A production process and production system of aviation kerosene

Abstract

The application discloses a production process and a production system of aviation coal, and the aviation coal production system comprises a first hydrogenation reaction zone, a second hydrogenation reaction zone, a first gas-liquid separator, a second gas-liquid separator, a first fractional distillation column, a second fractional distillation column and a mixing unit. The application also provides an aviation coal production process using the aviation coal production system, and the process can obtain ideal aviation coal products with qualified indexes and improve the product yield by using part of streams obtained by dividing the coal tar fraction after moderate hydrorefining treatment as the high specific gravity aviation coal component.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coal tar processing, and particularly relates to a method for producing aviation kerosene from coal tar. BACKGROUND

[0002] High-density aviation kerosene is a kind of fuel with high density (generally 0.835 g / cm 3 above) and high volumetric heat value (generally 35.8 MJ / m 3 above). Compared with ordinary aviation kerosene (density 0.77-0.81 g / cm 3 ), high-density aviation kerosene can increase the heat value per unit volume of fuel, and effectively increase the energy carried by the fuel tank of a spacecraft when the volume of the fuel tank is constant, which is an important guarantee for high-speed and long-range flight of the spacecraft. For example, compared with fuel with a density of 780 kg / m 3 (volumetric heat value about 33 x 10 3 MJ / m 3 ), fuel with a density of 840 kg / m 3 (volumetric heat value about 36 x 10 3 MJ / m 3 ) can carry about 8% more energy under the same fuel volume condition. Therefore, developing a high-density aviation kerosene production process has become one of the hot research directions in the field.

[0003] CN102304387A discloses a production method of coal-based high-density jet fuel, which comprises the following steps: coal liquefaction light oil and liquefaction distillate oil from a coal direct liquefaction process enter an expanded bed hydroprocessing reactor with forced internal circulation, and are contacted with hydrogen and a hydroprocessing catalyst; the outlet stream of the expanded bed hydroprocessing reactor is separated and fractionated to obtain light distillate oil, medium distillate oil and heavy distillate oil; the light distillate oil and the medium distillate oil are mixed and then enter a deep hydrofining fixed bed reactor, and are contacted with hydrogen and a hydrofining catalyst for reaction; the outlet stream of the deep hydrofining fixed bed reactor is separated and fractionated to obtain high-density jet fuel; wherein a liquid collection cup is arranged at the upper part of the hydroprocessing reactor, and the collected liquid is transported through a pipeline and is sent to the bottom of the hydroprocessing reactor after being pressurized by a forced circulation pump. The method of the present application uses an expanded bed reactor with forced internal circulation, and the liquid in the collection cup at the upper part of the reactor needs to be returned to the reactor for further hydroprocessing by a forced circulation pump, which accordingly increases the device investment and energy consumption. Moreover, the method of the present application uses two sets of separation and fractionation systems, and the operation process is complex, the device investment and operation cost are high, and the atmospheric distillation range index does not meet the GJB1603 high-density jet fuel standard.

[0004] CN107057779A discloses a high-density jet fuel, comprising RP-3 jet fuel and a high-density fuel blending component, wherein the high-density fuel blending component is obtained by hydrorefining inferior heavy oil, and the distillation range of the high-density fuel blending component is 180-300℃, and the high-density fuel blending component is composed of naphthenes and aromatics and tail oil. The physicochemical properties of the high-density fuel blending component meet the standard of No. 3 jet fuel. Although the density of the obtained jet fuel reaches 960-980 kg / m 3 , the distillation range and the content of aromatics of the jet fuel do not meet the standard of GJB1603 high-density jet fuel.

[0005] US4401837 discloses a method for producing high-density fuel, which mainly comprises thermal polymerization of bridged dicyclopentadiene, separation of the trimer fraction from the thermal polymerization product, and then hydrogenation and isomerization of the trimer fraction. The method has a complex process flow and high cost of raw materials.

[0006] CN105694970A discloses a method for producing high-density jet fuel by hydrogenation of low-temperature coal tar, which comprises mixing and heating low-temperature coal tar and hydrogen, and then passing the mixture through a hydrogenation protection catalyst and a hydrogenation refining catalyst in sequence to perform hydrogenation reaction. The hydrogenation product is fractionated to obtain naphtha, crude jet fuel and tail oil, and the crude jet fuel is refined by clay to obtain high-density No. 6 jet fuel. Although the method has a relatively simple process flow, the method needs to use 8wt% of clay for refining, and the refined clay is solid waste which is difficult to regenerate at present. The clay solid waste is generally treated by incineration and landfill, which causes great damage to the environment, and it is difficult to carry out industrial production under the current increasingly stringent environmental requirements.

