阅读说明：本技术 一种生物柴油和航空燃料的制备方法及其应用 (Preparation method and application of biodiesel and aviation fuel ) 是由 陈钦 李明时 张伟 张旭中 于 2021-08-18 设计创作，主要内容包括：本发明公开了一种生物柴油和航空燃料的制备方法及其应用,制备方法包括将原料油进行预处理后,将其与甲醇混合,然后依序经升压、加热和醇解反应处理后,制得粗脂肪甲酯、粗甘油和水,按预设条件对粗脂肪酸甲酯进行处理后,将处理产物导入加氢脱氧反应器中,并按预设参数和条件对其进行加氢脱氧处理,生成加氢脱氧处理产物,该加氢脱氧处理产物经加氢转化处理后,被选择性裂化反应,获得加氢转化生成物,该加氢转化生成物再经分离处理后,获得生物柴油、生物航空燃料；本方案工艺稳定可靠、成本低且产品性能稳定。(The invention discloses a preparation method and application of biodiesel and aviation fuel, wherein the preparation method comprises the steps of pretreating raw oil, mixing the raw oil with methanol, sequentially carrying out pressure boosting, heating and alcoholysis reaction treatment to obtain crude fatty acid methyl ester, crude glycerin and water, treating the crude fatty acid methyl ester according to preset conditions, introducing a treated product into a hydrodeoxygenation reactor, carrying out hydrodeoxygenation treatment on the treated product according to preset parameters and conditions to generate a hydrodeoxygenation treated product, carrying out hydrogenation conversion treatment on the hydrodeoxygenation treated product, carrying out selective cracking reaction to obtain a hydrogenation conversion product, and separating the hydrogenation conversion product to obtain the biodiesel and the aviation fuel; the technical scheme has stable and reliable process, low cost and stable product performance.)

1. The preparation method of the biodiesel and the aviation fuel is characterized by comprising the following steps: the method comprises the steps of pretreating raw oil, mixing the raw oil with methanol, sequentially performing pressure boosting, heating and alcoholysis reaction treatment on the raw oil to obtain crude fatty methyl ester, crude glycerin and water, treating the crude fatty acid methyl ester according to preset conditions, introducing a treated product into a hydrodeoxygenation reactor, performing hydrodeoxygenation treatment on the treated product according to preset parameters and conditions to generate a hydrodeoxygenated treated product, performing selective cracking reaction on the hydrodeoxygenated treated product to obtain a hydroconversion product, and separating the hydroconversion product to obtain the biodiesel and the biological aviation fuel.

2. The process for the preparation of biodiesel and aviation fuel according to claim 1, wherein: which comprises the following steps:

s01, pretreating raw oil, mixing the raw oil and methanol according to the volume ratio of 1-3: 1, and then placing the mixed system under the conditions of 6-12 Mpa of reaction pressure and 240-340 ℃ to enable the mixed system to have alcoholysis reaction for 90-150 min to prepare crude fatty acid methyl ester, crude glycerol and water;

s02, separating the crude fatty acid methyl ester and carrying out flash evaporation treatment on the crude fatty acid methyl ester to obtain refined fatty acid methyl ester;

s03, setting the temperature of the hydrodeoxygenation reactor at 280-300 ℃, setting the hydrogen pressure at 4.2-4.6 Mpa, pumping the refined fatty acid methyl ester into the hydrodeoxygenation reactor, and enabling the refined fatty acid methyl ester to be in contact with a hydrodeoxygenation catalyst loaded in the reactor to generate a hydrodeoxygenation reaction, so as to obtain a hydrodeoxygenation treatment product;

s04, carrying out contact reaction treatment on the hydrodeoxygenation product and a hydroconversion catalyst in a hydrogen atmosphere, and then selectively cracking and reacting the hydrodeoxygenation product under the hydroconversion condition to obtain a hydroconversion product;

and S05, introducing the hydroconversion product into a separation device for separation and fractionation treatment to obtain the biodiesel and the biological aviation fuel.

3. The process for the preparation of biodiesel and aviation fuel according to claim 2, wherein: in step S01, the raw oil is pretreated after being filtered by a screen, heated and boiled, sieved by a secondary filter screen, decolorized and sieved by a tertiary filter screen to remove suspended matters; wherein the heating and boiling time is 5-10 min.

