CN115232644A - Method for co-refining biological oil and heavy oil to prepare aviation oil - Google Patents
Method for co-refining biological oil and heavy oil to prepare aviation oil Download PDFInfo
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- CN115232644A CN115232644A CN202210532177.0A CN202210532177A CN115232644A CN 115232644 A CN115232644 A CN 115232644A CN 202210532177 A CN202210532177 A CN 202210532177A CN 115232644 A CN115232644 A CN 115232644A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a method for refining aviation oil by using bio-oil and heavy oil, belonging to the technical field of oil refining. Mixing the biological hydrogenated oil and the heavy oil hydrogenated oil, sequentially performing hydrocracking on the mixture by a three-layer catalyst bed, and then performing distillation separation to obtain the aviation oil, the naphtha and the diesel oil; wherein the first catalyst bed layer catalyst is a hydroisomerization catalyst; the second catalyst bed layer catalyst is a hydrocracking catalyst; the third catalyst bed layer catalyst is a hydrofining catalyst; the biological hydrogenated oil is prepared by taking biological oil as a raw material and performing hydrofining, and the heavy oil hydrogenated oil is prepared by taking heavy oil as a raw material and performing hydrofining. According to the invention, the biological oil is deoxidized and is mixed with the existing heavy oil under the condition that the mixing ratio of the biological oil is 50%, so that the co-refining of the aviation oil is realized, the co-refining is carried out by adopting the method disclosed by the invention, the service life and the efficiency of the catalyst are not influenced, the product quality can be improved, the hydrogen consumption is reduced, and the content of the biological oil in the aviation oil product is close to the mixing ratio.
Description
Technical Field
The invention relates to the technical field of oil refining, in particular to a method for refining aviation oil by using bio-oil and heavy oil together.
Background
Aiming at the increase of aviation carbon emission reduction targets and aviation energy requirements, biomass aviation fuel becomes aviation alternative fuel which bears the responsibility firstly. However, because the independent refining of aviation fuel from biomass has high investment, complex operation and high cost, how to combine with the existing oil refining technology and facilities becomes an internationally recognized solution with both economic and technical attractiveness.
In the face of the worldwide tendency of crude oil to be heavy, light weight utilization of heavy oil is rapidly developed and applied. And removing impurity atoms from the heavy oil through hydrofining, and then performing hydrocracking isomerization to obtain a fuel product which meets the special performance requirements and comprises the aviation jet fuel. Bio-oils have similar properties to heavy oils such as the need to remove heteroatoms and also the need to crack to form aviation fuels.
However, the main problems of the hydroprocessing and/or hydrocracking CO-refining of the biomass feedstock and the existing oil refining device are that the heteroatom of the bio-oil is mainly oxygen, and the water and CO formed in the deoxygenation process not only affect the desulfurization and denitrification efficiency, but also reduce the service life of the heavy oil catalyst, so that the current ASTM standard only allows CO-refining of less than 5% of bio-oil and heavy oil, and cannot realize high-proportion refining of bio-oil.
Disclosure of Invention
The invention aims to provide a method for co-refining grease and heavy oil to prepare aviation oil, which aims to solve the problems in the prior art. On the basis of realizing low hydrogen consumption and high aviation fuel selectivity, the high-quality aviation fuel with low sulfur, low oxygen and low nitrogen is obtained.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: the method for co-refining the aviation oil by the biological oil and the heavy oil comprises the following steps: mixing the biological hydrogenated oil and the heavy oil hydrogenated oil, sequentially carrying out hydrocracking on the mixture by three catalyst beds, and then carrying out distillation separation to obtain the aviation oil, the naphtha and the diesel oil;
wherein the first catalyst bed catalyst is a hydroisomerization catalyst;
the second catalyst bed layer catalyst is a hydrocracking catalyst;
the third catalyst bed layer catalyst is a hydrofining catalyst;
the biological hydrogenated oil is prepared by taking biological oil as a raw material and performing hydrofining, and the heavy oil hydrogenated oil is prepared by taking heavy oil as a raw material and performing hydrofining.
Furthermore, the blending ratio of the biological hydrogenated oil and the heavy oil hydrogenated oil is less than or equal to 50wt%.
