is only for describing specific embodiments and is not used to limit the present disclosure. In addition, for the numerical range in the present disclosure, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. The intermediate value within any stated value or stated range and every smaller range between any other stated value or intermediate value within the stated range are also included in the present disclosure. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0031] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this present disclosure relates. Although the present disclosure only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure. All documents mentioned in this specification are incorporated by reference to disclose and describe methods and / or materials related to the documents. In case of conflict with any incorporated document, the contents of this specification shall prevail.

[0032] It is obvious to those skilled in the art that many improvements and changes can be made to the specific embodiments of the present disclosure without departing from the scope or concept of the present disclosure. Other embodiments will be apparent to the skilled person from the description of the present disclosure. The specification and example of this application are only exemplary.

[0033] The terms “including”, “comprising”, “having” and “containing” used in this article are all open terms, which means including but not limited to.

[0034] The raw materials used in the present disclosure are commercially available or can be prepared by the prior art.

[0035] The present disclosure provides a method for preparing a transportation fuel from a hydrothermal liquefaction produced bio-crude oil, comprising the following steps:

[0036] 1) subjecting a hydrothermal liquefaction produced bio-crude oil to distillation to obtain a purified bio-oil and a distillation residue,

[0037] 2) subjecting the purified bio-oil to hydrocracking to obtain a cracked bio-oil,

[0038] 3) subjecting the cracked bio-oil to catalytic hydrogenation to obtain a refined bio-oil, and

[0039] 4) subjecting the refined bio-oil to fractionation to obtain a transportation fuel.

[0040] In the present disclosure, a hydrothermal liquefaction produced bio-crude oil is firstly subjected to distillation to obtain a purified bio-oil and a distillation residue.

[0041] The present disclosure has no special limitation on the source of the hydrothermal liquefaction produced bio-crude oil, which could be prepared from any biomass and hydrothermal liquefaction method. In the examples of the present disclosure, the hydrothermal liquefaction produced bio-crude oil is prepared by a method consisting of the following steps:

[0042] mixing a biomass raw material with water to obtain a mixture, subjecting the mixture to hydrothermal liquefaction to obtain a liquid phase, a gas phase and a residue, and separating the liquid phase to obtain a water phase and a bio-crude oil,

[0043] wherein the biomass raw material is selected from the group consisting of a Spirulina dry powder, a sewage sludge and a kitchen waste, a ratio of the biomass raw material to water is 1 g: 6 mL, the hydrothermal liquefaction is performed at a temperature of 300° C. for 30 min.

[0044] In the present disclosure, the distillation could be a conventional distillation such as atmospheric distillation or vacuum distillation. In the example of the present disclosure, the distillation is performed at normal pressure (i.e. standard atmospheric pressure).

[0045] In some embodiments of the present disclosure, the distillation is performed at a temperature of 150-350° C., preferably 160-300° C., further preferably 180-250° C., and even more preferably 200-220° C.

[0046] In the present disclosure, there is no limit to the duration of the distillation, which varies according to different raw materials, and the distillation could be ended until no liquid flows out any more. In the example of the present disclosure, the distillation is ended when there is no liquid collected in a vacuum receiver of a distillation device.

[0047] In some embodiments of the present disclosure, the method further comprises subjecting the distillation residue to metal recovery, and then preparing into a biochar for biological return to the farmland. In some embodiments of the present disclosure, the metal recovery could be performed by a conventional recovery method in the field, and the preparation method of the biochar includes but is not limited to pyrolysis and roasting. The biochar could be returned to farmland to improve the soil or used as a catalyst.

[0048] In the present disclosure, after obtaining the purified bio-oil, the purified bio-oil is subjected to hydrocracking to obtain a cracked bio-oil.