4. The process for the preparation of biodiesel and aviation fuel according to claim 2, wherein: in the step S01, the mixed system is placed under the conditions of a reaction pressure of 7-8 Mpa and a temperature of 290-300 ℃, and alcoholysis reaction is carried out on the mixed system for 125-140 min;

in the step S02, carrying out flash evaporation treatment on the crude fatty acid methyl ester through flash evaporation equipment at the temperature of 280-380 ℃ and the pressure of 2-4 kpa;

in step S03, the temperature of the hydrodeoxygenation reactor is set to 290 +/-3 ℃, the hydrogen pressure is set to 4.4 +/-1 Mpa, and the volume ratio of the hydrogen to the refined fatty acid methyl ester is 600-800 Nm³/m³；

In step S04, at a preset temperature of 265 to 275 ℃ and a preset hydrogen pressure of 4.0 to 5.0Mpa, the hydrodeoxygenation product and the hydroconversion catalyst are subjected to a contact reaction treatment, so that the hydrodeoxygenation-isomerization reaction is performed, and the hydrodeoxygenation product is subjected to a selective cracking reaction under the hydroconversion condition, thereby obtaining a hydroconversion product.

5. The process for the preparation of biodiesel and aviation fuel according to claim 2, wherein: in step S03, the preparation method of the hydrodeoxygenation catalyst comprises:

(011) mixing and dissolving phenol and formaldehyde in a sodium hydroxide solution according to a molar ratio of 1: 0.5, removing water to obtain a phenolic resin solution, adding P123 serving as an active agent and n-decane serving as an organic solvent into the phenolic resin solution, uniformly mixing, performing evaporation and thermal polymerization, placing a product into a cylindrical mold, roasting and carbonizing at 700 +/-20 ℃ for 3.5 hours, and naturally cooling to normal temperature to obtain a columnar mesoporous carbon-based material;

(012) placing 100g of carbon-based mesoporous material with a columnar structure in a nitrogen atmosphere for activation treatment for 4 hours at the temperature of 450-460 ℃, then stopping nitrogen supply, and placing the carbon-based mesoporous material in a negative pressure environment with-10 Kpa for negative pressure treatment for 8 minutes to obtain a pretreated carbon-based mesoporous material;

(013) immersing the pretreated carbon-based mesoporous material in 200ml of active component precursor solution (NH) with the concentration of 0.2mol/L₄)₆Mo₇O₂₄·4H₂In O, enabling an active component precursor solution to be in a low-speed flowing state of 0.07m/min, after immersion treatment for 20min, taking out the pretreated carbon-based mesoporous material, placing the pretreated carbon-based mesoporous material in a nitrogen atmosphere, and performing vacuum drying treatment for 1.5h at the temperature of 100-110 ℃ to obtain a catalyst precursor;

(014) placing a catalyst precursor into a reactor, introducing a reducing gas into the reactor, heating the temperature of the reactor to 300 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 0.5h, heating the temperature of the reactor to 600 ℃ at a heating rate of 5-8 ℃/min, keeping the temperature for 1h, heating the temperature of the reactor to 820 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 2.5h, preparing an active component attached to the carbon-based mesoporous material, keeping the atmosphere of the reducing gas, and naturally cooling the reactor to normal temperature to prepare the hydrodeoxygenation catalyst.

6. The process for the preparation of biodiesel and aviation fuel according to claim 5, wherein: in the step (011), the pore volume of the carbon-based mesoporous material is 1.7-1.8 cm³(ii)/g; the specific surface area of the carbon-based mesoporous material is 1500-1600 m²The pore diameter is 8-12 nm.

7. The process for the preparation of biodiesel and aviation fuel according to claim 2, wherein: in step S04, the preparation method of the hydroconversion catalyst includes:

(021) dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

(022) placing the mixed material in a reaction kettle, then pre-mixing the template agent, the pore-expanding agent and deionized water, then adding the mixed material into the reaction kettle, stirring and mixing the mixed material, placing the mixed material in an environment of 90-95 ℃ for drying treatment for 1h, adjusting the temperature of the reaction kettle to 130-135 ℃ for crystallization treatment for 16h, finally heating the temperature of a reaction system to 620-630 ℃ for roasting treatment for 6h, and preparing the nickel-doped SAPO-11 carrier;

(023) mixing an SAPO-11 carrier, pseudo-boehmite, sesbania powder and an acetic acid solution, grinding, stirring, extruding and molding, and drying at 110 +/-2 ℃ for 2 hours to prepare a catalyst precursor;

(024) putting a catalyst precursor in a hydrogen atmosphere at a temperature of 420-430 ℃, carrying out reduction reaction treatment for 4h, then reducing the temperature of a system to 130 +/-5 ℃, then introducing a phosphating solution for soaking treatment, keeping the flow rate of the phosphating solution at 1.0m/min for circulation after introducing the phosphating solution, then heating the temperature of the system to 230 +/-5 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 3h, then heating the temperature of the system to 370 +/-5 ℃ at a heating rate of 3 ℃/min, discharging the phosphating solution after keeping the temperature for 3h, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining a hydro-conversion catalyst after the temperature of the system is restored to normal temperature;

wherein, in the step (021), the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 1.3: 0.4: 50: 0.6; in the step (022), the addition molar ratio of the template agent, the pore-expanding agent and the deionized water is 3.5: 0.6: 10.