Further, the preparation of the biological hydrogenated oil specifically comprises the following steps:
(1) Performing methyl esterification treatment on the biological oil to obtain biological purified oil;
(2) And (4) subjecting the biological purified oil to catalyst hydrofining (deoxidation and denitrification, and entering a buffer tank) to obtain the biological hydrogenated oil.
Further, the methyl esterification treatment specifically comprises: carrying out methanol-hydrothermal reaction at 120-240 deg.c and 6.0-10.0 MPa; the volume fraction of the methanol in the methanol-hydrothermal reaction is 30-60%, and the reaction time is 5-60 min.
Furthermore, the catalyst is of a three-layer catalyst bed structure, the first catalyst bed is a catalyst protective agent and a demetalization catalyst, the second catalyst bed is a hydrodeoxygenation catalyst, and the third catalyst bed is a hydrodenitrogenation catalyst; the hydrogen partial pressure of the hydrofining is 6-10 MPa, and the hydrogen-oil ratio is 600-1200 m 3 /m 3 The temperature is 280-375 ℃, and the empty tower flow rate is 0.25-2 h -1 . Further, the catalyst protective agent and the demetallization catalyst are Ni/A1 2 O 3 And/or Mo/A1 2 O 3 (ii) a The hydrodeoxygenation catalyst is Ni-Mo/Al 2 O 3 And/or Ni-W/Al 2 O 3 (ii) a The hydrodenitrogenation catalyst is Ni-Mo-W/Al 2 O 3 -P and/or Ni-W/Al 2 O 3 。
Further, the step (2) is specifically: the biological purified oil is subjected to flash separation after being subjected to hydrorefining by a catalyst to obtain the biological hydrogenated oil; the temperature of the flash separation is 120-160 ℃, and the pressure is 0.1-0.3 Mpa.
Further, the main components in the biological oil are fatty acid glyceride, fatty acid methyl ester and fatty acid; the biological oil comprises waste oil, microalgae oil, jatropha oil, soybean oil or rapeseed oil.
The main component of the bio-purified oil is fatty acid methyl ester, and the bio-purified oil contains a small amount of oil ester and fatty acid, and the oxygen content is less than 12%.
Further, the preparation of the heavy oil hydrogenated oil specifically comprises the following steps: and (4) carrying out hydrofining (desulfurization and denitrification, and entering a buffer tank) on the heavy oil by using a catalyst to obtain the heavy oil hydrogenated oil.
Furthermore, the catalyst is of a three-layer catalyst bed structure, the first catalyst bed is a catalyst protective agent and a demetalization catalyst, the second catalyst bed is a hydrodesulfurization catalyst, and the third catalyst bed is a hydrodenitrogenation catalyst; the hydrogen partial pressure of the hydrofining is 6-10 MPa, and the hydrogen-oil ratio is 600-1200 m 3 /m 3 The temperature is 280-375 ℃, and the empty tower flow velocity is 0.25-2 h -1 。
Further, the catalyst protective agent and the demetallization catalyst are Ni/A1 2 O 3 And/or Co/A1 2 O 3 (ii) a The hydrodesulfurization catalyst is Co-Mo/Al 2 O 3 And/or Ni-Mo/SiO 2 -P 2 O 5 (ii) a The hydrodenitrogenation catalyst is Ni-Mo/Al 2 O 3 -P and/or Ni-W/Al 2 O 3 。
Further, the sulfur content of the heavy oil is less than 1.5%, and the nitrogen content is less than 0.5%; the heavy oil comprises one or more of vacuum wax oil, straight-run wax oil and coking wax oil.
Further, the hydroisomerization catalyst comprises Ni-Mo-W/zeolite-Al 2 O 3 -SiO 2 、Ni-W/SiO 2 -Al 2 O 3 、Pt/Al 2 O 3 One or more of-F, niO 3-6%, moO 3 10 to 20 percent; the hydrocracking catalyst comprises Ni-W/USY and Ni-W/SiO 2 -Al 2 O 3 、Ni-Mo/B 2 O 3 -A1 2 O 3 One or more of (a); the hydrofining catalyst comprises Ni-W/Al 2 O 3 And/or Ni-Mo-W/SiO 2 -A1 2 O 3 (ii) a The hydrogen partial pressure of the hydrocracking is 12-15 MPa, and the hydrogen-oil ratio is 1000-1500 m 3 /m 3 The temperature is 360-450 ℃, and the empty tower flow rate is 0.5-2 h -1 。
In the above catalyst, "/" is preceded by an active ingredient and, "/" is followed by a support.