[0049] In some embodiments of the present disclosure, the hydrocracking is performed at a temperature of 300-550° C., preferably 320-500° C., further preferably 350-450° C., and even more preferably 400-420° C. In some embodiments of the present disclosure, the hydrocracking is performed for 0.5-6 h, preferably 2-5 h, further preferably 3-4 h. In some embodiments of the present disclosure, the hydrocracking is performed at a hydrogen pressure of 5-20 MPa, preferably 8-16 MPa, further preferably 10-12 MPa. In some embodiments of the present disclosure, the hydrocracking is performed at a hydrogen-oil ratio of 0.005-0.03, preferably 0.01-0.02, and even more preferably 0.015.

[0050] In some embodiments of the present disclosure, the hydrocracking is performed in the presence of a hydrocracking catalyst, the hydrocracking catalyst being a bifunctional catalyst consisting of a metal hydrogenation component and an acidic carrier.

[0051] In some embodiments of the present disclosure, the metal hydrogenation component comprises at least one selected from the group consisting of oxides of metal elements in groups VIB and VIII, sulfides of metal elements in groups VIB and VIII, and precious metals,

[0052] wherein the metal elements in groups VIB and VIII comprise Fe, Co, Ni, Cr, Mo, W, etc., preferably W and Ni;

[0053] In some embodiments of the present disclosure, the acidic carrier comprises at least one selected from the group consisting of an aluminosilicate ore, an artificial zeolite, an amorphous aluminium silicate and a molecular sieve, preferably the amorphous aluminium silicate.

[0054] In some embodiments of the present disclosure, the hydrocracking catalyst is FC-14 catalyst.

[0055] In some embodiments of the present disclosure, the hydrocracking catalyst is presulfurized before use, so as to improve the catalytic effects of the catalyst. In the examples of the present disclosure, the hydrocracking catalyst is presulfurized by a dry presulfurization method, and specifically performed as follows: in the presence of hydrogen-nitrogen mixed gas, the hydrocracking catalyst is mixed with dimethyl sulfide, and then subjected to reaction at a temperature of 150-350° C.; when a concentration of hydrogen sulfide in a circulating gas no longer changes, the presulfurization is completed, wherein a mass ratio of the hydrocracking catalyst to dimethyl sulfide is 2:1.

[0056] In some embodiments of the present disclosure, a mass ratio of the purified bio-oil to the hydrocracking catalyst is in a range of 1.6-20:1, preferably 2-5:1.

[0057] In some embodiments of the present disclosure, the purified bio-oil and the hydrocracking catalyst are mixed and then subjected to the hydrocracking under stirring, such that the materials are evenly mixed during the hydrocracking. The present disclosure has no special requirement on the stirring, as long as the purified bio-oil and the hydrocrack catalyst can be uniformly mixed.

[0058] In some embodiments of the present disclosure, the hydrocracking is performed in an environment of hydrogen. In the examples of the present disclosure, before the hydrocracking, a reactor is charged with nitrogen to ensure an oxygen-free environment, and then charged with hydrogen to replace nitrogen in the reactor, such that the reactor is only filled with hydrogen.

[0059] In some embodiments of the present disclosure, after the hydrocracking, a first reaction product from the hydrocracking is subjected to post-treatment to obtain the cracked bio-oil, the post-treatment preferably comprises the following steps: cooling the first reaction product, then filtering to obtain a liquid phase product, and subjecting the liquid phase product to phase separation to obtain an oil phase, namely the cracked bio-oil. In some embodiments of the present disclosure, the first reaction product is cooled by cooling the reactor with water; the filtration is preferably performed by filtering the first reaction product through a metal mesh, thus separating the hydrocracking catalyst. The present disclosure has no special requirements for the phase separation of the liquid phase product, as long as a water phase can be separated from the oil phase. In the examples of the present disclosure, the phase separation is performed by centrifugation, wherein the centrifugation is performed at a rotational speed of 3000-5000 rpm, preferably 4000 rpm for 3-8 min, preferably 5 min.

[0060] In the examples of the present disclosure, in order to improve the yield, the inside of the reactor, the metal mesh and the hydrocracking catalyst are washed with acetone to obtain a washing solution, and then the washing solution is distilled to remove the acetone, and the obtained residue is recovered and combined with the cracked bio-oil for further steps. In the examples of the present disclosure, the washing solution is distilled by a rotary evaporator.