In addition, the adding molar ratio of the components of the aluminum source, the phosphorus source, the silicon source, the deionized water, the nickel source, the template agent and the pore-expanding agent in the reaction kettle in the step (022) is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6; in the step (023), the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 75: 14: 3.5, the mass concentration of the acetic acid solution is 35%, and the adding amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier.

8. The process for the preparation of biodiesel and aviation fuel according to claim 7, wherein: the above-mentionedThe aluminum source of the aluminum alloy is aluminum hydroxide; the phosphorus source is phosphoric acid solution; the silicon source is tetraethoxysilane; the nickel source is basic nickel carbonate; the template agent is dodecyl dimethyl tertiary amine; the pore-expanding agent is n-butyl alcohol; the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3 percent, and the liquid volume space velocity is 2.5h^-1。

9. A method for recycling waste animal and vegetable oils, characterized in that it comprises a method for producing biodiesel and aviation fuel according to any one of claims 1 to 8.

10. The method for recycling waste animal and vegetable oil according to claim 9, wherein the waste animal and vegetable oil comprises more than one of animal oil, vegetable oil and swill oil.

Technical Field

The invention relates to the technical fields of fuel preparation and waste oil recycling, in particular to a preparation method and application of biodiesel and aviation fuel.

Background

Biodiesel, which is an energy source that is popular in the time, is widely regarded as one of supplementary energy sources for fossil energy because of its advantages of being environmentally friendly and renewable. Since the main chemical composition of biodiesel is fatty acid methyl ester, it is usually made by transesterification of vegetable fats and oils (fatty acid triglycerides) with methanol. Biodiesel has relatively high condensation point and cloud point, and has poor chemical stability, high oxygen content and low energy density, so that the biodiesel is difficult to be completely compatible with traditional fossil diesel, thereby limiting the application of the biodiesel.

Nowadays, with the abundance of living standard and daily consumption of people, the base number of waste oil is increasing, the source of the waste oil is becoming wider and wider, and the waste oil is usually rich in precursors which can be used as biodiesel and aviation fuel, and if the waste oil can be recycled and treated and combined with process reaction to change waste into valuable, the waste oil is a topic with positive practical significance.

Disclosure of Invention

Aiming at the situation of the prior art, the invention aims to provide a preparation method and application of biodiesel and aviation fuel, which have stable and reliable process, low cost and stable product performance.

In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:

a process for preparing biologic diesel oil and aviation fuel includes pretreating raw oil, mixing it with methanol, boosting pressure, heating and alcoholysis for reaction to obtain raw methyl ester, raw glycerin and water, treating the raw methyl ester, hydrodeoxidizing, selective cracking for obtaining the product, and separating.

As a possible implementation manner, further, the scheme specifically includes the following steps:

s01, pretreating raw oil, mixing the raw oil and methanol according to the volume ratio of 1-3: 1, and then placing the mixed system under the conditions of 6-12 Mpa of reaction pressure and 240-340 ℃ to enable the mixed system to have alcoholysis reaction for 90-150 min to prepare crude fatty acid methyl ester, crude glycerol and water;

s02, separating the crude fatty acid methyl ester and carrying out flash evaporation treatment on the crude fatty acid methyl ester to obtain refined fatty acid methyl ester;

s03, setting the temperature of the hydrodeoxygenation reactor at 280-300 ℃, setting the hydrogen pressure at 4.2-4.6 Mpa, pumping the refined fatty acid methyl ester into the hydrodeoxygenation reactor, and enabling the refined fatty acid methyl ester to be in contact with a hydrodeoxygenation catalyst loaded in the reactor to generate a hydrodeoxygenation reaction, so as to obtain a hydrodeoxygenation treatment product;

s04, carrying out contact reaction treatment on the hydrodeoxygenation product and a hydroconversion catalyst in a hydrogen atmosphere, and then selectively cracking and reacting the hydrodeoxygenation product under the hydroconversion condition to obtain a hydroconversion product;

and S05, introducing the hydroconversion product into a separation device for separation and fractionation treatment to obtain the biodiesel and the biological aviation fuel.

