CN114437820A - Hydrocracking method for producing aviation kerosene - Google Patents
Hydrocracking method for producing aviation kerosene Download PDFInfo
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- CN114437820A CN114437820A CN202011230327.XA CN202011230327A CN114437820A CN 114437820 A CN114437820 A CN 114437820A CN 202011230327 A CN202011230327 A CN 202011230327A CN 114437820 A CN114437820 A CN 114437820A
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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
- C10G67/14—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 including at least two different refining steps in the absence of hydrogen
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention relates to the field of oil refining, in particular to a hydrocracking method for producing aviation kerosene. The method comprises the following steps: 1) in the presence of hydrogen, raw oil sequentially flows through a hydrofining reaction zone and a hydrocracking reaction zone to carry out contact reaction, and a liquid-phase product obtained in the hydrocracking reaction zone is fractionated to obtain naphtha fraction, kerosene fraction, diesel fraction and tail oil fraction; 2) carrying out gas-liquid separation on the kerosene fraction obtained in the step 1) to respectively obtain a gas phase capable of being recycled for fractionation and a liquid phase which is taken as a aviation kerosene product and is discharged from a device; wherein, in the step 1), the conditions of the hydrocracking reaction zone are controlled, so that the conversion rate of distillate oil with the temperature of more than 350 ℃ in the raw oil is 65-88%. The method provided by the invention can economically and flexibly effectively improve the quality of the aviation kerosene of the hydrocracking device, and the aviation kerosene with high aromatic hydrocarbon and low density can be obtained by the method.
Description
Technical Field
The invention relates to the field of oil refining, in particular to a hydrocracking method for producing aviation kerosene.
Background
Hydrocracking is a catalytic conversion process in which raw oil undergoes hydrogenation, desulfurization, denitrification, rearrangement of molecular skeleton structure, cracking and other reactions at high temperature and high pressure in the presence of a catalyst, and is one of the main technological means for deep processing of heavy oil. The raw materials which can be processed by the method have wide range, comprise straight-run gasoline, diesel oil, straight-run wax oil, atmospheric residue oil, vacuum residue oil and other raw materials obtained by secondary processing, such as catalytic diesel oil, catalytic clarified oil, coking diesel oil, coking wax oil, deasphalted oil and the like, can be produced into various products with good quality, and can be used for directly producing high-quality clean fuels such as liquefied gas, gasoline, kerosene, jet fuel, diesel oil and the like and high-quality petrochemical raw materials such as light naphtha, heavy naphtha, tail oil and the like.
The light naphtha can be directly used for blending and producing high-octane gasoline and can also be used for producing ethylene raw materials. The heavy naphtha has high potential aromatic hydrocarbon content and low sulfur and nitrogen content, and is a high-quality feed for producing high-octane gasoline or light aromatic hydrocarbon by catalytic reforming.
In the hydrocracking process, straight-run wax oil, coker wax oil, catalytic diesel oil and/or coker diesel oil are used as raw material oil, and products such as naphtha, middle distillate oil (including aviation kerosene and diesel oil) and tail oil can be obtained, but the aviation kerosene quality is closely related to the feeding property, the reaction hydrogen partial pressure, the conversion depth, the process flow and the operation time of the device.
The most desirable components in jet fuel compositions are monocyclic cycloalkanes and branched paraffins, which have excellent flammability, thermal stability and low temperature flow properties. Smoke point is an important indicator of jet fuel: the smoke point, also known as the smokeless flame height, is the maximum height in millimeters of a fuel flame measured in a specially made lamp when the flame is not emitting smoke, and the higher the smoke point, the less prone the fuel to form soot. The naphthene and aromatic contents of more than two rings are closely related to the index of smoke point, and generally, the higher the contents of polycyclic naphthene and aromatic hydrocarbon are, the lower the smoke point is.
The relationship among smoke point, density and aromatics is as follows: the more aromatic hydrocarbons, the lower the smoke point, and the lower the smoke point, the more carbon deposits are formed. Meanwhile, the higher the aromatic hydrocarbon content, the higher the density; the lower the aromatic content, the lower the density.
For jet fuels, a higher mass heating value is required. The larger the mass heat value is, the larger the thrust of the engine is, and the lower the fuel consumption rate is. The calorific value of jet fuel is related to density and chemical composition. Of the three aromatic, paraffinic and naphthenic hydrocarbons, the aromatic hydrocarbon has the highest density and the lowest mass thermal value.
However, depending on the particular requirements of the customer, the requirement that the aromatic content of the jet fuel be not less than 8% is primarily to aid in the stability of the engine internals of the aircraft, while meeting density, freeze point and end point requirements. The jet fuel has strict requirements on the properties, and is narrower than the comprehensive properties of the jet fuel required by the national standard.