[0061] In the present disclosure, after the cracked bio-oil is obtained, the cracked bio-oil is subjected to catalytic hydrogenation to obtain a refined bio-oil.

[0062] In some embodiments of the present disclosure, the catalytic hydrogenation is performed at a temperature of 200-400° C., preferably 250-380° C., further preferably 280-360° C., and even more preferably 300-350° C. In some embodiment of the present disclosure, the catalytic hydrogenation is performed for 1-6 h, preferably 2-5 h, and further preferably 3-4 h. In some embodiments of the present disclosure, the catalytic hydrogenation is performed at a hydrogen pressure of 2-10 MPa, preferably 3-6 MPa, and further preferably 4-5 MPa. In some embodiments of the present disclosure, the catalytic hydrogenation is performed at a hydrogen-oil ratio of 0.01-0.04, preferably 0.02-0.03.

[0063] In some embodiments of the present disclosure, the catalytic hydrogenation is performed in the presence of a hydrogenation catalyst, and the hydrogenation catalyst comprising at least one selected from the group consisting of an NiMo / Al2O3 catalyst and a Pt / Al2O3 catalyst, preferably NiMo / Al2O3 catalyst.

[0064] In some embodiments of the present disclosure, when the above hydrogenation catalyst is used, the hydrogenation catalyst is presulfurized before use, so as to improve the catalytic effects of the catalyst. In the examples of the present disclosure, the hydrogenation catalyst is presulfurized by a dry presulfurization method, and specifically performed as follows: in the presence of hydrogen-nitrogen mixed gas, the hydrogenation catalyst is mixed with dimethyl sulfide, and then subjected to reaction at a temperature of 150-350° C.; when a concentration of hydrogen sulfide in a circulating gas no longer changes, the presulfurization is completed, wherein a mass ratio of the hydrogenation catalyst to dimethyl sulfide is 2:1.

[0065] In some embodiments of the present disclosure, a mass ratio of the cracked bio-oil to the hydrogenation catalyst is 2:1.

[0066] In some embodiments of the present disclosure, the catalytic hydrogenation is performed in an environment of hydrogen. In the examples of the present disclosure, before the catalytic hydrogenation, a reactor is charged with nitrogen to ensure an oxygen-free environment, and then charged with hydrogen to replace nitrogen in the reactor, such that the reactor is only filled with hydrogen.

[0067] In some embodiments of the present disclosure, after the catalytic hydrogenation, a second reaction product from the catalytic hydrogenation is subjected to post-treatment to obtain the refined bio-oil. The post-treatment of the second reaction product is the same as that of hydrocracking, and will not be repeated herein.

[0068] In the present disclosure, after the refined bio-oil is obtained, the refined bio-oil is subjected to fractionation to obtain a transportation fuel.

[0069] In some embodiments of the present disclosure, the transportation fuel includes a gasoline, a jet fuel and a diesel fuel.

[0070] In some embodiments of the present disclosure, the gasoline is collected when the fractionation is performed at a temperature of 30-150° C., the jet fuel is collected when the fractionation is performed at a temperature of 150-250° C., and the diesel fuel is collected when the fractionation is performed at a temperature of 250-350° C.

[0071] The technical solutions provided by the present disclosure will be described in detail with examples below, but they cannot be understood as limiting the scope of the present disclosure.Example 1

[0072] 1) 2 g Spirulina dry powder was used as a biomass raw material, added with 12 mL water to obtain a mixture. The mixture was subjected to hydrothermal liquefaction at a temperature of 300° C. for 30 min to obtain a liquid phase, a gas phase and an algae residue. The liquid phase was subjected to phase separation to obtain a water phase and a bio-crude oil.

[0073] 2) The bio-crude oil obtained in step 1) was subjected to distillation at a temperature of 200° C. under atmospheric pressure until no liquid flowed out of a vacuum receiver of a distillation device, to obtain a purified bio-oil and a distillation residue. The distillation residue was subjected to metal recovery and then prepared into biochar by pyrolysis.

