CN115232644A - Method for co-refining jet fuel with bio-oil and heavy oil - Google Patents

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

Method for co-refining jet fuel with bio-oil and heavy oil

technical field

The invention relates to the technical field of oil refining, in particular to a method for co-refining aviation oil with bio-oil and heavy oil.

Background technique

In response to the aviation carbon emission reduction target and the growth of aviation energy demand, biomass aviation fuel has become the first aviation alternative fuel to assume this responsibility. However, due to the high investment, complex operation and high cost of biomass refining aviation fuel alone, how to combine with existing refining technology and facilities has become an internationally recognized solution that is both economically and technically attractive.

Faced with the tendency of crude oil to become heavier worldwide, the lightweight utilization of heavy oil has been rapidly developed and applied. Heavy oil is hydrorefined to remove impurity atoms, and then hydrocracked and isomerized to obtain fuel products including aviation jet fuel that meet special performance requirements. Bio-oil and heavy oil have similar properties such as the need to remove heteroatoms and also need to be cracked to form aviation fuel.

However, the main problem of combining biomass raw materials with existing oil refining units for hydrotreating and/or hydrocracking co-refining is that the heteroatoms of bio-oil are mainly oxygen, and the water and CO formed in the deoxygenation process not only affect the desulfurization and denitrification efficiency , and also reduces the service life of the heavy oil catalyst. Therefore, the current ASTM standard only allows less than 5% bio-oil to be co-refined with heavy oil, and cannot achieve high-proportion refining of bio-oil.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method for co-refining aviation oil with grease and heavy oil, so as to solve the problems existing in the prior art. The method of the present invention not only improves the quality of bio-oil by optimizing the catalyst and method for deoxygenation, but also can achieve high-mixture Co-refining of mixed bio-oil and heavy oil. On the basis of realizing low hydrogen consumption and high aviation fuel selectivity, high-quality aviation fuel with low sulfur, low oxygen and low nitrogen can be obtained.

For achieving the above object, the present invention provides the following scheme:

One of the technical solutions of the present invention: a method for co-refining aviation oil from bio-oil and heavy oil, comprising the following steps: mixing the bio-hydrogenated oil and the heavy-oil hydrogenated oil, followed by hydrocracking of three-layer catalyst beds, followed by distillation and separation, obtaining the jet fuel, naphtha and diesel oil;

Wherein, the first catalyst bed catalyst is a hydroisomerization catalyst;

The second catalyst bed catalyst is a hydrocracking catalyst;

The third catalyst bed catalyst is a hydrorefining catalyst;

The bio-hydrogenated oil is prepared by using bio-oil as a raw material through hydrorefining, and the heavy-oil hydrogenated oil is prepared by using heavy oil as a raw material through hydro-refining.

Further, the mixing ratio of the biological hydrogenated oil and the heavy oil hydrogenated oil is ≤50wt%.

Further, the preparation of the biologically hydrogenated oil specifically includes:

(1) methyl esterification is carried out to bio-oil to obtain bio-purified oil;

(2) The biologically purified oil is subjected to catalyst hydrorefining (deoxygenation, denitrification, and entering a buffer tank) to obtain the biologically hydrogenated oil.

Further, the methyl esterification treatment specifically includes: performing methanol-hydrothermal reaction under the conditions of a temperature of 120-240° C. and a pressure of 6.0-10.0 Mpa; the volume fraction of methanol in the methanol-hydrothermal reaction is 30 %～60%, the reaction time is 5～60min.

Further, the catalyst has a three-layer catalyst bed structure, the first catalyst bed is a catalyst protection agent 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 hydrorefining is 6-10MPa, the hydrogen-oil ratio is 600-1200m ³ /m ³ , the temperature is 280-375°C, and the superficial flow rate is 0.25-2h ^-1 . Further, the catalyst protection agent and the demetallization catalyst are Ni/A1 ₂ O ₃ and/or Mo/A1 ₂ O ₃ ; the hydrodeoxygenation catalyst is Ni-Mo/Al ₂ O ₃ and/or Ni- W/Al ₂ O ₃ ; 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 as follows: the biologically purified oil is subjected to catalyst hydrorefining and then flashed and separated to obtain the biologically hydrogenated oil; the temperature of the flashing separation is 120-160°C, and the pressure It is 0.1～0.3Mpa.