USY is Y type molecular sieve.
Further, the catalyst level gradation and the process conditions in the preparation of the bio-hydrogenated oil can be adjusted according to the content of the heteroatom in the raw material.
Furthermore, the grading of the catalyst layer and the condition of the method can be adjusted according to the content of the heteroatom in the raw material when the heavy oil hydrogenation oil is prepared;
furthermore, the catalyst level grading and the method condition during the preparation of the aviation fuel can be adjusted according to the condensation point requirement of the product and the aviation fuel selectivity.
The second technical scheme of the invention is as follows: a aviation oil preparation device is used for the method for co-refining the aviation oil by the biological oil and the heavy oil, and comprises a hydrofining reactor 1, a hydrofining reactor 2, a hydrocracking reactor, a biological oil heating furnace, a heavy oil heating furnace, a separating tank, a separator, a fractionator and a purifier;
wherein, the bio-oil heating furnace is communicated with the inlet of the hydrofining reactor 1, and the outlet of the hydrofining reactor 1 is communicated with the separating tank;
the heavy oil heating furnace is communicated with the inlet of the hydrofining reactor 2, and the outlet of the heavy oil hydrofining reactor 2 is communicated with the separating tank;
the separating tank is communicated with inlets of the hydrocracking reactor and the purifier, and an outlet of the hydrocracking reactor is sequentially connected with the separator and the fractionator; the separator is connected with the purifier.
The invention discloses the following technical effects:
according to the method, the biological oil is deoxidized to be mixed with the existing heavy oil under the condition that the mixing ratio is 50%, so that the co-refining of the aviation oil is realized, the method is adopted for co-refining, the service life and the efficiency of the catalyst are not influenced, the product quality can be improved, the hydrogen consumption is reduced (by 3% -5%), the biological carbon content in the aviation oil product is close to the mixing ratio, and the obtained aviation oil product meets the requirements of ASTM standard fluidity, volatility, combustibility and cleanliness.
The desulfurization and denitrification efficiency of the invention is above 99%, and the operation activity of the catalyst for co-refining the bio-oil and the heavy oil is equivalent to the activity of hydrogenating the heavy oil alone.
The invention can meet the quality requirement of the oil product only by matching the temperature, the pressure, the reaction time and the catalyst, and changes which condition can generate adverse effect on the performance of the prepared aviation oil, thereby causing that the co-refining is not that the oil product can not meet the requirement, and even causing that the catalyst is easy to inactivate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a diagram of an apparatus for producing aviation oil according to the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, 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 invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and materials in connection with which they pertain. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The following examples of the invention all adopt the aviation oil preparation device of figure 1 to prepare aviation oil;
the aviation oil preparation device shown in figure 1 of the invention consists of a hydrofining reactor 1, a hydrofining reactor 2, a hydrocracking reactor, a bio-oil heating furnace, a heavy oil heating furnace, an off-tank, a separator, a purifier and a fractionator;
wherein, the bio-oil heating furnace is connected with an inlet of the hydrofining reactor 1, and an outlet of the hydrofining reactor 1 is communicated with the separating tank;
the heavy oil heating furnace is communicated with the inlet of the hydrofining reactor 2, and the outlet of the hydrofining reactor 2 is communicated with the separating tank;
the separating tank is connected with inlets of the hydrocracking reactor and the purifier, and an outlet of the hydrocracking reactor is sequentially connected with the separator and the fractionator; the separator is connected with the purifier;
the specific device is shown in figure 1.