As a preferred embodiment, preferably, in step S01, the raw oil is subjected to screen filtration, boiling by heating, secondary screening, decolorization, and tertiary screening to remove suspended matters, and then the pretreatment is completed; wherein the heating and boiling time is 5-10 min.

As a preferred selection embodiment, preferably, in step S01, the mixed system is placed under a reaction pressure of 7 to 8Mpa and a temperature of 290 to 300 ℃ to allow alcoholysis reaction of the mixed system, wherein the reaction time is 125 to 140 min;

in the step S02, carrying out flash evaporation treatment on the crude fatty acid methyl ester through flash evaporation equipment at the temperature of 280-380 ℃ and the pressure of 2-4 kpa;

in step S03, the temperature of the hydrodeoxygenation reactor is set to 290 +/-3 ℃, the hydrogen pressure is set to 4.4 +/-1 Mpa, and the volume ratio of the hydrogen to the refined fatty acid methyl ester is 600-800 Nm³/m³；

In step S04, at a preset temperature of 265 to 275 ℃ and a preset hydrogen pressure of 4.0 to 5.0Mpa, the hydrodeoxygenation product and the hydroconversion catalyst are subjected to a contact reaction treatment, so that the hydrodeoxygenation-isomerization reaction is performed, and the hydrodeoxygenation product is subjected to a selective cracking reaction under the hydroconversion condition, thereby obtaining a hydroconversion product.

As a preferred alternative, preferably, in step S03, the preparation method of the hydrodeoxygenation catalyst comprises:

(011) mixing and dissolving phenol and formaldehyde in a sodium hydroxide solution according to a molar ratio of 1: 0.5, removing water to obtain a phenolic resin solution, adding P123 serving as an active agent and n-decane serving as an organic solvent into the phenolic resin solution, uniformly mixing, performing evaporation and thermal polymerization, placing a product into a cylindrical mold, roasting and carbonizing at 700 +/-20 ℃ for 3.5 hours, and naturally cooling to normal temperature to obtain a columnar mesoporous carbon-based material;

(012) placing 100g of carbon-based mesoporous material with a columnar structure in a nitrogen atmosphere for activation treatment for 4 hours at the temperature of 450-460 ℃, then stopping nitrogen supply, and placing the carbon-based mesoporous material in a negative pressure environment with-10 Kpa for negative pressure treatment for 8 minutes to obtain a pretreated carbon-based mesoporous material;

(013) immersing the pretreated carbon-based mesoporous material in 200ml of active component precursor solution (NH) with the concentration of 0.2mol/L₄)₆Mo₇O₂₄·4H₂And in O, enabling the active component precursor solution to be in a low-speed flowing state of 0.07m/min, after immersion treatment for 20min, taking out the pretreated carbon-based mesoporous material, placing the pretreated carbon-based mesoporous material in a nitrogen atmosphere, and performing vacuum drying treatment for 1.5h at the temperature of 100-110 ℃ to prepare the active componentObtaining a catalyst precursor;

(014) placing a catalyst precursor into a reactor, introducing a reducing gas into the reactor, heating the temperature of the reactor to 300 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 0.5h, heating the temperature of the reactor to 600 ℃ at a heating rate of 5-8 ℃/min, keeping the temperature for 1h, heating the temperature of the reactor to 820 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 2.5h, preparing an active component attached to the carbon-based mesoporous material, keeping the atmosphere of the reducing gas, and naturally cooling the reactor to normal temperature to prepare the hydrodeoxygenation catalyst.

As a preferred alternative embodiment, in the step (011), the pore volume of the carbon-based mesoporous material is preferably 1.7 to 1.8cm³(ii)/g; the specific surface area of the carbon-based mesoporous material is 1500-1600 m²The pore diameter is 8-12 nm.

As a preferred alternative, preferably, in step S04, the preparation method of the hydroconversion catalyst is:

(021) dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

(022) placing the mixed material in a reaction kettle, then pre-mixing the template agent, the pore-expanding agent and deionized water, then adding the mixed material into the reaction kettle, stirring and mixing the mixed material, placing the mixed material in an environment of 90-95 ℃ for drying treatment for 1h, adjusting the temperature of the reaction kettle to 130-135 ℃ for crystallization treatment for 16h, finally heating the temperature of a reaction system to 620-630 ℃ for roasting treatment for 6h, and preparing the nickel-doped SAPO-11 carrier;

(023) mixing an SAPO-11 carrier, pseudo-boehmite, sesbania powder and an acetic acid solution, grinding, stirring, extruding and molding, and drying at 110 +/-2 ℃ for 2 hours to prepare a catalyst precursor;