For the existing hydrocracking device, the reaction hydrogen partial pressure, the process flow is relatively fixed, the conversion depth is also generally difficult to greatly adjust due to the bottleneck of a subsequent fractionation system, and the aviation kerosene quality of the device is generally greatly influenced under the great trend of obvious deterioration trend of the feeding property.
Therefore, how to guarantee the quality of the aviation kerosene and how to improve the aromatic hydrocarbon content of the aviation kerosene is an urgent problem to be solved.
CN103013559A discloses a method for improving the yield of hydrocracking aviation kerosene, which comprises returning heavy diesel oil fraction to raw oil for continuous reaction, wherein the mass percentage of the circulating heavy diesel oil fraction in the total weight of the diesel oil fraction is 10-100%. The method can increase the yield of the aviation kerosene on the original basis, but fails to provide a scheme for effectively improving the quality of the existing aviation kerosene.
CN106520195A discloses a hydrocracking method for improving the quality of aviation kerosene, which comprises introducing kerosene fraction into a kerosene fractionating tower for fractionation to obtain light aviation kerosene fraction, medium aviation kerosene fraction and heavy aviation kerosene fraction, extracting part of the medium aviation kerosene fraction, and taking the light aviation kerosene fraction, the heavy aviation kerosene fraction and the optional rest of the medium aviation kerosene fraction as aviation kerosene product. A kerosene fractionation tower that can split the product into three streams is needed to implement the process.
CN106520197A discloses a hydrocracking method for producing aviation kerosene from inferior raw oil, which comprises introducing the obtained kerosene fraction into a kerosene fractionating tower for fractionation to obtain light aviation kerosene fraction and heavy aviation kerosene fraction, recycling at least part of the heavy aviation kerosene fraction back to the raw material tank and/or hydrofining reaction zone, and taking the light aviation kerosene fraction and the optional rest heavy aviation kerosene fraction as aviation kerosene product outlet device. The method needs to add a kerosene fractionating tower to a raw material tank and/or a hydrofining reactor, and has higher safety risk for the running device; the kerosene production is reduced after recycling of the kerosene.
The quality of the aviation kerosene obtained by the method provided by the prior art is almost impossible if the requirement of the national standard is exceeded.
Disclosure of Invention
The invention aims to overcome the defects that the aviation kerosene obtained by the method in the prior art cannot simultaneously meet the requirements of aromatic hydrocarbon content, density, final distillation point and freezing point in a narrow range, and the aviation kerosene serving as a special customer-required aviation fuel is limited in application.
In order to achieve the above object, the present invention provides a hydrocracking process for producing aviation kerosene, comprising:
1) in the presence of hydrogen, raw oil sequentially flows through a hydrofining reaction zone containing a hydrofining catalyst and a hydrocracking reaction zone containing a hydrocracking catalyst and a post-refining catalyst to perform contact reaction, and a liquid-phase product obtained in the hydrocracking reaction zone is fractionated to obtain a naphtha fraction, a kerosene fraction, a diesel fraction and a tail oil fraction;
2) carrying out gas-liquid separation on the kerosene fraction obtained in the step 1) to respectively obtain a gas phase which can be recycled to the step 1) for fractionation and a liquid phase which is taken as a aviation kerosene product and is discharged from a device;
wherein, in the step 1), the conditions of the hydrocracking reaction zone are controlled, so that the conversion rate of distillate oil with the temperature of more than 350 ℃ in the raw oil is 65-88%.
The method provided by the invention can effectively improve the quality of aviation kerosene of the hydrocracking device.
The aviation kerosene provided by the method has the characteristics of high aromatic hydrocarbon content and low density.
Compared with other methods for improving the quality of aviation kerosene of the hydrocracking device, the method provided by the invention can be carried out by adopting the existing hydrocracking device, the equipment is not required to be improved, and the cost is saved.
The method can be carried out by adopting a hydrocracking process with double agents connected in series and one-time passing, and has simple process and flexible operation.
The high-smoke-point and low-density aviation fuel obtained by the method can be used as aviation fuel with higher performance requirements.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. Many devices such as pumps, heat exchangers, compressors, etc. have been omitted from the figure, but are well known to those skilled in the art. In the drawings:
FIG. 1 is a schematic process flow diagram of a preferred embodiment of the process according to the invention.