Further, the main components in the biological oil are fatty acid glycerides, fatty acid methyl esters, and fatty acids; the biological oil includes waste oil, microalgae oil, jatropha oil, soybean oil or rapeseed oil.

The main component in the biological purification oil is fatty acid methyl ester, and 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 includes: hydrorefining the heavy oil through a catalyst (desulfurization, denitrification, and entering a buffer tank) to obtain the heavy oil hydrogenated oil.

Further, the catalyst has a three-layer catalyst bed structure, the first catalyst bed is a catalyst protection agent 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 hydrorefining is 6-10MPa, the hydrogen-oil ratio is 600-1200m ³ /m ³ , the temperature is 280-375°C, and the superficial flow rate is 0.25-2h ^-1 .

Further, the catalyst protection agent and the demetallization catalyst are Ni/A1 ₂ O ₃ and/or Co/A1 ₂ O ₃ ; the hydrodesulfurization catalyst is Co-Mo/Al ₂ O ₃ and/or Ni- Mo/SiO ₂ -P ₂ O ₅ ; 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 includes one or more of vacuum wax oil, straight-run wax oil, and coker wax oil.

Further, the hydroisomerization catalyst includes one of Ni-Mo-W/zeolite-Al ₂ O ₃ -SiO ₂ , Ni-W/SiO ₂ -Al ₂ O ₃ , and Pt/Al ₂ O ₃ -F or more, wherein NiO 3-6%, MoO ₃ 10-20%; the hydrocracking catalyst includes Ni-W/USY, Ni-W/SiO ₂ -Al ₂ O ₃ , Ni-Mo/B ₂ O One or more of ₃ -A1 ₂ O ₃ ; the hydrorefining catalyst includes Ni-W/Al ₂ O ₃ and/or Ni-Mo-W/SiO ₂ -A1 ₂ O ₃ ; the hydrocracking The hydrogen partial pressure is 12-15MPa, the hydrogen-oil ratio is 1000-1500m ³ /m ³ , the temperature is 360-450°C, and the superficial flow rate is 0.5-2h ^-1 .

In the above catalysts, the one in front of "/" is the active ingredient, and the one behind "/" is the carrier.

USY is Y-type molecular sieve.

Further, the catalyst level gradation and method conditions during the preparation of the bio-hydrogenated oil can be adjusted according to the content of heteroatoms in the raw material.

Further, the catalyst level gradation and method conditions can be adjusted according to the heteroatom content in the raw material during the preparation of the heavy oil hydrogenated oil;

Furthermore, the catalyst level gradation and method conditions during the preparation of the jet fuel can be adjusted according to the product's requirements for the condensation point and the jet fuel selectivity.

The second technical solution of the present invention: a jet fuel preparation device, used for the above-mentioned method for co-refining jet fuel with bio-oil and heavy oil, comprising a hydrotreating reactor 1, a hydrotreating reactor 2, and a hydrocracking reactor , Bio-oil heating furnace, heavy oil heating furnace, separation tank, separator, fractionator, purifier;

Wherein, the bio-oil heating furnace is communicated with the inlet of the hydrotreating reactor 1, and the outlet of the hydrotreating reactor 1 is communicated with the separation tank;

The heavy oil heating furnace is communicated with the inlet of the hydrotreating reactor 2, and the outlet of the heavy oil hydrotreating reactor 2 is communicated with the separation tank;

The separation tank is connected with the inlet of the hydrocracking reactor and the purifier, the outlet of the hydrocracking reactor is connected with the separator and the fractionator in turn; the separator is connected with the purifier.