(024) placing the catalyst precursor in a hydrogen atmosphere at a temperature of 420-430 ℃ for reduction reaction treatment for 4h, then the temperature of the system is reduced to 130 +/-5 ℃, then the phosphating solution is introduced for soaking treatment, and after the phosphating solution is introduced, the phosphating solution is kept to circulate at the flow rate of 1.0m/min (the phosphating solution adopts a circulating low-speed flowing mode to greatly improve the soaking diffusion speed and fully contact with a catalyst precursor), then the temperature of the system is increased to 230 plus or minus 5 ℃ at the heating rate of 3 ℃/min, after the temperature is kept for 3 hours, the temperature of the system is increased to 370 plus or minus 5 ℃ at the heating rate of 3 ℃/min, after the temperature is kept for 3 hours, discharging the phosphating solution, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling until the system temperature returns to the normal temperature, and preparing a hydro-conversion catalyst;

wherein, in the step (021), the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 1.3: 0.4: 50: 0.6; in the step (022), the addition molar ratio of the template agent, the pore-expanding agent and the deionized water is 3.5: 0.6: 10.

In addition, the adding molar ratio of the components of the aluminum source, the phosphorus source, the silicon source, the deionized water, the nickel source, the template agent and the pore-expanding agent in the reaction kettle in the step (022) is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6; in the step (023), the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 75: 14: 3.5, the mass concentration of the acetic acid solution is 35%, and the adding amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier.

As a preferred alternative, it is preferred that the aluminum source is aluminum hydroxide; the phosphorus source is phosphoric acid solution; the silicon source is tetraethoxysilane; the nickel source is basic nickel carbonate; the template agent is dodecyl dimethyl tertiary amine; the pore-expanding agent is n-butyl alcohol; the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3 percent, and the liquid volume space velocity is 2.5h^-1。

Based on the preparation method, the invention also provides a method for recycling the waste animal and vegetable oil, which comprises the preparation method of the biodiesel and the aviation fuel.

As a preferred embodiment, preferably, the waste animal and vegetable oil includes more than one of animal oil, vegetable oil and fat, and swill oil and fat.

By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: the technical scheme is ingenious, raw oil is pretreated and subjected to alcoholysis reaction, the obtained crude fatty acid methyl ester is subjected to secondary treatment, the treated product is introduced into a hydrodeoxygenation reactor to be subjected to hydrodeoxygenation treatment, the generated hydrodeoxygenation treatment product is subjected to hydroconversion treatment and then is subjected to selective cracking reaction to obtain a hydroconversion product, and the hydroconversion product is subjected to separation treatment to obtain biodiesel and biological aviation fuel.

Drawings

The invention will be further explained with reference to the drawings and the detailed description below:

FIG. 1 is a schematic flow chart of a preparation method of the present invention;

FIG. 2 is a schematic flow diagram of the components of the materials in the preparation method of the invention.

Detailed Description

As shown in fig. 1 or fig. 2, the preparation method of biodiesel and aviation fuel of the present invention specifically comprises the following steps:

s01, pretreating raw oil, mixing the raw oil and methanol according to the volume ratio of 1-3: 1, and then placing the mixed system under the conditions of 6-12 Mpa of reaction pressure and 240-340 ℃ to enable the mixed system to have alcoholysis reaction for 90-150 min to prepare crude fatty acid methyl ester, crude glycerol and water;

s02, separating the crude fatty acid methyl ester and carrying out flash evaporation treatment on the crude fatty acid methyl ester to obtain refined fatty acid methyl ester;

s03, setting the temperature of the hydrodeoxygenation reactor at 280-300 ℃, setting the hydrogen pressure at 4.2-4.6 Mpa, pumping the refined fatty acid methyl ester into the hydrodeoxygenation reactor, and enabling the refined fatty acid methyl ester to be in contact with a hydrodeoxygenation catalyst loaded in the reactor to generate a hydrodeoxygenation reaction, so as to obtain a hydrodeoxygenation treatment product;

s04, carrying out contact reaction treatment on the hydrodeoxygenation product and a hydroconversion catalyst in a hydrogen atmosphere, and then selectively cracking and reacting the hydrodeoxygenation product under the hydroconversion condition to obtain a hydroconversion product;

and S05, introducing the hydroconversion product into a separation device for separation and fractionation treatment to obtain the biodiesel and the biological aviation fuel.

The method for pretreating the raw oil in the step S01 comprises the following steps: the raw oil is subjected to screen filtering, heating boiling, secondary filter screen sieving, decoloring treatment and tertiary filter screen sieving to remove suspended matters, and then pretreatment is completed; wherein the heating and boiling time is 5-10 min.