[0007] According to the above analysis, the existing process route for producing high-density aviation kerosene has defects such as complex process route, unsatisfied product properties, great influence on the environment, etc. SUMMARY

[0008] In the research process of the production process of high specific gravity aviation kerosene, it is found that the high specific gravity aviation kerosene needs to control many indexes, such as density, freezing point, aromatic hydrocarbon content, sulfur content, viscosity and the like, and the indexes are associated with each other, influence each other, and some indexes are incompatible. In addition, compared with ordinary No. 3 aviation kerosene, the distillation range of the high specific gravity aviation kerosene is narrower, and the initial boiling point temperature is higher, so it is more difficult to balance the indexes. If only the density is adjusted, many operation modes can be realized, but when the density is adjusted, the smoke point, freezing point, product composition, and weight heat value are affected to different degrees. Among these contradictions, the density, freezing point, smoke point and aromatic hydrocarbon composition are the main contradictions. The goal pursued in the field is to obtain ideal high specific gravity aviation kerosene products with all indexes qualified. The technical scheme of the present application is proposed based on solving the above technical problems. The coal tar fraction after moderate hydrofining treatment is divided, and the distillation fraction after the division is mixed with another part of the fraction after the hydro-upgrading treatment to obtain the high specific gravity aviation kerosene. The product yield is improved while meeting the various indexes of the high specific gravity aviation kerosene.

[0009] The present application aims to overcome the technical problems of the existing production method of high specific gravity aviation kerosene, such as high equipment requirement, complex process flow, low density, unqualified product freezing point, and low product yield. The present application provides an aviation kerosene production process and a production system. The production process is simple, and the device does not need to be greatly changed. The high-quality aviation kerosene product meeting the GJB1603 No. 6 jet fuel standard can be obtained from the full distillation coal tar and other poor raw materials relying on the existing production device. The density can reach 0.840 g / cm 3 The freezing point is less than -50℃.

[0010] The present application provides an aviation kerosene production process, which comprises the following steps:

[0011] (1) The coal tar raw material and hydrogen enter the first hydrogenation reaction zone to react under the contact condition;

[0012] (2) The reaction effluent obtained in the first hydrogenation reaction zone in step (1) is separated to obtain gas, a first liquid phase stream, a second liquid phase stream and a third liquid phase stream;

[0013] (3) The third liquid phase stream obtained in step (2) and hydrogen enter the second hydrogenation reaction zone to react;

[0014] (4) The reaction effluent obtained in the second hydrogenation reaction zone in step (3) is separated to obtain gas, a first liquid phase stream, a second liquid phase stream and a third liquid phase stream;

[0015] (5) The 102 liquid phase stream obtained in step (2) and the 202 liquid phase stream obtained in step (4) are mixed to obtain a jet fuel product.

[0016] Further, in the above jet fuel production process, as a specific embodiment, the coal tar raw material can be selected from one or more of low-temperature coal tar, medium-low-temperature coal tar, medium-temperature coal tar, and high-temperature coal tar, or can be mixed with anthracene oil, and specifically can be a mixture of one or more of low-temperature coal tar, medium-low-temperature coal tar, medium-temperature coal tar, and high-temperature coal tar and anthracene oil.

[0017] Further, in the above jet fuel production process, as a specific embodiment, the coal tar raw material in step (1) is preferably first subjected to a dehydration and mechanical impurity removal treatment, and the treated coal tar raw material has a water content of not more than 0.15wt%, a metal content of not more than 20μg / g, and an ash content of not more than 0.01wt%.

[0018] Further, in the above jet fuel production process, as a specific embodiment, the first hydrogenation reaction zone in step (1) is provided with at least one hydrogenation reactor, which can be selected from at least one of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

[0019] Further, in the above jet fuel production process, as a specific embodiment, the first hydrogenation reaction zone is loaded with a hydrogenation guard catalyst and a hydrogenation refining catalyst, and preferably the hydrogenation guard catalyst and the hydrogenation refining catalyst are loaded in sequence in the direction of flow of the liquid phase material, and further, the ratio of the hydrogenation guard catalyst to the hydrogenation refining catalyst is 5:60-75:90 based on the loading volume ratio.