Description of the reference numerals
1. Raw oil 2, hydrogen
3. A hydrofining reaction zone 4 and a hydrocracking reaction zone
5. High pressure separator 6, low pressure separator
7. Hydrogen sulfide stripping tower 8 and fractionating tower
9. Naphtha fraction 10 and kerosene fraction
11. Diesel fraction 12, tail oil fraction
13. Aviation kerosene stripping tower 14 and aviation kerosene product
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the present invention provides a hydrocracking process for producing aviation kerosene, the process comprising:
1) in the presence of hydrogen, raw oil sequentially flows through a hydrofining reaction zone containing a hydrofining catalyst and a hydrocracking reaction zone containing a hydrocracking catalyst and a post-refining catalyst to perform contact reaction, and a liquid-phase product obtained in the hydrocracking reaction zone is fractionated to obtain a naphtha fraction, a kerosene fraction, a diesel fraction and a tail oil fraction;
2) carrying out gas-liquid separation on the kerosene fraction obtained in the step 1) to respectively obtain a gas phase which can be recycled to the step 1) for fractionation and a liquid phase which is taken as a aviation kerosene product and is discharged from a device;
wherein, in the step 1), the conditions of the hydrocracking reaction zone are controlled so that the conversion rate of distillate oil with the raw oil of more than 350 ℃ is 65-88%.
Preferably, in the step 1), the conditions of the hydrocracking reaction zone are controlled so that the conversion rate of distillate oil with raw oil of more than 350 ℃ is 68-85%.
By adopting the method provided by the invention, the aviation kerosene meeting the following specific index requirements can be produced without changing the existing device and process: aromatic hydrocarbon content (representing total content of monocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon) is not less than 8 vol%, final distillation point is not more than 275 deg.C, and density is not more than 810kg/m3The smoke point is not less than 25mm, the freezing point is not more than-50 ℃, and other indexes meet the standard of GB 6537-2018.
In the present invention, the hydrofining reaction zone refers to a region where the feedstock oil can undergo a hydrofining reaction, in which the feedstock oil undergoes at least one reaction selected from hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization with hydrogen, and a hydrosaturation reaction of unsaturated hydrocarbons.
In the present invention, the hydrocracking reaction zone refers to a zone where the feedstock oil can undergo a hydrocracking reaction, and in this zone the feedstock oil can undergo at least one of hydrogenation saturation, impurity removal, and a cracking reaction with hydrogen.
Preferably, the inventors of the present invention have found that by using the following hydrofinishing catalyst, hydrocracking catalyst and post-refining catalyst, a higher smoke point is obtained for aviation kerosene.
Preferably, the hydrofining catalyst in the hydrofining reaction zone comprises a carrier and an active metal element loaded on the carrier, wherein the carrier comprises amorphous alumina and/or amorphous silica-alumina; the active metal elements include at least one of group VIB non-noble metal elements and group VIII non-noble metal elements.
Preferably, in the hydrocracking reaction zone, the hydrocracking catalyst contains a carrier selected from at least one of alumina, amorphous silica-alumina and zeolite and an active component element supported on the carrier; the active component elements are noble metal elements and/or non-noble metal elements; the non-noble metal elements are VIB group metal elements and/or VIII group metal elements; preferably, in the hydrocracking catalyst, the VIB group metal element is Mo and/or W, and the VIII group metal element is Co and/or Ni; the noble metal element is Pt element and/or Pd element; the amorphous silica-alumina comprises silica and/or alumina.
Preferably, the post-refining catalyst in the hydrocracking reaction zone comprises a carrier and an active metal element loaded on the carrier, wherein the carrier comprises amorphous alumina and/or amorphous silica-alumina, and the commonly used carrier can also be gamma-Al2O3(ii) a The active metal elements comprise non-noble metal elements of group VIBAt least one of elemental and non-noble group VIII metal elements, with commonly used active metals including at least one of Mo, W, Co, and Ni. More preferably, in the post-refining catalyst of the present invention, the group VIB metal element is Mo and/or W, and the group VIII metal element is Co and/or Ni.
Preferably, the inventors of the present invention have found that the aromatic content of the aviation kerosene obtained by the process of the present invention is lower when the following hydrofinishing catalyst, hydrocracking catalyst and post-refining catalyst are used in combination. The hydrofining catalyst is RN-32V and RN-410; the hydrocracking catalyst is RHC-3, RHC-133 and RHC-131, the post-refining catalyst is RN-410, and the catalysts are all produced by ChangLing division of catalysts of China petrochemical company Limited; and the loading volume ratio of the hydrocracking catalyst to the post-refining catalyst is (10-13): 1.
preferably, the packing volume ratio of the RN-32V to the RN-410 is (1-2): 1.
preferably, the loading volume ratio of said RHC-3, said RHC-133 and said RHC-131 is (0.2-0.8): (0.2-0.8): 1. with such a packing volume ratio, the aromatic content and density of the aviation kerosene product of the present invention can be further increased.
It will be appreciated by those skilled in the art that the above list of catalysts should not be considered as limiting the invention, but merely as preferred examples thereof.