As a preferred selection embodiment, preferably, in step S01, the mixed system is placed under a reaction pressure of 7 to 8Mpa and a temperature of 290 to 300 ℃ to allow alcoholysis reaction of the mixed system, wherein the reaction time is 125 to 140 min; in the step S02, carrying out flash evaporation treatment on the crude fatty acid methyl ester through flash evaporation equipment at the temperature of 280-380 ℃ and the pressure of 2-4 kpa; in step S03, the temperature of the hydrodeoxygenation reactor is set to 290 +/-3 ℃, the hydrogen pressure is set to 4.4 +/-1 Mpa, and the volume ratio of the hydrogen to the refined fatty acid methyl ester is 600-800 Nm³/m³(ii) a In step S04, at a preset temperature of 265 to 275 ℃ and a preset hydrogen pressure of 4.0 to 5.0Mpa, the hydrodeoxygenation product and the hydroconversion catalyst are subjected to a contact reaction treatment, so that the hydrodeoxygenation-isomerization reaction is performed, and the hydrodeoxygenation product is subjected to a selective cracking reaction under the hydroconversion condition, thereby obtaining a hydroconversion product.

In this embodiment, as a preferred alternative, preferably, in step S03, the preparation method of the hydrodeoxygenation catalyst comprises:

(011) mixing and dissolving phenol and formaldehyde in a sodium hydroxide solution according to a molar ratio of 1: 0.5, removing water to obtain a phenolic resin solution, adding P123 serving as an active agent and n-decane serving as an organic solvent into the phenolic resin solution, uniformly mixing, performing evaporation and thermal polymerization, placing a product into a cylindrical mold, roasting and carbonizing at 700 +/-20 ℃ for 3.5 hours, and naturally cooling to normal temperature to obtain a columnar mesoporous carbon-based material;

(012) placing 100g of carbon-based mesoporous material with a columnar structure in a nitrogen atmosphere for activation treatment for 4 hours at the temperature of 450-460 ℃, then stopping nitrogen supply, and placing the carbon-based mesoporous material in a negative pressure environment with-10 Kpa for negative pressure treatment for 8 minutes to obtain a pretreated carbon-based mesoporous material;

(013) immersing the pretreated carbon-based mesoporous material in 200ml of active component precursor solution (NH) with the concentration of 0.2mol/L₄)₆Mo₇O₂₄·4H₂In O, enabling an active component precursor solution to be in a low-speed flowing state of 0.07m/min, after immersion treatment for 20min, taking out the pretreated carbon-based mesoporous material, placing the pretreated carbon-based mesoporous material in a nitrogen atmosphere, and performing vacuum drying treatment for 1.5h at the temperature of 100-110 ℃ to obtain a catalyst precursor;

(014) placing a catalyst precursor into a reactor, introducing a reducing gas into the reactor, heating the temperature of the reactor to 300 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 0.5h, heating the temperature of the reactor to 600 ℃ at a heating rate of 5-8 ℃/min, keeping the temperature for 1h, heating the temperature of the reactor to 820 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 2.5h, preparing an active component attached to the carbon-based mesoporous material, keeping the atmosphere of the reducing gas, and naturally cooling the reactor to normal temperature to prepare the hydrodeoxygenation catalyst.

In this embodiment, as a preferred embodiment, preferably, in step (011), the pore volume of the carbon-based mesoporous material is 1.7-1.8 cm³(ii)/g; the specific surface area of the carbon-based mesoporous material is 1500-1600 m²The pore diameter is 8-12 nm.

In this embodiment, as a preferred alternative, preferably, in step S04, the preparation method of the hydroconversion catalyst is:

(021) dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

(022) placing the mixed material in a reaction kettle, then pre-mixing the template agent, the pore-expanding agent and deionized water, then adding the mixed material into the reaction kettle, stirring and mixing the mixed material, placing the mixed material in an environment of 90-95 ℃ for drying treatment for 1h, adjusting the temperature of the reaction kettle to 130-135 ℃ for crystallization treatment for 16h, finally heating the temperature of a reaction system to 620-630 ℃ for roasting treatment for 6h, and preparing the nickel-doped SAPO-11 carrier;

(023) mixing an SAPO-11 carrier, pseudo-boehmite, sesbania powder and an acetic acid solution, grinding, stirring, extruding and molding, and drying at 110 +/-2 ℃ for 2 hours to prepare a catalyst precursor;