[0074] 3) 4 g of FC-14 hydrocracking catalyst was mixed with 2 g of dimethyl sulfide, and then subjected to presulfurization at a temperature of 150-350° C. in the presence of a hydrogen and nitrogen mixture, until the concentration of hydrogen sulfide in a circulating gas did not change any more, to obtain a presulfurized FC-14 hydrocracking catalyst.

[0075] 6 g of NiMo / Al2O3 catalyst was mixed with 3 g of dimethyl sulfide, and then subjected to presulfurization at a temperature of 150-350° C. in the presence of a hydrogen and nitrogen mixture, until the concentration of hydrogen sulfide in a circulating gas did not change any more, to obtain to obtain a presulfurized NiMo / Al2O3 catalyst.

[0076] 4) 4 g of the purified bio-oil and 2 g the presulfurized FC-14 hydrocracking catalyst into a 25 mL reactor. The reactor was repeatedly charged with nitrogen to ensure an oxygen-free environment, and then charged with hydrogen to remove residual nitrogen in the reactor and continuously charged with hydrogen to an initial pressure of 10 MPa. A stirring was started, the reactor is set at a temperature of 400° C., and kept at this temperature for 4 h for a reaction, with a weight hourly space velocity (WHSV) of 0.5 g / g cat·h, and a hydrogen-oil ratio of 0.015. After the reaction, a first reaction product from the reaction was subjected to a post-treatment as follows: the reactor was cooled with water, and a first reaction product from the reaction was filtered through a metal mesh to remove the FC-14 hydrocracking catalyst to obtain a liquid phase product; the liquid phase product was centrifuged at a rotational speed of 4000 rpm for 5 min to separate an oil phase from a water phase; the oil phase was collected, and recorded as bio-oil 1; the reactor, metal mesh and FC-14 hydrocracking catalyst were washed with 100 mL acetone to obtain a washing solution, and the washing solution was distilled by a rotary evaporator to remove acetone to obtain a residue recorded as bio-oil 2. Bio-oil 1 and bio-oil 2 were combined to obtain a cracked bio-oil.

[0077] 5) 6 g of the cracked bio-oil and 3 g of the presulfurized NiMo / Al2O3 catalyst were added into another 25 mL reactor. The reactor was repeatedly charged with nitrogen to ensure an oxygen-free environment, and then charged with hydrogen to remove residual nitrogen in the reactor and continuously charged with hydrogen to an initial pressure of 4 MPa. The reactor is set at a temperature of 350° C., and kept at this temperature for 4 h for a reaction, with a WHSV of 0.5 g / g cat·h, and a hydrogen-oil ratio of 0.02. After the reaction, a second reaction product from the reaction was subjected to a post-treatment as that of step 4), to obtain a refined bio-oil,

[0078] 6) The refined bio-oil obtained in step 5) was subjected to fractionation, in which a fraction at a temperature of 30-150° C. was collected to obtain a 20% gasoline; continuously heating, a fraction at a temperature of 150-250° C. was collected to obtain a 45% jet duel; and finally continuously heating, a fraction at a temperature of 250-350° C. was collected to obtain a 35% diesel fuel.

[0079] The elemental composition, hydrogen / carbon ratio (H / C) and high heating value (HHV) of the products obtained in step 1), step 2), step 4) and step 5) (i.e., the hydrothermal liquefaction produced bio-crude oil (A), purified bio-oil (B), cracked bio-oil (C) and refined bio-oil (D)) were analyzed, and the obtained results are shown in Table 1.TABLE 1-1Related parameters of bio-oilsProductCategoryC(wt %)H(wt %)O(wt %)N(wt %)H / CHHV(MJ / kg)A75.0 ± 0.310.6 ± 0.16.9 ± 0.37.5 ± 0.11.66 ± 0.0237.9 ± 0.2B79.3 ± 0.311.1 ± 0.13.9 ± 0.35.7 ± 0.11.68 ± 0.0240.3 ± 0.2C82.7 ± 0.411.7 ± 0.21.4 ± 0.54.2 ± 0.21.69 ± 0.0142.5 ± 0.2D85.6 ± 0.212.3 ± 0.20.2 ± 0.41.9 ± 0.11.72 ± 0.0244.3 ± 0.3

[0080] It can be seen from Table 1-1 that the process of the present disclosure has excellent upgrading effect on hydrothermal liquefaction produced bio-crude oil.