Preferably, in step 1), the reaction conditions of the hydrofining reaction zone include: the reaction temperature is 375-385 ℃, the hydrogen partial pressure is 12-13MPa, and the volume ratio of hydrogen to oil is (900-1200): 1, the volume space velocity is 0.7-1h-1。
Preferably, in step 1), the reaction conditions of the hydrocracking reaction zone include: the reaction temperature is 370-390 ℃, the hydrogen partial pressure is 12-13MPa, and the volume ratio of hydrogen to oil is (900-1200): 1, the volume space velocity is 1-1.4h-1。
Preferably, in step 1), the fractionation is carried out in a fractionation column in which the side draw starting temperature of the kerosene fraction is 170-185 ℃.
Preferably, the fractionation column feed temperature is 330-.
Preferably, in step 1), the overhead pressure of the fractionation column is 0.06 to 0.08MPa, and herein, a gauge pressure is referred to unless otherwise specified.
Preferably, the overhead temperature of the fractionation column is 115-120 ℃.
Preferably, the ratio of the flow rate of the liquid-phase product obtained from the bottom of the low-pressure separator to the processing amount is controlled to be 18-38 wt%.
Preferably, the temperature of the aviation kerosene extraction of the fractionating tower is controlled between 170 ℃ and 185 ℃.
Preferably, in step 1), the method further comprises: according to the flowing direction of reactant flow, a high-pressure separator and a low-pressure separator are sequentially arranged between the hydrocracking reaction zone and the fractionating tower to carry out first gas-liquid separation; the liquid phase product obtained from the bottom of the low pressure separator is then introduced into a hydrogen sulfide stripper to remove hydrogen sulfide therefrom.
Preferably, in step 1), the gas-liquid separation of the kerosene fraction is carried out in a kerosene stripper.
In the present invention, there is no particular limitation on the operating conditions in the high-pressure separator, the low-pressure separator, the hydrogen sulfide stripper, the fractionating tower and the aviation kerosene stripper, and those skilled in the art can select suitable operating conditions for separation and fractionation according to the conventional technical means in the field after understanding the technical scheme of the present invention. The invention will not be described in detail here.
In the present invention, it is preferred that the cut points of the naphtha fraction and the kerosene fraction are 140-160 ℃; the cut points of the kerosene fraction and the diesel fraction are 220-280 ℃; the cut points of the diesel fraction and the tail oil fraction are 305-330 ℃. Illustratively, in the present invention, it is preferred that the cut point of the naphtha fraction and the kerosene fraction is 155 ℃; the cut points of the kerosene fraction and the diesel fraction are 270 ℃; the diesel fraction and the tail oil fraction have a cut point of 320 ℃. More preferably, in the present invention, the cut point of the naphtha fraction and the kerosene fraction is 150 ℃; the cut points of the kerosene fraction and the diesel fraction are 260 ℃; the diesel fraction and the tail oil fraction have a cut point of 310 ℃.
In the present invention, the raw oil used is at least one selected from the group consisting of straight-run wax oil, coker wax oil, catalytic diesel oil and coker diesel oil.
Preferably, the raw oil is straight-run wax oil and catalytic diesel oil, and the weight ratio of the straight-run wax oil to the catalytic diesel oil is (6-8): 1.
preferably, the raw oil is straight-run wax oil and coker diesel oil, and the weight ratio of the straight-run wax oil to the coker diesel oil is (5.7-6.5): 1.
preferably, the distillation range of the straight-run wax oil is in the range of 260-550 ℃, which means that the initial distillation point and the final distillation point of the straight-run wax oil fall in the range of 260-550 ℃.
Preferably, the distillation range of the catalytic diesel oil is in the range of 200 ℃ to 350 ℃, which means that the initial distillation point and the final distillation point of the catalytic diesel oil fall in the range of 200 ℃ to 350 ℃.
Preferably, the distillation range of the coker gas oil is in the range of 200 ℃ to 370 ℃, which means that the initial and final distillation points of the coker gas oil fall in the range of 200 ℃ to 370 ℃.
According to a preferred embodiment of the invention, the process of the invention is carried out using a process scheme as shown in fig. 1, in particular as follows:
In particular, the method of the invention also comprises the following specific advantages:
(1) by adopting the method provided by the invention, the aviation kerosene with different index requirements can be produced under the condition of not changing the flow and equipment by adjusting the raw material proportion and the process parameters;
(2) simultaneously, the performance index requirements of high aviation kerosene aromatic hydrocarbon content, low density and low final boiling point are met, and the method is simple to operate and low in cost;
(3) the method of the invention can obtain the aviation kerosene with higher quality than the national standard.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, various raw materials used were commercially available without specific description. The straight-run wax oil used is shown in Table 1, the catalytic diesel oil used is shown in Table 2, and the coker diesel oil used is shown in Table 3.