The catalyst protective agent and the demetallization catalyst are Ni/A1 2 O 3 And/or Mo/A1 2 O 3 (ii) a The hydrodeoxygenation catalyst is Ni-Mo/Al 2 O 3 And/or Ni-W/Al 2 O 3 (ii) a The hydrodenitrogenation catalyst is Ni-Mo-W/Al 2 O 3 -P and/or Ni-W/Al 2 O 3
Catalyst Ni/A1 used in the invention 2 O 3 The loading capacity of the medium NiO is 3-6%; catalyst Ni/A1 used in the examples of the present invention 2 O 3 The loading amount of the medium NiO is 3.9%;
catalyst Mo/A1 used in the invention 2 O 3 Medium MoO 3 The loading amount of the catalyst is 10 to 20 percent; catalyst Mo/A1 used in the examples of the present invention 2 O 3 Medium MoO 3 The supported amount of (A) was 19%;
catalyst Ni-Mo/Al used in the invention 2 O 3 The load capacity of the medium NiO is 3 to 6 percent, and the MoO content is 3 The loading amount of the catalyst is 10 to 20 percent; catalyst Ni-Mo/Al used in examples of the invention 2 O 3 The load of the medium NiO is 3.9 percent, and the MoO content 3 The supported amount of (b) was 19%;
catalyst Ni-W/Al used in the invention 2 O 3 The supported amount of the medium NiO is 3 to 8 percent, WO 3 The loading amount of the catalyst is 20 to 25 percent; catalyst Ni-W/Al used in examples of the present invention 2 O 3 The loading amount of the medium NiO is 5.2 percent, and the content of the medium NiO in the medium NiO is WO 3 The loading of (a) was 24.2%;
catalyst Ni-Mo-W/Al used in the invention 2 O 3 The load of NiO in-P is 3 to 5 percent, WO 3 The load capacity of the catalyst is 8 to 15 percent, and the MoO 3 The loading amount of the catalyst is 8-15%; catalyst Ni-Mo-W/Al used in examples of the invention 2 O 3 The NiO loading of the P is 5 percent, WO 3 The supported amount of (A) is 12%, moO 3 The loading amount of (2) is 10%;
catalyst Co/A1 used in the invention 2 O 3 The loading capacity of the medium CoO is 3-6%; catalyst Co/A1 used in the examples of the present invention 2 O 3 The loading of medium CoO is 5.6 percent;
catalyst Co-M used in the inventiono/Al 2 O 3 The supported amount of medium CoO is 3-6%, moO 3 The loading amount of the catalyst is 10 to 20 percent; co-Mo/Al catalyst used in examples of the present invention 2 O 3 The loading of medium CoO is 5%, moO 3 The loading amount of (2) is 16%;
the catalyst used in the invention is Ni-Mo/SiO 2 -P 2 O 5 The load capacity of the medium NiO is 3 to 6 percent, and the MoO content is 3 The loading amount of the catalyst is 10-20%; catalyst used in the examples of the present invention was Ni-Mo/SiO 2 -P 2 O 5 The loading amount of the medium NiO is 3.9 percent, and the MoO content is 3 The supported amount of (A) was 19%;
catalyst Ni-Mo/Al used in the invention 2 O 3 The load amount of NiO in-P is 3 to 6 percent, moO 3 The loading amount of the catalyst is 10 to 20 percent; catalyst Ni-Mo/Al used in examples of the invention 2 O 3 The load of NiO in-P is 3.9 percent, moO 3 The supported amount of (A) was 19%;
catalyst Ni-W/Al used in the invention 2 O 3 The load capacity of the medium NiO is 3 to 8 percent, and WO 3 The load capacity of the catalyst is 20 to 25 percent; catalyst Ni-W/Al used in examples of the present invention 2 O 3 The loading amount of the medium NiO is 5.2 percent, and the content of the medium NiO in the medium NiO is WO 3 The loading of (a) was 24.2%;
catalyst Ni-Mo-W/zeolite-Al used in the invention 2 O 3 -SiO 2 The load capacity of the medium NiO is 3 to 6 percent, and the MoO 3 The supported amount of (b) is 8-15%, WO 3 The loading amount of the catalyst is 10-20%; catalyst Ni-Mo-W/Zeolite-Al used in examples of the invention 2 O 3 -SiO 2 The load of the medium NiO is 3.5 percent, and the MoO content 3 In an amount of 12%, WO 3 The loading amount of (2) is 10%;