(024) putting a catalyst precursor in a hydrogen atmosphere at a temperature of 420-430 ℃, carrying out reduction reaction treatment for 4h, then reducing the temperature of a system to 130 +/-5 ℃, then introducing a phosphating solution for soaking treatment, keeping the flow rate of the phosphating solution at 1.0m/min for circulation after introducing the phosphating solution, then heating the temperature of the system to 230 +/-5 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 3h, then heating the temperature of the system to 370 +/-5 ℃ at a heating rate of 3 ℃/min, discharging the phosphating solution after keeping the temperature for 3h, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining a hydro-conversion catalyst after the temperature of the system is restored to normal temperature;

wherein, in the step (021), the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 1.3: 0.4: 50: 0.6; in step S02, the addition molar ratio of the template agent, the pore-expanding agent and the deionized water is 3.5: 0.6: 10.

In addition, the adding molar ratio of the components of the aluminum source, the phosphorus source, the silicon source, the deionized water, the nickel source, the template agent and the pore-expanding agent in the reaction kettle in the step (022) is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6; in the step (023), the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 75: 14: 3.5, the mass concentration of the acetic acid solution is 35%, and the adding amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier.

In this embodiment, as a preferred embodiment, preferably, the aluminum source is aluminum hydroxide; the phosphorus source is phosphoric acid solution; the silicon source is tetraethoxysilane; the nickel source is basic nickel carbonate; the template agent is dodecyl dimethyl tertiary amine; the pore-expanding agent is n-butyl alcohol; the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3 percent, and the liquid volume space velocity is 2.5h^-1。

The present solution is further illustrated below with reference to the following examples:

the preparation method of the biodiesel and the aviation fuel comprises the following steps:

s01, taking catering swill and swill as raw material oil, filtering by a screen, heating and boiling for 10min, sieving by a secondary filter screen, decoloring, sieving by a tertiary filter screen to remove suspended matters, and finishing pretreatment; then mixing the pretreated raw oil and methanol according to the volume ratio of 2: 1, and then placing the mixed system under the conditions of 8Mpa of reaction pressure and 290 +/-5 ℃ to ensure that the mixed system has alcoholysis reaction for 130min to prepare crude fatty acid methyl ester, crude glycerin and water;

s02, carrying out flash evaporation treatment on the crude fatty acid methyl ester through flash evaporation equipment at the temperature of 330 +/-5 ℃ and the pressure of 3kpa, preparing refined fatty acid methyl ester after the flash evaporation treatment, and separating out fatty acid methyl ester with low condensation point, wherein the refined fatty acid methyl ester can be used as first-generation biodiesel;

s03, setting the temperature of the hydrodeoxygenation reactor at 290 +/-3 ℃, setting the hydrogen pressure at 4.4 +/-1 Mpa and setting the volume ratio of the hydrogen to the refined fatty acid methyl ester at 700Nm³/m³Pumping the methyl ester of the essential fatty acid into a hydrodeoxygenation reactor, and enabling the methyl ester of the essential fatty acid to be in contact with a hydrodeoxygenation catalyst loaded in the reactor to generate a hydrodeoxygenation reaction so as to obtain a hydrodeoxygenation treatment product;

s04, carrying out contact reaction treatment on the hydrodeoxygenation product and a hydrogenation conversion catalyst at a preset temperature of 265-275 ℃ and a preset hydrogen pressure of 4.0-5.0 Mpa to carry out hydrodeoxygenation-isomerization reaction, and carrying out selective cracking reaction on the hydrodeoxygenation product under the hydrogenation conversion condition to obtain a hydrogenation conversion product;

and S05, introducing the hydroconversion product into a separation device for separation and fractionation to obtain biodiesel, biological aviation fuel and biological gasoline.

In step S03 of this example, the preparation method of the hydrodeoxygenation catalyst loaded in the hydrodeoxygenation reactor is as follows:

(011) mixing and dissolving phenol and formaldehyde in a sodium hydroxide solution according to a molar ratio of 1: 0.5, removing water to obtain a phenolic resin solution, adding P123 serving as an active agent and n-decane serving as an organic solvent into the phenolic resin solution, uniformly mixing, performing evaporation and thermal polymerization, placing a product into a cylindrical mold, roasting and carbonizing at 700 +/-20 ℃ for 3.5 hours, and naturally cooling to normal temperature to obtain a carbon-based mesoporous material with a cylindrical structure, wherein the pore volume of the carbon-based mesoporous material is 1.7-1.8 cm³(ii)/g; the specific surface area of the carbon-based mesoporous material is 1500-1600 m²The pore diameter is 8-12 nm;