In the following examples and comparative examples, hydrofinishing catalysts, hydrocracking catalysts and post-refining catalysts developed by the institute of petrochemical science (RIPP) of China were used, the hydrofinishing catalysts used were RN-32V and RN-410 (packing volume ratio of 1.6: 1), and the chemical composition mainly comprised MoO3And NiO; the hydrocracking catalyst used is RHC-3, RHC-133 and RHC-131 (loading volume ratio is 0.5: 0.5: 1), and the chemical composition mainly comprises WO3And NiO; the used post-refining catalyst is RN-410, and the catalysts are all produced by catalyst ChangLing division of China petrochemical company Limited; and the loading volume ratio of the hydrocracking catalyst to the post-refining catalyst is 11.4: 1.
in the following examples and comparative examples, the conversion of distillate oil of feedstock oil > 350 ℃ was calculated by the following formula,
conversion rate of distillate oil with raw oil more than 350 ℃ ═ 100% (> 350 ℃ mass fraction in raw oil-350 ℃ mass fraction in produced oil)/350 ℃ mass fraction in raw oil
Wherein, the mass fraction of the fraction of more than 350 ℃ in the raw oil is obtained by testing and analyzing the distillation range and the yield, and the mass fraction of the fraction of more than 350 ℃ in the generated oil is obtained by testing and analyzing the distillation range and the yield.
Table 1: straight-run wax oil property
| Straight-run wax oil A | Straight-run wax oil B | |
| Density (20 ℃), kg/m3 | 914.2 | 910.5 |
| 2％(v/v)，℃ | 269.0 | 268.1 |
| 10％(v/v)，℃ | 339.8 | 339.8 |
| 30％(v/v)，℃ | 376.8 | 375.1 |
| 50％(v/v)，℃ | 405.0 | 409.0 |
| 70％(v/v)，℃ | 430.8 | 432.7 |
| 90％(v/v)，℃ | 466.2 | 467.1 |
| 97％(v/v)，℃ | 500.0 | 510.0 |
| Sulfur mass fraction,% of | 2.4 | 2.2 |
| Nitrogen mass fraction,% of | 0.09 | 0.09 |
| Chlorine content, mg/kg | 2.4 | 2.4 |
| BMCI value | 50.0 | 50.0 |
Table 2: catalytic diesel oil property
Table 3: properties of coking diesel oil
| Coking diesel oil D | |
| Density (20 ℃), kg/m3 | 880.7 |
| 2％(v/v)，℃ | 210.0 |
| 10％(v/v)，℃ | 245.0 |
| 50％(v/v)，℃ | 296.0 |
| 90％(v/v)，℃ | 338.0 |
| 350 ℃ distillate volume, mL | 361.0 |
| Freezing point, DEG C | -17.0 |
| Nitrogen mass fraction,% of | 0.13 |
| Cetane index | 60.0 |
| Paraffin content, volume% | 28.1 |
| Naphthenes content, volume% | 29.5 |
| Aromatic content, volume% | 42.4 |
Example 1
When the processing amount is 200t/h, introducing 175t/h of straight-run wax oil A shown in table 1 and 25t/h of catalytic diesel oil C shown in table 2 and hydrogen into a hydrofining reaction zone containing a hydrofining catalyst, a hydrocracking catalyst and a hydrocracking reaction zone of a post-refining catalyst for reaction, wherein the hydrogen partial pressure is 12.2MPa, and the volume ratio of hydrogen to oil is 980: 1, the average temperature of the hydrofining reaction zone is 381 ℃, and the volume space velocity of the hydrofining reaction zone is 0.8h-1The average temperature of the hydrocracking reaction zone is 386.5 ℃, and the volume space velocity of the hydrocracking reaction zone is 1.2h-1The conversion rate of distillate oil with raw oil more than 350 ℃ is 83.6 percent; then, the reaction effluent of the hydrocracking reaction zone is sequentially introduced into a high-pressure separator and a low-pressure separator for gas-liquid separation to obtain a liquid-phase product, the liquid-phase product is sequentially introduced into a hydrogen sulfide stripping tower and a fractionating tower for fractionation in the fractionating tower, the flow rate of the liquid-phase product obtained from the bottom of the low-pressure separator (hereinafter, referred to as low oil separation flow rate) is controlled at 70t/h, the feeding temperature of the fractionating tower is 331 ℃, the side line extraction temperature of the fractionating tower is 174 ℃, the temperature of the top of the fractionating tower is 118 ℃, and the pressure of the top of the fractionating tower is 0.07MPa (gauge pressure), thus obtaining naphtha fraction, kerosene fraction, diesel fraction and tail oil fraction (the cutting points of the naphtha fraction and the kerosene fraction are 150 ℃; and the kerosene fraction and the tail oil fraction are cutThe cutting point of the diesel oil fraction is 260 ℃; the cut point of the diesel fraction and the tail oil fraction is 310 ℃, the same below). And introducing the obtained kerosene fraction into a aviation kerosene stripping tower for further fractionation to obtain an aviation kerosene product at the bottom of the tower. The properties of the aviation kerosene product are shown in Table 4.