the catalyst used in the invention is Ni-W/SiO 2 -Al 2 O 3 The load capacity of the medium NiO is 3 to 8 percent, and WO 3 The load capacity of the catalyst is 20 to 25 percent; catalyst Ni-W/SiO used in the examples of the present invention 2 -Al 2 O 3 The loading amount of the medium NiO is 5.2 percent, and the content of the medium NiO in the medium NiO is WO 3 The loading of (a) was 24.2%;
for use in the inventionCatalyst Pt/Al of 2 O 3 The loading amount of Pt in F is 0.3-1.0%; pt/Al catalyst used in the examples of the present invention 2 O 3 The loading of Pt in F is 0.5%;
the load capacity of NiO in the catalyst Ni-W/USY used by the invention is 3% -8%, and WO 3 The load capacity of the catalyst is 20 to 25 percent; the load capacity of NiO in the catalyst Ni-W/USY used in the embodiment of the invention is 5.2 percent, and WO 3 The loading of (a) was 24.2%;
catalyst Ni-Mo/B used in the invention 2 O 3 -A1 2 O 3 The load capacity of the medium NiO is 3 to 5 percent, and the MoO content is 3 The loading amount of the catalyst is 8-15%; catalyst Ni-Mo/B used in the examples of the present invention 2 O 3 -A1 2 O 3 The load of the medium NiO is 5 percent, and the MoO 3 The loading amount of (2) was 12%;
the catalyst used in the invention is Ni-Mo-W/SiO 2 -A1 2 O 3 The load capacity of the medium NiO is 3 to 5 percent, and the MoO content is 3 The loading amount of the catalyst is 8 to 15 percent, WO 3 The load capacity of the catalyst is 8 to 15 percent; catalyst used in the examples of the present invention was Ni-Mo-W/SiO 2 -A1 2 O 3 The loading amount of the medium NiO is 5 percent, and the MoO 3 In an amount of 10%, WO 3 The loading of (b) was 12%.
In the examples of the present invention, the raw materials were obtained from commercial sources unless otherwise specified.
Example 1
The method for co-refining the aviation oil by the biological oil and the heavy oil comprises the following steps:
(1) Adding microalgae into methanol water solution (the volume fraction of methanol in the methanol water solution is 50%), performing methanol-hydrothermal reaction at 200 deg.C for 30min, allowing glyceride, phospholipid, glycolipid, and fatty acid in microalgae to enter oil phase via methyl esterification, allowing most of protein and carbohydrate decomposition products to enter water phase, and decomposing small molecular substance CO 2 ，H 2 ，CH 4 Entering a gas phase; then the microalgae purified oil is obtained by flash separation under the conditions that the temperature is 130 ℃ and the pressure is 0.2Mpa, wherein the oxygen content of the microalgae purified oil is 10.5 percent, and the nitrogen content is 3.6 percent.
(2) Preparing microalgae hydrogenated oil: introducing the microalgae purified oil into a bio-oil heating furnace to be heated to 125 ℃, then introducing the microalgae purified oil into the hydrofining reactor 1 from an inlet at the top of the hydrofining reactor 1, and enabling the microalgae purified oil to pass through a first catalyst bed layer, a second catalyst bed layer and a third catalyst bed layer to obtain microalgae hydrogenated oil (simultaneously realizing deoxidation and denitrification); the height ratio of the three catalyst beds is 0.2 -1 (ii) a The catalyst of the first catalyst bed layer is Ni/Al 2 O 3 ，Ni/Al 2 O 3 As a catalyst protective agent, the catalyst also has catalytic activity, the bed temperature is 280-300 ℃, and the hydrogen-oil ratio is 800-1000; the catalyst of the second catalyst bed layer is Ni-Mo/Al 2 O 3 The bed temperature is 300-350 ℃, and the hydrogen-oil ratio is 1000-1200; the catalyst of the third catalyst bed layer is Ni-Mo-W/Al 2 O 3 P, the bed temperature is 350-375 ℃, and the hydrogen-oil ratio is 900-1200.