[0081] The diesel fuel, jet fuel and gasoline obtained in step 5) were tested respectively according to the test methods in the technical requirements for automotive diesel fuels China VI0 (GB 19147-2016), No. 3 jet fuel (GB 6537-2018) and automotive gasoline VIA92 (GB 17930-2016). The results are shown in tables 1-2, 1-3 and 1-4.TABLE 1-2Comparative analysis of diesel fuel propertiesLowerUpperSamplePropertyUnitlimitlimitvalueDensity (20° C.)kg / m3810845836Cetane number / 51 / 55Cetane index / 46 / 50Sulfur contentmg / kg / 100.25Flash point° C.≥60 / 70Polycyclic aromaticwt % / 75hydrocarbonTotal pollutant contentmg / kg / 2410Carbon residue (on 10%wt % / 0.300.03distillation residue)Lubricity, corrected wearμm / 460220scar diameter (60° C.)Content of polycyclicwt % / 73aromatic hydrocarbonsAsh contentwt % / 0.01<0.01Copper strip corrosion / / Class 1Class 1b(3 h at 50° C.)Aciditymg / / 74(based on KOH)100 mLOxidation stabilitymg / / 2.52.1(based on total100 mLinsolubles)Water content% / / Trace(Volume fraction)Kinematic viscosity (20° C.)mm2 / s3.08.06.4Condensation point° C. / 0−10Cold filter plugging point° C. / 40Fatty acid methyl ester% / 1.00.2content (volume fraction)Boiling range° C. / 50% / 30028090% / 35533595% / 365345TABLE 1-3Comparative analysis of jet fuel propertiesLowerUpperSamplePropertyUnitlimitlimitvalueAppearanceConformityColour / +25°+32°Total acid numbermg / g0.0150.01(based on KOH)Aromatic hydrocarbon%20.012.5(Volume fraction)Alkene%5.03.0(Volume fraction)Total sulfurwt %0.20.05Thiol sulfurwt %0.0020.000Freezing point° C.−47−60Kinetic viscosity (20° C.)mm2 / s1.251.40Kinetic viscosity (−20° C.)mm2 / s8.07.5Net heatMJ / kg42.845.6Smoke pointmm25.029.5Copper strip corrosion / Class 1Class 1b(2 h at 100° C.)Silver sheet corrosion / Class 1Class 1(4 h at 50° C.)Pressure dropkPa3.32.8(2.5 h at 260° C.)Wall rating / Class 3Class 2(2.5 h at 260° C.)Gum contentmg / 75.8100 mLInterface situation / Class 1bClass 1Degree of separation / Class 2Class 1Solid particle pollutantmg / L1.00.04contentElectrical conductivitypS / m50600280Water segregation index / 8594(without antistatic agent)Wear scar diameter WSDmm0.650.45Boiling range° C.10%20516550%232185Final boiling point300250Percent residue%1.50.8(Volume fraction)%1.51.2Percent loss(Volume fraction)Flash point (closed)° C.3845Density (20° C.)kg / m3775830795TABLE 1-4Comparative analysis of gasoline propertiesLowerUpperSamplePropertyUnitlimitlimitvalueResearch octane number / 9295Antiknock index / 8791Lead contentg / L0.0050Vapour pressurekPa408565(1101-0430)6555(0501-1031)Gum contentmg / 3020(unwashed)100 mL52.4(solvent washing)Induction periodmin480565Sulfur contentmg / kg103Thiol (doctor test)wt %PassCopper strip corrosion / Class 1Class 1b(3 h at 50° C.)Water soluble acids / Noand alkalisMechanical impurities / Noand moistureBenzene content%0.80.3(Volume fraction)Aromatic hydrocarbon content%3528(Volume fraction)Alkene content%1812(Volume fraction))Oxygen contentwt %2.71.0Methanol contentwt %0.30Mn contentg / L0.0020Fe contentg / L0.010.002Density (20° C.)kg / m3720775735Boiling range° C.10%705050%1109590%190135Final boiling point205150Percent residue(Volume fraction %)20.5The test results show that the transportation fuel prepared by this process meets the corresponding standards of China and the effect is excellent.Example 2Example 2 was performed according to Example 1, except that the bio-crude oil was prepared from sewage sludge