The present invention discloses the following technical effects:

The invention realizes the co-refining of aviation oil by blending with the existing heavy oil under the condition of a mixing ratio of 50% by deoxidizing the bio-oil, and using the method of the invention for co-refining not only does not affect the service life of the catalyst and efficiency, and can improve product quality and reduce hydrogen consumption (reduce 3% to 5%), the bio-carbon content in jet fuel products is close to the blending ratio, and the obtained jet fuel products meet ASTM standards for fluidity, volatility, flammability, cleanliness sexual demands.

The desulfurization and denitrification efficiency of the invention is above 99%, and the operation activity of the co-refining catalyst of bio-oil and heavy oil is equivalent to the activity of hydrogenating heavy oil alone.

In the present invention, the quality requirements of oil products can only be achieved through the mutual matching of temperature, pressure, reaction time and catalyst. Any change in any of the conditions will have an adverse effect on the performance of the prepared jet oil, resulting in that the co-refining is not up to the oil quality. To the requirements, and even cause the catalyst to be easily deactivated.

Description of drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings required in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some of the present invention. In the embodiments, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.

FIG. 1 is a diagram of the device for preparing jet fuel according to the present invention.

Detailed ways

Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.

It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention. Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless otherwise defined, 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 relates. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and materials in connection with which the documents are referred. In the event of conflict with any incorporated document, the content of this specification controls.

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 invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present application are only exemplary.

As used herein, "comprising," "including," "having," "containing," and the like, are open-ended terms, meaning including but not limited to.

The following embodiments of the present invention all use the jet fuel preparation device shown in FIG. 1 to prepare jet fuel;

Fig. 1 of the present invention, the jet fuel preparation device is composed of a hydrotreating reactor 1, a hydrotreating reactor 2, a hydrocracking reactor, a bio-oil heating furnace, a heavy oil heating furnace, a separation tank, a separator, a purifier, and a fractionator. ;

Wherein, the bio-oil heating furnace is connected with the inlet of the hydrotreating reactor 1, and the outlet of the hydrotreating reactor 1 is connected with the separation tank;

The heavy oil heating furnace is communicated with the inlet of the hydrotreating reactor 2, and the outlet of the hydrotreating reactor 2 is communicated with the separation tank;

The separation tank is connected with the inlet of the hydrocracking reactor and the purifier, and the outlet of the hydrocracking reactor is connected with the separator and the fractionator in turn; the separator is connected with the purifier;

The specific device diagram is shown in Figure 1.

The catalyst protection agent and the demetallization catalyst are Ni/A1 ₂ O ₃ and/or Mo/A1 ₂ O ₃ ; the hydrodeoxygenation catalyst is Ni-Mo/Al ₂ O ₃ and/or Ni-W/Al ₂ O ₃ ; the hydrodenitrogenation catalyst is Ni-Mo-W/Al ₂ O ₃ -P and/or Ni-W/Al ₂ O ₃

The loading amount of NiO in the catalyst Ni/A1 ₂ O ₃ used in the present invention is 3-6%; the loading amount of NiO in the catalyst Ni/A1 ₂ O ₃ used in the embodiment of the present invention is 3.9%;

The loading of MoO ₃ in the catalyst Mo/A1 ₂ O ₃ used in the present invention is 10-20%; the loading amount of MoO ₃ in the catalyst Mo/A1 ₂ O ₃ used in the examples of the present invention is 19%;

In the catalyst Ni-Mo/Al ₂ O ₃ used in the present invention, the loading of NiO is 3-6%, and the loading of MoO ₃ is 10-20%; the catalyst Ni-Mo/Al ₂ O used in the examples of the present invention The loading of NiO in ₃ is 3.9%, and the loading of MoO ₃ is 19%;

In the catalyst Ni-W/Al ₂ O ₃ used in the present invention, the loading amount of NiO is 3-8%, and the loading amount of WO ₃ is 20%-25%; the catalyst Ni-W/Al ₂ used in the embodiment of the present invention is The loading of NiO in _O3 is 5.2%, and the loading _of WO3 is 24.2%;