(3) Preparation of heavy oil hydrogenated oil: introducing heavy oil (the heavy oil is a mixed oil of straight-run residual oil and vacuum residual oil with the mass ratio of 2:1, the sulfur content is 0.5%, and the nitrogen content is 0.25%) into a heavy oil heating furnace, heating to 90-150 ℃, then introducing the heavy oil into a hydrofining reactor 2 from an inlet at the top of the hydrofining reactor 2, and allowing the heavy oil to pass through a first catalyst bed layer, then a second catalyst bed layer, and finally a third catalyst bed layer to obtain heavy oil hydrogenated oil (desulfurization and denitrification); the height ratio of the three catalyst beds is 0.3 -1 (ii) a The catalyst of the first catalyst bed layer is Ni/Al 2 O 3 ，Ni/Al 2 O 3 As a catalyst protective agent, the catalyst also has catalytic activity, the bed temperature is 280-300 ℃, and the hydrogen-oil ratio is 800-1000; the catalyst of the second catalyst bed layer is Co-Mo/Al 2 O 3 The bed temperature is 300-330 ℃, and the hydrogen-oil ratio is 800-1000; the catalyst of the third catalyst bed layer is Ni-Mo/Al with the mass ratio of 0.8 2 O 3 P and Ni-W/Al 2 O, bed temperature350-375 ℃, and the hydrogen-oil ratio is 900-1200.
(4) Introducing the microalgae hydrogenated oil (deoxygenation and denitrification) and the heavy oil hydrogenated oil (desulfurization and denitrification) prepared in the steps (2) and (3) into a separation tank according to the mass ratio of 1; height ratio of three layers of catalyst beds: 1.1 -1 (ii) a The catalyst of the first catalyst bed layer is Ni-W/SiO 2 -Al 2 O 3 The temperature of the bed layer is 360-380 ℃, and the hydrogen-oil ratio is 1200-1500; the catalyst of the second catalyst bed layer is Ni-W/USY and Ni-W/SiO with the mass ratio of 0.8 to 1.2 2 -Al 2 O 3 The bed temperature is 380-400 ℃, and the hydrogen-oil ratio is 1200-1500; the catalyst of the third catalyst bed layer is Ni-W/Al with the mass ratio of 0.8 2 O 3 And Ni-Mo-W/SiO 2 -A1 2 O 3 The bed temperature is 400-430 deg.C, and the hydrogen-oil ratio is 1200-1500.
(5) And (5) introducing the product oil prepared in the step (4) into a separator, introducing the separated gas into a purifier, introducing the separated liquid into a fractionator, and fractionating to obtain naphtha, diesel oil and kerosene (aviation oil).
The prepared aviation oil meets the requirements of ASTM standard fluidity, volatility, combustibility and cleanliness, wherein the content of the biological oil is 51.5%, the content of S in the aviation oil is less than 1ppm, and the content of N in the aviation oil is less than 1ppm.
Example 2
(1) Desalting and dehydrating waste oil to obtain desalted and dehydrated waste oil, adding desalted and dehydrated waste oil into methanol water solution (the volume fraction of methanol in the methanol water solution is 50%), performing methanol-hydrothermal reaction at 200 deg.C for 30min, allowing glycerolipid, phospholipid, glycolipid and fatty acid in microalgae to enter oil phase through methyl esterification, allowing protein and carbohydrate decomposition products to enter water phase, and separatingDecomposed small molecular substance CO 2 ，H 2 ，CH 4 Entering a gas phase; then the waste grease purified oil is obtained by flash separation under the conditions that the temperature is 130 ℃ and the pressure is 0.2Mpa, wherein the oxygen content of the waste grease purified oil is 11.9 percent and the nitrogen content is 0.05 percent.
(2) Preparing the hydrogenated oil of the waste oil: introducing the waste grease purified oil into a biological oil heating furnace to be heated to 110-150 ℃, then introducing the waste grease purified oil into a hydrofining reactor 1 from an inlet at the top of the hydrofining reactor 1, and enabling the microalgae purified oil to pass through a first catalyst bed layer, a second catalyst bed layer and a third catalyst bed layer to obtain waste grease hydrogenated oil (deoxidation and denitrification); the height ratio of the three layers of catalyst beds is 0.2 -1 (ii) a The catalyst of the first catalyst bed layer is Ni/Al 2 O 3 ，Ni/Al 2 O 3 As a catalyst protective agent, the catalyst also has catalytic activity, the bed temperature is 280-300 ℃, and the hydrogen-oil ratio is 800-1000; the catalyst of the second catalyst bed layer is Ni-Mo/Al 2 O 3 The bed temperature is 300-350 ℃, and the hydrogen-oil ratio is 1000-1200; the catalyst of the third catalyst bed layer is Ni-Mo-W/Al 2 O 3 P, the bed temperature is 350-375 ℃, and the hydrogen-oil ratio is 900-1200.