[0084] Correspondingly, related parameters of the bio-oils obtained during this example were tested, and the results are shown in Table 2-1.TABLE 2-1 Related parameters of bio-oilsProductcategoryC(wt %)H(wt %)O(wt %)N(wt %)H / CHHV(MJ / kg)A75.0 ± 0.410.1 ± 0.211.2 ± 0.1 3.7 ± 0.21.62 ± 0.0337.0 ± 0.3B80.3 ± 0.211.3 ± 0.16.3 ± 0.23.1 ± 0.21.69 ± 0.0240.8 ± 0.2C84.4 ± 0.212.5 ± 0.11.2 ± 0.11.9 ± 0.21.78 ± 0.0244.2 ± 0.4D85.6 ± 0.212.7 ± 0.20.0 ± 0.01.7 ± 0.11.78 ± 0.0145.0 ± 0.2

[0085] From Table 2-1, it can be seen that the process of the present disclosure still has excellent upgrading effect for hydrothermal liquefaction produced bio-crude oil with a high oxygen content, and by this method, heteroatoms can be effectively removed.

[0086] Key parameters of the prepared transportation fuel were tested with the same test methods as those in Example 1. The results are shown in Tables 2-2, 2-3 and 2-4.TABLE 2-2Comparative analysis of diesel fuel propertiesLowerUpperSamplePropertyUnitlimitlimitvalueDensity (20° C.)kg / m3810845816Cetane number / 51 / 58Sulfur contentmg / kg / 100.15Flash point° C.≥60 / 78Carbon residue (on 10%wt % / 0.300.05distillation residue)Ashwt % / 0.01<0.01Copper strip corrosion / / Class 1Class 1b(3 h at 50° C.)Aciditymg / / 72(based on KOH)100 mLOxidation stabilitymg / / 2.51.8(based on total insolubles)100 mLWater content% / / Trace(Volume fraction)Kinematic viscosity (20° C.)mm2 / s3.08.05.8Condensation point° C. / 0−12Boiling range° C. / 50% / 30027690% / 35533095% / 365340TABLE 2-3Comparative analysis of jet fuel propertiesLowerUpperSamplePropertyUnitlimitlimitvalueAppearanceConformityColour / +25°+30°Total acid numbermg / g0.0150.008(based on KOH)Aromatic hydrocarbon%20.010.5(Volume fraction)Alkene%5.02.4(Volume fraction)Total sulfurwt %0.20.08Freezing point° C.−47−65Kinetic viscosity (20° C.)mm2 / s1.251.37Kinetic viscosity (−20° C.)mm2 / s8.07.2Net heatMJ / kg42.845.2Smoke pointmm25.032.4Copper strip corrosionClass 1Class 1b(2 h at 100° C.)Silver sheet corrosionClass 1Class 1(4 h at 50° C.)Pressure dropkPa3.32.4(2.5 h at 260° C.)Gum contentmg / 73.2100 mLSolid particle pollutantmg / L1.00.02contentElectrical conductivitypS / m50600320Water segregation index / 8590(without antistatic agent)Wear scar diameter WSDmm0.650.30Boiling range° C.10%20516850%232190Final boiling point300245Percent residue%1.50.5(Volume fraction)%1.51.0Percent loss(Volume fraction)Flash point (closed)° C.3847Density (20° C.)kg / m3775830786TABLE 2-4Comparative analysis of gasoline propertiesLowerUpperSamplePropertyUnitlimitlimitvalueResearch octane number / 9294Antiknock index / 8792Lead contentg / L0.0050Gum contentmg / 3025(unwashed)100 mL53.6(solvent washing)Induction periodmin480525Sulfur contentmg / kg102Copper strip corrosion / Class 1Class 1b(3 h at 50° C.)Water soluble acids / Noand alkalisMechanical impurities / Noand moistureOxygen contentwt %2.70.2Methanol contentwt %0.30Mn contentg / L0.0020Fe contentg / L0.010.006Density (20° C.)kg / m3720775748Boiling range° C.10%705550%11010090%190140Final boiling point205145Percent residue(Volume fraction %)20.8The test results show that the transportation fuel prepared by the process of the present disclosure meets the corresponding standards of China and the effect is excellent.Example 3Example 3 was performed according to Example 1, except that the bio-crude oil was prepared from kitchen waste