In the catalyst Ni-Mo-W/Al ₂ O ₃ -P used in the invention, the loading of NiO is 3-5%, the loading of WO ₃ is 8-15%, and the loading of MoO ₃ is 8-15% ; In the catalyst Ni-Mo-W/Al ₂ O ₃ -P used in the embodiment of the present invention, the loading of NiO is 5%, the loading of WO ₃ is 12%, and the loading of MoO ₃ is 10%;

The loading amount of CoO in the catalyst Co/A1 ₂ O ₃ used in the present invention is 3-6%; the loading amount of CoO in the catalyst Co/A1 ₂ O ₃ used in the embodiment of the present invention is 5.6%;

The loading amount of CoO in the catalyst Co-Mo/Al ₂ O ₃ used in the present invention is 3-6%, and the loading amount of MoO ₃ is 10-20%; the catalyst Co-Mo/Al ₂ O used in the embodiment of the present invention The loading of CoO in ₃ is ₅ %, and the loading of MoO is 16%;

In the catalyst Ni-Mo/SiO ₂ -P ₂ O ₅ used in the present invention, the loading of NiO is 3-6%, and the loading of MoO ₃ is 10-20%; The loading of NiO in SiO ₂ -P ₂ O ₅ is 3.9% and that of MoO ₃ is 19%;

In the catalyst Ni-Mo/Al ₂ O ₃ -P used in the present invention, the loading of NiO is 3-6%, and the loading of MoO ₃ is 10-20%; the catalyst Ni-Mo/Al used in the embodiment of the present invention The loading of NiO in _{2O3 -} P is 3.9%, and the loading of MoO3 is ₁₉ %;

In the catalyst Ni-W/Al ₂ O ₃ used in the present invention, the loading of NiO is 3% to 8%, and the loading of WO ₃ is 20% to 25%; the catalyst Ni-W/Al used in the examples of the present invention The loading _of NiO in _2O3 is 5.2%, and the loading _of WO3 is 24.2%;

In the catalyst Ni-Mo-W/zeolite-Al ₂ O ₃ -SiO ₂ used in the present invention, the loading amount of NiO is 3-6%, the loading amount of MoO ₃ is 8-15%, and the loading amount of WO ₃ is 10-10% 20%; in the catalyst Ni-Mo-W/zeolite-Al ₂ O ₃ -SiO ₂ used in the examples of the present invention, the loading amount of NiO is 3.5%, the loading amount of MoO ₃ is 12%, and the loading amount of WO ₃ is 10%;

In the catalyst Ni-W/SiO ₂ -Al ₂ O ₃ used in the present invention, the loading of NiO is 3% to 8%, and the loading of WO ₃ is 20% to 25%; The loading of NiO in W/SiO ₂ -Al ₂ O ₃ is 5.2%, and the loading of WO ₃ is 24.2%;

The loading of Pt in the catalyst Pt/Al ₂ O ₃ -F used in the present invention is 0.3-1.0%; the loading of Pt in the catalyst Pt/Al ₂ O ₃ -F used in the embodiment of the present invention is 0.5%;

The loading amount of NiO in the catalyst Ni-W/USY used in the present invention is 3% to 8%, and the loading amount of WO ₃ is 20% to 25%; The loading is 5.2%, and the loading of WO ₃ is 24.2%;

In the catalyst Ni-Mo/B ₂ O ₃ -A1 ₂ O ₃ used in the present invention, the loading of NiO is 3% to 5%, and the loading of MoO ₃ is 8 to 15%; the catalyst Ni used in the embodiment of the present invention is Ni The loading of NiO in -Mo/B ₂ O ₃ -A1 ₂ O ₃ is 5%, and the loading of MoO ₃ is 12%;

In the catalyst Ni-Mo-W/SiO ₂ -A1 ₂ O ₃ used in the present invention, the loading of NiO is 3% to 5%, the loading of MoO ₃ is 8% to 15%, and the loading of WO ₃ is 8% ～15%; in the catalyst Ni-Mo-W/SiO ₂ -A1 ₂ O ₃ used in the examples of the present invention, the loading amount of NiO is 5%, the loading amount of MoO ₃ is 10%, and the loading amount of WO ₃ is 12% %.