Example 2
When the processing amount is 200t/h, 175t/h of straight-run wax oil A shown in Table 1 and 25t/h of catalytic diesel oil C shown in Table 2 are adopted, and the process is carried out by adopting the same flow as example 1, except that the process conditions are as follows: the hydrogen partial pressure is 12MPa, and the volume ratio of hydrogen to oil is 1200: 1, the average temperature of the hydrofining reaction zone is 375 ℃, and the volume space velocity of the hydrofining reaction zone is 0.7h-1The average temperature of the hydrocracking reaction zone is 370 ℃, and the volume space velocity of the hydrocracking reaction zone is 1h-1The low oil flow is controlled at 75t/h, the conversion rate of distillate oil with raw oil being more than 350 ℃ is 68 percent, the feeding temperature of a fractionating tower is 333 ℃, the side line extraction temperature of the fractionating tower is controlled at 170 ℃, the top temperature of the fractionating tower is 115 ℃, the top pressure of the fractionating tower is 0.06MPa, and the properties of the aviation kerosene product are shown in Table 4.
Example 3
When the processing amount is 200t/h, 175t/h of straight-run wax oil A shown in Table 1 and 25t/h of catalytic diesel oil C shown in Table 2 are adopted, and the process is carried out by adopting the same flow as example 1, except that the process conditions are as follows: the hydrogen partial pressure is 13MPa, and the volume ratio of hydrogen to oil is 900: 1, the average temperature of the hydrofining reaction zone is 385 ℃, and the volume space velocity of the hydrofining reaction zone is 1h-1The average temperature of the hydrocracking reaction zone is 390 ℃, and the volume space velocity of the hydrocracking reaction zone is 1.4h-1The low oil flow is controlled at 72t/h, the conversion rate of distillate oil with raw oil being more than 350 ℃ is 85 percent, the feeding temperature of a fractionating tower is 333 ℃, the side line extraction temperature of the fractionating tower is 185 ℃, the top temperature of the fractionating tower is 120 ℃, the top pressure of the fractionating tower is 0.08MPa, and the properties of the aviation kerosene product are shown in Table 4.
Example 4
At a working capacity of 185t/h, 157.5t/h of straight-run paraffin oil B shown in Table 1 and 27.5t/h of coker diesel oil D shown in Table 3 were used, and the same procedure as in example 1 was usedThe difference lies in that the process conditions are as follows: the hydrogen partial pressure is 12.2MPa, and the volume ratio of hydrogen to oil is 1200: 1, the average temperature of the hydrofining reaction zone is 380 ℃, and the volume space velocity of the hydrofining reaction zone is 0.8h-1The average temperature of the hydrocracking reaction zone is 374.5 ℃, and the volume space velocity of the hydrocracking reaction zone is 1.1h-1The low oil flow is controlled at 42t/h, the conversion rate of distillate oil with raw oil being more than 350 ℃ is 71.3 percent, the feeding temperature of a fractionating tower is 325 ℃, the side line extraction temperature of the fractionating tower is controlled at 181 ℃, the top temperature of the fractionating tower is 118 ℃, the top pressure of the fractionating tower is 0.07MPa, and the properties of the aviation kerosene product are shown in Table 4.
Example 5
At 185t/h, 157.5t/h of straight run waxy oil B shown in Table 1 and 27.5t/h of coker diesel oil D shown in Table 3 were used, and the same procedure as in example 1 was followed, except that the process conditions were as follows: the hydrogen partial pressure is 13MPa, and the volume ratio of hydrogen to oil is 1200: 1, the average temperature of the hydrofining reaction zone is 385 ℃, and the volume space velocity of the hydrofining reaction zone is 0.7h-1The average temperature of the hydrocracking reaction zone is 370 ℃, and the volume space velocity of the hydrocracking reaction zone is 1.4h-1The low oil flow is controlled at 37.0t/h, the conversion rate of distillate oil with raw oil being more than 350 ℃ is 85 percent, the feeding temperature of a fractionating tower is 325 ℃, the side line extraction temperature of the fractionating tower is controlled at 175 ℃, the top temperature of the fractionating tower is 120 ℃, the top pressure of the fractionating tower is 0.06MPa, and the properties of the aviation kerosene product are shown in Table 4.