[0020] Further, in the above jet fuel production process, as a specific embodiment, the hydrogenation guard catalyst can be a commercially available hydrogenation guard catalyst or can be produced according to the method disclosed in the prior art. For example, the FZC series hydrogenation guard catalyst developed and produced by SINOPEC (Dalian) Petroleum Chemical Research Institute (FRIPP) can be used. The hydrogenation guard catalyst generally uses a porous refractory inorganic oxide (such as alumina) as a carrier, oxides of metals of Group VIB and / or Group VIII such as W, Mo, Co, and Ni as active components, and can optionally add other various additives such as P, Si, F, B, etc. The hydrogenation guard catalyst is generally subjected to a pre-sulfidation treatment before use to ensure that the hydrogenation active metals are in a sulfidized state during the reaction.

[0021] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the hydrofining catalyst in step (1) refers to a single catalyst or a series of catalysts with the functions of hydrodemetallization, hydrodesulfurization, hydrodeoxygenation, hydrodenitrogenation, etc. Generally, the hydrofining catalyst comprises a carrier and a hydrogenation metal component, and contains, based on the weight of the catalyst, 10wt%-35wt% of active metal components of Group VIB in the periodic table, such as W and / or Mo, preferably 15wt%-30wt%, and 1wt%-7wt% of metal oxides of Group VIII, such as Co and / or Ni, preferably 1.5wt%-6wt%, based on the weight of the catalyst. The catalyst should be sulfided before use to ensure that the hydrogenation active metal is in a sulfided state during the reaction. The carrier is generally an inorganic refractory oxide, which can be one or more of alumina, amorphous silica-alumina, silica, titania, etc. The hydrofining catalyst can be a commercially available catalyst in the art, or can be prepared according to general knowledge in the art. The commercially available catalysts that can be selected include 3936, 3996, FF-16, FF-22, FF-26, etc. hydrofining catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute (FRIPP).

[0022] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the operating conditions of the first hydrogenation reaction zone in step (1) are as follows: the reaction pressure is 5.0-20.0 MPa, preferably 12.0-15.0 MPa; the reaction temperature is 250-420℃, preferably 330-400℃; the hydrogen / oil volume ratio is 500:1-1500:1, preferably 800:1-1200:1; and the volume space velocity is 0.1-1.2 h -1 , preferably 0.3-0.7 h -1 .

[0023] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the cutting temperatures of the 101st liquid phase stream and the 102nd liquid phase stream in step (2) are 195-210℃, preferably 195-200℃; and the cutting temperatures of the 102nd liquid phase stream and the 103rd liquid phase stream are 205-220℃, preferably 205-215℃. After using the above-mentioned cutting scheme, the initial boiling point of the 102nd liquid phase stream is 195-210℃, preferably 195-200℃; and the final boiling point is 205-220℃, preferably 205-215℃.

[0024] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the second hydrogenation reaction zone in step (3) is provided with at least one hydrogenation reactor, which can be selected from at least one of a fixed-bed hydrogenation reactor, a boiling-bed hydrogenation reactor, and a suspended-bed hydrogenation reactor.

[0025] Further, in the above-mentioned production process of marine fuel oil, as a specific embodiment, the second hydrogenation reaction zone in step (3) is loaded with a hydro-upgrading catalyst, preferably a hydro-upgrading catalyst containing amorphous silica-alumina and modified Y zeolite. Further, the hydro-upgrading catalyst contains 20wt%-60wt% amorphous silica-alumina, 5wt%-25wt% modified Y zeolite, 10wt%-30wt% Group VIB metal (calculated as oxide), and 4wt%-10wt% Group VIII metal (calculated as oxide), and the catalyst should be pre-sulfided before use to ensure that the hydrogenation active metals are in a sulfided state during the reaction. The hydro-upgrading catalyst can also contain components such as alumina, zirconia, titania, etc. The specific surface area of the hydro-upgrading catalyst is 220-300m 2 / g, the pore volume is 0.3-0.6mL / g, the pore volume of pores with a diameter of 3-10nm accounts for 75%-95% of the total pore volume, preferably 85%-95%, and the infrared acidity is 0.3-0.5mmol / g. The hydro-upgrading catalyst can be selected from ordinary commercial catalysts in the field or prepared according to general knowledge in the field. Commercial catalysts that can be selected include 3824, 3903, 3971, 3976, FC-12, FC-28, FC-32, FC-36, FC-46, FC-50, FC-60, FC-66, FC-76, etc. hydro-upgrading catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute Co., Ltd.