The raw materials in the examples of the present invention are all obtained from purchasing channels unless otherwise specified.

Example 1

The method of co-refining jet fuel with bio-oil and heavy oil:

(1) Add the microalgae to the methanol aqueous solution (the volume fraction of methanol in the methanol aqueous solution is 50%), and then carry out a methanol-hydrothermal reaction at 200° C. for 30 minutes, and the glycerolipids, phospholipids, glycolipids, fatty acids in the microalgae Enter the oil phase through methyl esterification, most of the protein and carbohydrate decomposition products enter the water phase, and the decomposed small molecular substances CO ₂ , H ₂ , CH ₄ enter the gas phase; then the temperature is 130 ° C and the pressure is 0.2Mpa conditions The microalgae purified oil is obtained by the lower flash separation, and the oxygen content of the microalgae purified oil is 10.5% and the nitrogen content is 3.6%.

(2) Preparation of microalgae hydrogenated oil: the microalgae purified oil was passed into the bio-oil heating furnace and heated to 125°C, and then the microalgae purified oil was passed into the hydrotreating reactor from the inlet at the top of the hydrotreating reactor 1 1. The microalgae purified oil first passes through the first catalyst bed, then passes through the second catalyst bed, and finally passes through the third catalyst bed to obtain the microalgae hydrogenated oil (deoxygenation and denitrification are simultaneously realized); three catalyst beds The layer height ratio is 0.2:1.1:1.3, the pressure in the hydrotreating reactor is controlled to be 6-8MPa, and the superficial flow rate is 0.25-2h ^-1 ; the catalyst of the first catalyst bed is Ni/Al ₂ O ₃ , Ni /Al ₂ O ₃ as a catalyst protection agent, also has catalytic activity, the bed temperature is 280-300 ℃, the hydrogen-oil ratio is 800-1000; the catalyst of the second catalyst bed is Ni-Mo/Al ₂ O ₃ , the bed The layer temperature is 300-350 ℃, the hydrogen-oil ratio is 1000-1200; the catalyst of the third catalyst bed 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: the heavy oil (heavy oil is the mixed oil of straight-run residual oil and vacuum residual oil with a mass ratio of 2:1, the sulfur content is 0.5%, and the nitrogen content is 0.25%) is passed into the heavy oil The heating furnace is heated to 90-150°C, and then the heavy oil is passed into the hydrotreating reactor 2 from the inlet at the top of the hydrotreating reactor 2, so that the heavy oil first passes through the first catalyst bed, and then passes through the second catalyst bed, Finally, the heavy oil hydrogenated oil (desulfurization and denitrification) is obtained through the third catalyst bed; the height ratio of the three-layer catalyst bed is 0.3:1.0:1.5, the pressure in the hydrotreating reactor is controlled to be 8MPa, and the superficial flow rate is 1h. ^-1 ; the catalyst of the first catalyst bed is Ni/Al ₂ O ₃ , and Ni/Al ₂ O ₃ is used as a catalyst protective agent, which also has catalytic activity, the bed temperature is 280-300° C., and the hydrogen-oil ratio is 800-1000 The catalyst of the second catalyst bed is Co-Mo/Al ₂ O ₃ , the bed temperature is 300～330 ℃, the hydrogen oil ratio is 800～1000; The catalyst of the third catalyst bed is the mass ratio of 0.8:1.2 Ni-Mo/Al ₂ O ₃ -P and Ni-W/Al ₂ O, the bed temperature is 350～375℃, and the hydrogen oil ratio is 900～1200.