Example 6
At 185t/h, 157.5t/h of straight run waxy oil B shown in Table 1 and 27.5t/h of coker diesel oil D shown in Table 3 were used, and the same procedure as in example 1 was followed, except that the process conditions were as follows: the hydrogen partial pressure is 12MPa, and the volume ratio of hydrogen to oil is 900: 1, the average temperature of the hydrofining reaction zone is 375 ℃, and the volume space velocity of the hydrofining reaction zone is 1h-1The average temperature of the hydrocracking reaction zone is 390 ℃, and the volume space velocity of the hydrocracking reaction zone is 1h-1The low oil separation flow is controlled to be 34.0t/h, the conversion rate of distillate oil with raw oil of more than 350 ℃ is 68 percent, the feeding temperature of a fractionating tower is 325 ℃, the side line extraction temperature of the fractionating tower is controlled to be 170 ℃,the top temperature of the fractionation column was 115 ℃ and the top pressure of the fractionation column was 0.08MPa, and the properties of the aviation kerosene product are shown in Table 4.
Example 7
The same raw materials, catalysts and procedures as in example 1 were used except that the conditions in the hydrocracking reaction zone were controlled such that the average temperature in the hydrocracking reaction zone was 387.5 ℃, the conversion of distillate oil with raw material oil > 350 ℃ was 86.5%, the low oil fraction flow rate was controlled at 65.0t/h, and the properties of the aviation kerosene products are shown in table 4.
Example 8
The same raw materials, catalysts and procedures as in example 1 were used except that the conditions in the hydrocracking reaction zone were controlled such that the average temperature in the hydrocracking reaction zone was 388.2 ℃, the conversion of distillate oil with raw material oil > 350 ℃ was 88%, the low-molecular oil flow rate was controlled at 72.0t/h, and the properties of the aviation kerosene products are shown in Table 4.
Example 9
The same raw materials, catalysts and procedures as in example 1 were used except that the conditions in the hydrocracking reaction zone were controlled such that the average temperature in the hydrocracking reaction zone was 381.0 ℃, the conversion of distillate oil with raw material oil > 350 ℃ was 65%, the low-distillate oil flow rate was controlled at 59.0t/h, and the properties of the aviation kerosene products are as shown in Table 4.
Comparative example 1
The same raw materials, catalysts and procedures as in example 1 were used, except that the conditions in the hydrocracking reaction zone were controlled to raise the temperature of each bed in the cracking reactor to 390.5 ℃, and further to raise the conversion of distillate oil with raw oil > 350 ℃, the conversion being 92%, and the properties of the aviation kerosene products are shown in table 4.
Comparative example 2
The same raw materials, catalysts and procedures as in example 4 were used, except that the conditions in the hydrocracking reaction zone were controlled to lower the temperature of each bed in the cracking reactor to 368.5 ℃, and further to lower the conversion of distillate oil with raw oil > 350 ℃, the conversion was 62.5%, and the properties of the aviation kerosene products are shown in table 4.
TABLE 4
| Aviation kerosene product | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Density (20 ℃ C.)/(kg/m)3) | 809.1 | 808.7 | 809.0 | 810.0 | 807.9 | 809.1 |
| Smoke point/mm | 25.2 | 26.1 | 25.6 | 25.7 | 25.5 | 25.7 |
| Aromatic content/(vol%) | 8.5 | 9.0 | 9.5 | 9.0 | 9.5 | 10.0 |
| End point/. degree.C | 269.9 | 263.1 | 260.6 | 254.0 | 255.6 | 252.6 |
| Freezing point/. degree.C | -60.7 | -60 | -65.8 | -53.9 | -55.2 | -55.7 |
Table 4 (continuation 1)
| Aviation kerosene product | Example 1 | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 |
| Density (20 ℃ C.)/(kg/m)3) | 809.1 | 809.5 | 809.7 | 810.0 | 799.5 | 815.9 |
| Smoke point/mm | 25.2 | 25.3 | 25.0 | 25.3 | 27.7 | 22.1 |
| Volume content of aromatic hydrocarbons/(%) | 8.5 | 8.2 | 8.3 | 8.0 | 5.4 | 11.5 |
| End point/. degree.C | 269.9 | 267.5 | 255.9 | 258.7 | 265.8 | 279.5 |
| Freezing point/. degree.C | -60.7 | -61.5 | -66.8 | -65.0 | -60.5 | -53.1 |
As can be seen from the experimental results in Table 4, the aviation kerosene product obtained by the hydrocracking method for producing aviation kerosene of the present invention simultaneously satisfies the performance index requirements of high aromatic content, low density and low end point, and can obtain aviation kerosene with higher quality than the national standard.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A hydrocracking process for producing aviation kerosene, the process comprising:
1) in the presence of hydrogen, raw oil sequentially flows through a hydrofining reaction zone containing a hydrofining catalyst and a hydrocracking reaction zone containing a hydrocracking catalyst and a post-refining catalyst to perform contact reaction, and a liquid-phase product obtained in the hydrocracking reaction zone is fractionated to obtain a naphtha fraction, a kerosene fraction, a diesel fraction and a tail oil fraction;
2) carrying out gas-liquid separation on the kerosene fraction obtained in the step 1) to respectively obtain a gas phase which can be recycled to the step 1) for fractionation and a liquid phase which is taken as a aviation kerosene product and is discharged from a device;
wherein, in the step 1), the conditions of the hydrocracking reaction zone are controlled, so that the conversion rate of distillate oil with the temperature of more than 350 ℃ in the raw oil is 65-88%.