[0089] Correspondingly, related parameters of the bio-oils obtained during this example were tested, and the results are shown in Table 3-1.TABLE 3-1 Related parameters of bio-oilsProductcategoryC(wt %)H(wt %)O(wt %)N(wt %)H / CHHV(MJ / kg)A76.6 ± 0.111.0 ± 0.111.8 ± 0.1 0.6 ± 0.01.72 ± 0.0238.7 ± 0.1B81.9 ± 0.213.1 ± 0.24.5 ± 0.10.5 ± 0.01.92 ± 0.0143.7 ± 0.1C84.8 ± 0.213.7 ± 0.11.2 ± 0.10.3 ± 0.01.94 ± 0.0245.8 ± 0.2D85.9 ± 0.214.1 ± 0.20.0 ± 0.00.0 ± 0.11.97 ± 0.0146.8 ± 0.1

[0090] From Table 3-1, it can be seen that the process of the present disclosure still has a good upgrading effect for raw materials with a high initial hydrogen-carbon ratio, such as hydrothermal liquefaction produced bio-crude oil from kitchen waste.

[0091] Key parameters of the prepared transportation fuel were tested, with the same test methods as those in Example 1. The results are shown in Tables 3-2, 3-3 and 3-4.TABLE 3-2Comparative analysis of diesel fuel propertiesLowerUpperSamplePropertyUnitlimitlimitvalueDensity (20° C.)kg / m3810845825Cetane number / 51 / 60Sulfur contentmg / kg / 100.08Flash point° C.≥60 / 75Carbon residue (on 10%wt % / 0.300.10distillation residue)Ashwt % / 0.01<0.01Copper strip corrosion / / Class 1Class 1b(3 h at 50° C.)Aciditymg / / 72.5(based on KOH)100 mLOxidation stabilitymg / / 2.51.4(based on total insolubles)100 mLWater content% / / Trace(Volume fraction)Kinematic viscosity (20° C.)mm2 / s3.08.06.8Condensation point° C. / 0−15Boiling range° C. / 50% / 30027090% / 35532595% / 365335TABLE 3-3Comparative analysis of jet fuel propertiesLowerUpperSamplePropertyUnitlimitlimitvalueAppearanceConformityColour / +25°+27°Total acid numbermg / g0.0150.006(based on KOH)Aromatic hydrocarbon%20.013.5(Volume fraction)Alkene%5.02.6(Volume fraction)Total sulfurwt %0.20.05Freezing point° C.−47−60Kinetic viscosity (20° C.)mm2 / s1.251.40Kinetic viscosity (−20° C.)mm2 / s8.06.9Net heatMJ / kg42.846.4Smoke pointmm25.030.2Copper strip corrosion / Class 1Class 1b(2 h at 100° C.)Silver sheet corrosion / Class 1Class 1(4 h at 50° C.)Pressure dropkPa3.32.6(2.5 h at 260° C.)Gum contentmg / 72.6100 mLSolid particle pollutantmg / L1.00.03contentElectrical conductivitypS / m50600390Water segregation index / 8592(without antistatic agent)Wear scar diameter WSDmm0.650.45Boiling range° C.10%20516550%232185Final boiling point300240Percent residue%1.50.7(Volume fraction)%1.51.0Percent loss(Volume fraction)Flash point (closed)° C.3845Density (20° C.)kg / m3775830790TABLE 3-4Comparative analysis of gasoline propertiesLowerUpperSamplePropertyUnitlimitlimitvalueResearch octane number / 9293Antiknock index / 8794Lead contentg / L0.0050Gum contentmg / 3020(unwashed)100 mL52.8(solvent washing)Induction periodmin480542Sulfur contentmg / kg101.2Copper strip corrosion / Class 1Class 1b(3 h at 50° C.)Water soluble acids / Noand alkalisMechanical impurities / Noand moistureOxygen contentwt %2.70.0Methanol contentwt %0.30Mn contentg / L0.0020Fe contentg / L0.010.008Density (20° C.)kg / m3720775744Boiling range° C.10%705850%11010590%190140Final boiling point205148Percent residue21.2(Volume fraction %)The test results show that the transportation fuel prepared by the process of the present disclosure meets the corresponding standards of China and the effect is excellent.The above is only preferred embodiment of the present disclosure, and it shall be noted that a person skilled in the art could make several improvements and modifications without departing from the concept of the present disclosure, and these improvements and modifications shall also be regarded as falling within the scope of the present disclosure.