(4) The microalgae hydrogenated oil (deoxygenation, denitrification) and the heavy oil hydrogenation oil (desulfurization, denitrification) prepared in step (2) and step (3) are passed into the separation tank at a mass ratio of 1:1, and after separation The fractionated gaseous substances in the tank are passed into the purifier for purification, and the fractionated liquid is passed into the hydrocracking reactor from the inlet at the top of the hydrocracking reactor, so that the fractionated liquid first passes through the first catalyst bed, and then passes through the second catalyst bed, Finally, the product oil is obtained through the third catalyst bed; the height ratio of the three-layer catalyst bed is 1:1.1:0.3, the pressure in the control hydrotreating reactor is 13-15MPa, and the superficial flow rate is 0.5-1h ^-1 ; The catalyst of the first catalyst bed is Ni-W/SiO ₂ -Al ₂ O ₃ , the bed temperature is 360-380 ° C, and the hydrogen-oil ratio is 1200-1500; the catalyst of the second catalyst bed is a mass ratio of 0.8: Ni-W/USY and Ni-W/SiO ₂ -Al ₂ O ₃ of 0.8-1.2, the bed temperature is 380-400 ℃, the hydrogen-oil ratio is 1200-1500; the catalyst of the third catalyst bed is the mass ratio of 0.8: 0.8-1.2 Ni-W/Al ₂ O ₃ and Ni-Mo-W/SiO ₂ -A1 ₂ O ₃ , the bed temperature is 400-430°C, and the hydrogen-oil ratio is 1200-1500.

(5) The product oil prepared in step (4) is passed into the separator, the separated gas is passed into the purifier, the separated liquid is passed into the fractionator, and fractionated to obtain naphtha, diesel oil, and kerosene (jet fuel).

The prepared jet fuel meets the requirements of ASTM standards for fluidity, volatility, flammability and cleanliness, wherein the bio-oil content is 51.5%, the S content in the jet fuel is less than 1 ppm, and the N content is less than 1 ppm.

Example 2

(1) After desalination and dehydration of the waste oil and fat, the waste oil and fat of desalination and dehydration are obtained, and then the waste oil and fat of desalination and dehydration are added to the methanol aqueous solution (the volume fraction of methanol in the methanol aqueous solution is 50%), and then methanol-water is carried out at 200° C. Thermal reaction, reaction for 30min, glycerolipid, phospholipid, glycolipid and fatty acid in microalgae enter the oil phase through methyl esterification, most of the protein and carbohydrate decomposition products enter the water phase, and the decomposed small molecular substances CO ₂ , H ₂ , CH ₄ Enter the gas phase; then flash separation at a temperature of 130°C and a pressure of 0.2Mpa to obtain waste grease purification oil, the oxygen content of the waste grease purification oil is 11.9%, and the nitrogen content is 0.05%.