(3) Preparation of heavy oil hydrogenated oil: introducing heavy oil (the heavy oil is a mixture of vacuum wax oil, straight-run wax oil and coking wax oil with the mass ratio of 1; the height ratio of the three layers of catalyst beds is 0.2 -1 (ii) a The catalyst of the first catalyst bed layer is Ni/Al 2 O 3 ，Ni/Al 2 O 3 As catalyst protective agent, also has catalytic activity and bed layer temperature280-300 ℃ and the hydrogen-oil ratio of 800-1000; the catalyst of the second catalyst bed layer is Co-Mo/Al 2 O 3 The bed temperature is 300-330 ℃, and the hydrogen-oil ratio is 800-1000; the catalyst of the third catalyst bed layer is Ni-Mo/Al 2 O 3 P, the bed temperature is 350-375 ℃, and the hydrogen-oil ratio is 900-1200.
(4) Feeding the waste grease hydrogenated oil (deoxygenation and denitrification) and the heavy oil hydrogenated oil (desulfurization and denitrification) prepared in the steps (2) and (3) into a separation tank according to the mass ratio of 1; height ratio of three layers of catalyst beds: 1.3, controlling the pressure in the hydrofining reactor to be 13-15 MPa, and controlling the empty tower flow rate to be 0.75h -1 (ii) a The catalyst of the first catalyst bed layer is Ni-W/SiO with the mass ratio of 1 2 -Al 2 O and Pt/Al 2 O 3 -F 3 The temperature of the bed layer is 360-380 ℃, and the hydrogen-oil ratio is 1200-1500; the catalyst of the second catalyst bed layer is Ni-W/USY and Ni-W/SiO with the mass ratio of 1 2 -Al 2 O 3 The bed temperature is 380-400 ℃, and the hydrogen-oil ratio is 1200-1500; the catalyst of the third catalyst bed layer is Ni-W/Al with the mass ratio of 1 2 O 3 And Ni-Mo-W/SiO 2 -A1 2 O 3 The bed temperature is 400-430 deg.C, and the hydrogen-oil ratio is 1200-1500.
(5) And (4) introducing the product oil prepared in the step (4) into a separator, introducing the separated gas into a purifier, introducing the separated liquid into a fractionator, and fractionating to obtain naphtha, diesel oil and kerosene (aviation oil).
The prepared aviation oil meets the requirements of fluidity, volatility, combustibility and cleanliness in ASTM standard requirements, wherein the content of the biological oil is 50.1%, the content of S in the aviation oil is less than 1ppm, and the content of N in the aviation oil is less than 1ppm.
After the refining method (blending bio-oil refining) of examples 1-2 of the present invention was used for 1000 hours, the activities of the hydrorefining catalyst and the hydrocracking catalyst were comparable to those of the process without blending bio-oil refining.
The density of the aviation oil prepared in the embodiment 1-2 of the invention is 785-799 kg/m 3 The heat value is 42.7-43.8 MJ/kg, the freezing point is less than-47 ℃, the S content is less than 1ppm, and the N content is less than 1ppm.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The method for co-refining the aviation oil by the biological oil and the heavy oil is characterized by comprising the following steps of: mixing the biological hydrogenated oil and the heavy oil hydrogenated oil, sequentially performing hydrocracking on the mixture by a three-layer catalyst bed, and then performing distillation separation to obtain the aviation oil, the naphtha and the diesel oil;
wherein the first catalyst bed layer catalyst is a hydroisomerization catalyst;
the second catalyst bed layer catalyst is a hydrocracking catalyst;
the third catalyst bed layer catalyst is a hydrofining catalyst;
the biological hydrogenated oil is prepared by taking biological oil as a raw material and performing hydrofining, and the heavy oil hydrogenated oil is prepared by taking heavy oil as a raw material and performing hydrofining.
2. The method for co-refining the aviation oil by the bio-oil and the heavy oil according to claim 1, wherein the preparation of the bio-hydrogenated oil specifically comprises:
(1) Performing methyl esterification treatment on the biological oil to obtain biological purified oil;
(2) And (3) performing hydrofining on the biological purified oil by using a catalyst to obtain the biological hydrogenated oil.