Claims

1. A method for preparing a transportation fuel from a hydrothermal liquefaction produced bio-crude oil, comprising the following steps:1) subjecting a hydrothermal liquefaction produced bio-crude oil to distillation to obtain a purified bio-oil and a distillation residue,2) subjecting the purified bio-oil to hydrocracking to obtain a cracked bio-oil,3) subjecting the cracked bio-oil to catalytic hydrogenation to obtain a refined bio-oil, and4) subjecting the refined bio-oil to fractionation to obtain a transportation fuel.

2. The method of claim 1, wherein the distillation is performed at a temperature of 150-350° C.

3. The method of claim 1, wherein the hydrocracking is performed at a temperature of 300-550° C., a hydrogen pressure of 5-20 MPa, and a hydrogen-oil ratio of 0.005-0.03 for 0.5-6 h.

4. The method of claim 3, wherein the hydrocracking is performed in the presence of a hydrocracking catalyst, the hydrocracking catalyst being a bifunctional catalyst consisting of a metal hydrogenation component and an acidic carrier;the metal hydrogenation component comprises at least one selected from the group consisting of oxides of metal elements in groups VIB and VIII, sulfides of metal elements in groups VIB and VIII, and precious metals; andthe acidic carrier comprises at least one selected from the group consisting of an aluminosilicate ore, an artificial zeolite and a molecular sieve.

5. The method of claim 4, wherein the hydrocracking catalyst is presulfurized before use; a mass ratio of the purified bio-oil to the hydrocracking catalyst is in a range of 1.6-20:1.

6. The method of claim 1, wherein the catalytic hydrogenation is performed at a temperature of 200-400° C., a hydrogen pressure of 2-10 MPa, and a hydrogen-oil ratio of 0.01-0.04 for 1-6 h.

7. The method of claim 6, wherein the catalytic hydrogenation is performed in the presence of a hydrogenation catalyst, and the hydrogenation catalyst comprising at least one selected from the group consisting of an NiMo / Al2O3 catalyst and a Pt / Al2O3 catalyst.

8. The method of claim 7, wherein a mass ratio of the cracked bio-oil to the hydrogenation catalyst is 2:1.

9. The method of claim 1, wherein the transportation fuel comprises a gasoline, a jet fuel and a diesel fuel, and the gasoline is collected when the fractionation is performed at a temperature of 30-150° C., the jet fuel is collected when the fractionation is performed at a temperature of 150-250° C., and the diesel fuel is collected when the fractionation is performed at a temperature of 250-350° C.

10. The method of claim 1, further comprising subjecting the distillation residue to metal recovery, and then preparing into a biochar.