(012) placing 100g of carbon-based mesoporous material with a columnar structure in a nitrogen atmosphere for activation treatment for 4 hours at the temperature of 450-460 ℃, then stopping nitrogen supply, and placing the carbon-based mesoporous material in a negative pressure environment with-10 Kpa for negative pressure treatment for 8 minutes to obtain a pretreated carbon-based mesoporous material;

(013) immersing the pretreated carbon-based mesoporous material in 200ml of active component precursor solution (NH) with the concentration of 0.2mol/L₄)₆Mo₇O₂₄·4H₂In O, enabling an active component precursor solution to be in a low-speed flowing state of 0.07m/min, after immersion treatment for 20min, taking out the pretreated carbon-based mesoporous material, placing the pretreated carbon-based mesoporous material in a nitrogen atmosphere, and performing vacuum drying treatment for 1.5h at the temperature of 100-110 ℃ to obtain a catalyst precursor;

(014) placing a catalyst precursor into a reactor, introducing a reducing gas into the reactor, heating the temperature of the reactor to 300 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 0.5h, heating the temperature of the reactor to 600 ℃ at a heating rate of 5-8 ℃/min, keeping the temperature for 1h, heating the temperature of the reactor to 820 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 2.5h, preparing an active component attached to the carbon-based mesoporous material, keeping the atmosphere of the reducing gas, and naturally cooling the reactor to normal temperature to prepare the hydrodeoxygenation catalyst.

In step S04 of this example, the method for preparing the hydroconversion catalyst loaded in the hydroconversion reactor is as follows:

(021) dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material, wherein the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water to the nickel source is 1: 1.3: 0.4: 50: 0.6;

(022) placing the mixed material in a reaction kettle, then pre-mixing a template agent, a pore-expanding agent and deionized water, adding the pre-mixed material into the mixed material, stirring and mixing, placing the mixed material in an environment of 90-95 ℃ for drying treatment for 1 hour, adjusting the temperature of the reaction kettle to 130-135 ℃ for crystallization treatment for 16 hours, finally heating the reaction system to 620-630 ℃ for roasting treatment for 6 hours to prepare the nickel-doped SAPO-11 carrier, wherein the adding molar ratio of the template agent to the pore-expanding agent to deionized water is 3.5: 0.6: 10, and the adding molar ratio of the components of an aluminum source, a phosphorus source, a silicon source, deionized water to the nickel source to the pore-expanding agent in the reaction kettle is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6;

(023) mixing an SAPO-11 carrier, pseudo-boehmite, sesbania powder and an acetic acid solution, grinding, stirring, extruding for molding, and drying at 110 +/-2 ℃ for 2 hours to prepare a catalyst precursor, wherein the mixing mass ratio of the SAPO-11 carrier to the pseudo-boehmite to the sesbania powder is 75: 14: 3.5, the mass concentration of the acetic acid solution is 35%, and the adding amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier;

(024) putting a catalyst precursor in a hydrogen atmosphere at a temperature of 420-430 ℃, carrying out reduction reaction treatment for 4h, then reducing the temperature of a system to 130 +/-5 ℃, then introducing a phosphating solution for soaking treatment, keeping the flow rate of the phosphating solution at 1.0m/min for circulation after introducing the phosphating solution, then heating the temperature of the system to 230 +/-5 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 3h, then heating the temperature of the system to 370 +/-5 ℃ at a heating rate of 3 ℃/min, discharging the phosphating solution after keeping the temperature for 3h, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining a hydro-conversion catalyst after the temperature of the system is restored to normal temperature;

wherein the aluminum source is aluminum hydroxide; the phosphorus source is phosphoric acid solution; the silicon source is tetraethoxysilane; the nickel source is basic nickel carbonate; the template agent is dodecyl dimethyl tertiary amine; the pore-expanding agent is n-butyl alcohol; the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3 percent, and the liquid volume space velocity is 2.5h^-1。

Production index detection

Carrying out measurement statistics on the first-generation biodiesel obtained in the step S02, the second-generation biodiesel obtained in the step S05, the biological aviation fuel and the biological gasoline, and carrying out mathematical calculation on the measurement statistics and the input quantity of the raw oil to obtain a resource liquid oil product accounting for 89.4% of the raw oil; wherein, the first generation biodiesel accounts for 27 percent, the biological gasoline accounts for 8.3 percent, the biological aviation fuel accounts for 33.1 percent, and the second generation biodiesel accounts for 21 percent.

The foregoing is directed to embodiments of the present invention, and equivalents, modifications, substitutions and variations such as will occur to those skilled in the art, which fall within the scope and spirit of the appended claims.