3. The method for refining aviation oil from bio-oil and heavy oil according to claim 2, wherein the methyl esterification process comprises: carrying out methanol-hydrothermal reaction at 120-240 deg.c and 6.0-10.0 MPa; the volume fraction of the methanol in the methanol-hydrothermal reaction is 30-60%, and the reaction time is 5-60 min.
4. The method of claim 2, wherein the catalyst is a three-layer catalyst bed structure, the first catalyst bed is a catalyst protectant and a demetallization catalyst, the second catalyst bed is a hydrodeoxygenation catalyst, and the third catalyst bed is a hydrodenitrogenation catalyst; the hydrogen partial pressure of the hydrofining is 6-10 MPa, and the hydrogen-oil ratio is 600-1200 m 3 /m 3 The temperature is 280-375 ℃, and the empty tower flow velocity is 0.25-2 h -1 。
5. The method for co-refining bio-oil and heavy oil to produce aviation oil according to claim 4, wherein the catalyst protectant and demetallization catalyst is Ni/A1 2 O 3 And/or Mo/A1 2 O 3 (ii) a The hydrodeoxygenation catalyst is Ni-Mo/Al 2 O 3 And/or Ni-W/Al 2 O 3 (ii) a The hydrodenitrogenation catalyst is Ni-Mo-W/Al 2 O 3 -P and/or Ni-W/Al 2 O 3 。
6. The method for co-refining the aviation oil by the bio-oil and the heavy oil according to claim 1, wherein the preparation of the heavy oil hydrogenated oil specifically comprises: and (3) performing hydrogenation refining on heavy oil by using a catalyst to obtain the heavy oil hydrogenated oil.
7. The method of claim 6, wherein the catalyst is a three-layer catalyst bed structure, the first catalyst bed is a catalyst protectant and a demetallization catalyst, the second catalyst bed is a hydrodesulfurization catalyst, and the third catalyst bed is a hydrodenitrogenation catalyst; the hydrogen partial pressure of the hydrofining is 6-10 MPa, and the hydrogen-oil ratio is 600-1200 m 3 /m 3 Temperature of 280 &375 ℃ and the empty tower flow rate of 0.25 to 2h -1 。
8. The method for co-refining bio-oil and heavy oil to produce aviation oil according to claim 7, wherein the catalyst protectant and demetallization catalyst is Ni/A1 2 O 3 And/or Co/A1 2 O 3 (ii) a The hydrodesulfurization catalyst is Co-Mo/Al 2 O 3 And/or Ni-Mo/SiO 2 -P 2 O 5 (ii) a The hydrodenitrogenation catalyst is Ni-Mo/Al 2 O 3 -P and/or Ni-W/Al 2 O 3 。
9. The process of claim 1, wherein the hydroisomerization catalyst comprises Ni-Mo-W/zeolite-Al 2 O 3 -SiO 2 、Ni-W/SiO 2 -Al 2 O 3 、Pt/Al 2 O 3 -one or more of F; the hydrocracking catalyst comprises Ni-W/USY and Ni-W/SiO 2 -Al 2 O 3 、Ni-Mo/B 2 O 3 -A1 2 O 3 One or more of (a); the hydrofining catalyst comprises Ni-W/Al 2 O 3 And/or Ni-Mo-W/SiO 2 -A1 2 O 3 (ii) a The hydrogen partial pressure of the hydrocracking is 12-15 MPa, and the hydrogen-oil ratio is 1000-1500 m 3 /m 3 The temperature is 360-450 ℃, and the empty tower flow velocity is 0.5-2 h -1 。
10. A process for producing a marine oil by co-refining the bio-oil and the heavy oil according to any one of claims 1 to 7, comprising a hydrorefining reactor 1, a hydrorefining reactor 2, a hydrocracking reactor, a bio-oil heating furnace, a heavy oil heating furnace, a separation tank, a separator, a fractionator, and a purifier;
wherein, the bio-oil heating furnace is communicated with the inlet of the hydrofining reactor 1, and the outlet of the hydrofining reactor 1 is communicated with the separating tank;
the heavy oil heating furnace is communicated with the inlet of the hydrofining reactor 2, and the outlet of the hydrofining reactor 2 is communicated with the separating tank;
the separating tank is communicated with the inlets of the hydrocracking reactor and the purifier, and the outlet of the hydrocracking reactor is sequentially connected with the separator and the fractionator; the separator is connected with the purifier.
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