(2) Preparation of waste grease hydrogenation oil: the waste grease purification oil is passed into the bio-oil heating furnace and heated to 110-150°C, and then the waste grease purification oil is passed into the hydrotreating oil from the inlet at the top of the hydrotreating reactor 1 Reactor 1, the microalgae purified oil first passes through the first catalyst bed, then passes through the second catalyst bed, and finally passes through the third catalyst bed to obtain waste oil hydrogenation oil (deoxygenation, denitrification); three catalyst beds The layer height ratio is 0.2:1.3:1.3, the pressure in the hydrotreating reactor is controlled to be 6-8MPa, and the superficial flow rate is 0.75-1h ^-1 ; the catalyst of the first catalyst bed is Ni/Al ₂ O ₃ , Ni /Al ₂ O ₃ as a catalyst protection agent, also has catalytic activity, the bed temperature is 280-300 ℃, the hydrogen-oil ratio is 800-1000; the catalyst of the second catalyst bed is Ni-Mo/Al ₂ O ₃ , the bed The layer temperature is 300-350 ℃, the hydrogen-oil ratio is 1000-1200; the catalyst of the third catalyst bed 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: the heavy oil (heavy oil is a vacuum wax oil with a mass ratio of 1:2:0.5, a straight-run wax oil, a mixed oil of coking wax oil, the sulfur content is 0.45%, and the nitrogen content is 0.3%) into the heavy oil heating furnace to be heated to 110～150 ℃, and then pass the heavy oil into the hydrotreating reactor 2 from the inlet at the top of the hydrotreating reactor 2, so that the heavy oil first passes through the first catalyst bed, and then passes through the first catalyst bed. Two catalyst beds, and finally through the third catalyst bed to obtain heavy oil hydrogenated oil (desulfurization, denitrification); the height ratio of the three catalyst beds is 0.2:1.2:1.5, and the pressure in the hydrofinishing reactor is controlled to be 6 ～10MPa, the superficial flow rate is 1h ^-1 ; the catalyst of the first catalyst bed is Ni/Al ₂ O ₃ , and Ni/Al ₂ O ₃ is used as a catalyst protective agent, which also has catalytic activity, and the bed temperature is 280～300 ℃ , the hydrogen-oil ratio is 800-1000; the catalyst of the second catalyst bed 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 is It is Ni-Mo/Al ₂ O ₃ -P, the bed temperature is 350-375°C, and the hydrogen-oil ratio is 900-1200.

(4) The waste oil hydrogenation oil (deoxygenation, denitrification) and heavy oil hydrogenation oil (desulfurization, denitrification) prepared in step (2) and step (3) are put into the separation tank with a mass ratio of 1:1, and in the separation tank The gaseous substances from the internal fractionation are passed into the purifier for purification, and the fractionated liquid is passed into the hydrocracking reactor from the inlet at the top of the hydrocracking reactor, so that the fractionated liquid first passes through the first catalyst bed, then passes through the second catalyst bed, and finally The product oil is obtained through the third catalyst bed; the height ratio of the three-layer catalyst bed is 1:1.3:0.3, the pressure in the control hydrotreating reactor is 13-15MPa, and the superficial flow rate is 0.75h ^-1 ; the first The catalysts in the catalyst bed are Ni-W/SiO ₂ -Al ₂ O and Pt/Al ₂ O ₃ -F ₃ with a mass ratio of 1:1, the bed temperature is 360-380°C, and the hydrogen-oil ratio is 1200-1500 The catalyst of the second catalyst bed is Ni-W/USY and Ni-W/SiO ₂ -Al ₂ O ₃ whose mass ratio is 1:1, the bed temperature is 380～400 ℃, and the hydrogen oil ratio is 1200～1500 The catalyst of the third catalyst bed is Ni-W/Al ₂ O ₃ and Ni-Mo-W/SiO ₂ -A1 ₂ O ₃ with a mass ratio of 1:1, the bed temperature is 400-430 ° C, and the hydrogen oil The ratio is 1200-1500.

(5) The product oil prepared in step (4) is passed into the separator, the separated gas is passed into the purifier, the separated liquid is passed into the fractionator, and fractionated to obtain naphtha, diesel oil, and kerosene (jet fuel).

The prepared jet fuel meets the requirements of fluidity, volatility, flammability and cleanliness in the ASTM standard, wherein the bio-oil content is 50.1%, the S content in the jet fuel is less than 1 ppm, and the N content is less than 1 ppm.

After 1000 hours of using the refining method of Examples 1-2 of the present invention (refining by blending bio-oil), the activities of the hydrotreating catalyst and the hydrocracking catalyst are comparable to those of the process without bio-oil refining.

The density of the jet fuel prepared in Examples 1-2 of the present invention is 785-799 kg/m ³ , the calorific value is 42.7-43.8 MJ/kg, the freezing point is less than -47°C, the S content is less than 1 ppm, and the N content is less than 1 ppm.

The above-mentioned embodiments are only to describe the preferred modes of the present invention, but not to limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.

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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