2. The process of claim 1, wherein in step 1), the conditions of the hydrocracking reaction zone are controlled so that the conversion of distillate oil in the feed oil is 68-85% at > 350 ℃.
3. The process of claim 1 or 2, wherein in step 1), the reaction conditions of the hydrofinishing reaction zone comprise: the reaction temperature is 375-385 ℃, the hydrogen partial pressure is 12-13MPa, and the volume ratio of hydrogen to oil is (900-1200): 1, the volume space velocity is 0.7-1h-1。
4. The process of any one of claims 1-3, wherein in step 1), the reaction conditions of the hydrocracking reaction zone comprise: the reaction temperature is 370-390 ℃, the hydrogen partial pressure is 12-13MPa, and the volume ratio of hydrogen to oil is (900-1200): 1, the volume space velocity is 1-1.4h-1。
5. Process according to any one of claims 1-4, wherein in step 1) the fractionation is performed in a fractionation column wherein the side draw start temperature of the oil fraction is 170-.
6. The process as claimed in any one of claims 1 to 5, wherein, in step 1), the overhead pressure of the fractionation column is 0.06 to 0.08MPa, and the overhead temperature of the fractionation column is 115-120 ℃;
preferably, the ratio of the flow rate of the liquid-phase product obtained from the bottom of the low-pressure separator to the processing amount is controlled to be 18-38 wt%;
preferably, the temperature of the aviation kerosene extraction of the fractionating tower is controlled between 170 ℃ and 185 ℃.
7. The process according to any one of claims 1 to 6, wherein the hydrocracking catalyst in the hydrocracking reaction zone contains a carrier selected from at least one of alumina, amorphous silica-alumina and zeolite and an active component element supported on the carrier; the active component elements are noble metal elements and/or non-noble metal elements; the non-noble metal elements are VIB group metal elements and/or VIII group metal elements;
preferably, in the hydrocracking catalyst, the VIB group metal element is Mo and/or W, and the VIII group metal element is Co and/or Ni; the noble metal element is Pt element and/or Pd element; the amorphous silica-alumina comprises silica and/or alumina.
8. The method of any of claims 1-7, wherein the method further comprises: according to the flowing direction of reactant flow, a high-pressure separator and a low-pressure separator are sequentially arranged between the hydrocracking reaction zone and the fractionating tower to carry out first gas-liquid separation; the liquid phase product obtained from the bottom of the low pressure separator is then introduced into a hydrogen sulfide stripper to remove hydrogen sulfide therefrom.
9. The process according to any one of claims 1 to 8, wherein the feedstock oil is selected from at least one of virgin wax oil, coker wax oil, catalytic diesel oil and coker diesel oil.
10. The method according to claim 9, wherein the raw oil is virgin wax oil and catalytic diesel oil, and the weight ratio of the virgin wax oil to the catalytic diesel oil is (6-8): 1.
11. the method according to claim 9, wherein the raw oil is straight-run wax oil and coker diesel oil, and the weight ratio of the straight-run wax oil to the coker diesel oil is (5.7-6.5): 1.
12. the process according to any one of claims 9 to 11, wherein the straight run waxy oil has a boiling range between 260 ℃ and 550 ℃, the catalytic diesel has a boiling range between 200 ℃ and 350 ℃, and the coker diesel has a boiling range between 200 ℃ and 370 ℃.
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| CN103013559A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Hydrocracking method for selective increasing of aviation kerosene yield |
| CN105542851A (en) * | 2014-10-29 | 2016-05-04 | 中国石油化工股份有限公司 | Aviation kerosene production method |
| CN107460003A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of method for being hydrocracked increasing of aviation kerosene yield |
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| CN103013559A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Hydrocracking method for selective increasing of aviation kerosene yield |
| CN105542851A (en) * | 2014-10-29 | 2016-05-04 | 中国石油化工股份有限公司 | Aviation kerosene production method |
| CN107460003A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of method for being hydrocracked increasing of aviation kerosene yield |
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