[0026] Further, in the above-mentioned production process of marine fuel oil, as a specific embodiment, the second hydrogenation reaction zone in step (3) is also loaded with a hydro-upgrading pre-refining catalyst, which is mainly used for denitrification and saturation of polycyclic aromatic hydrocarbons, better plays the ring-opening performance of the hydro-upgrading catalyst, reduces the deactivation rate of the hydro-upgrading catalyst, and prolongs the operation cycle of the entire device. According to the flow direction of the liquid phase material, the hydro-upgrading pre-refining catalyst is arranged above the hydro-upgrading catalyst, and the loading volume ratio of the hydro-upgrading pre-refining catalyst to the hydro-upgrading catalyst is 5:75-60:40.

[0027] Further, in the above-mentioned production process of marine fuel oil, as a specific embodiment, the second hydrogenation reaction zone in step (3) is also loaded with a supplemental hydrofining catalyst, which is mainly used for saturated hydro-upgrading catalyst ring-opening and chain-breaking by-produced part of the olefins, and improves the quality of the oil produced in the upgrading reaction zone. According to the flow direction of the liquid phase material, the supplemental hydrofining catalyst is arranged in the lower part of the hydro-upgrading catalyst, and the loading volume ratio of the hydro-upgrading catalyst to the supplemental hydrofining catalyst is 25:50-100:5.

[0028] Further, in the above-mentioned production process of marine gas oil, as a specific embodiment, the hydrogenation modification pre-refining catalyst in the upper part of the second hydrogenation reaction zone and the make-up hydrofining catalyst in the bottom part of the second hydrogenation reaction zone generally comprise a carrier and a hydrogenation metal component, and based on the weight of the catalyst, comprise an active metal component in Group VIB of the Periodic Table, such as W and Mo, in the form of metal oxides, at 10 wt% to 40 wt%, preferably 15 wt% to 35 wt%; and a metal oxide in Group VIII, such as Co and Ni, in the form of metal oxides, at 1 wt% to 10 wt%, preferably 1.5 wt% to 8 wt%. The catalysts should be pre-sulfurized before use to ensure that the hydrogenation active metals are in the sulfidized state during the reaction. The carrier used in the hydrofining catalyst is an inorganic refractory oxide, such as alumina, amorphous silica-alumina, silicon oxide, titanium oxide, etc. The hydrogenation modification pre-refining catalyst and the make-up hydrofining catalyst can be selected from ordinary commercial catalysts in the field or can be prepared according to general knowledge in the field. Commercial catalysts that can be selected include FF-66 and FF-76 hydrofining catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute Co., Ltd.

[0029] Further, in the above-mentioned production process of marine gas oil, as a specific embodiment, the operating conditions of the hydrogenation modification reaction zone in step (3) are as follows: the reaction pressure is 5.0 to 20.0 MPa, preferably 12.0 to 15.0 MPa; the reaction temperature is 250 to 420°C, preferably 330 to 380°C; the hydrogen / oil volume ratio is 500:1 to 1500:1, preferably 800:1 to 1200:1; and the volume space velocity is 0.1 to 1.5 h -1 , preferably 0.4 to 1.2 h -1 .

[0030] Further, in the above-mentioned production process of marine gas oil, as a specific embodiment, the 101 liquid phase stream in step (2) enters the second hydrogenation reaction zone for treatment, and is preferably introduced through an inlet in the upper reactor shell of the hydrogenation modification catalyst bed in the second hydrogenation reaction zone. When the hydrogenation modification catalyst is arranged in multiple layers, the 101 liquid phase stream can also be divided into multiple streams for introduction into the second hydrogenation reaction zone.

[0031] Further, in the above-mentioned production process of marine gas oil, as a specific embodiment, the cutting temperature of the 201 liquid phase stream and the 202 liquid phase stream in step (4) is 195 to 210°C, preferably 195 to 200°C; and the cutting temperature of the 202 liquid phase stream and the 203 liquid phase stream is 250 to 315°C, preferably 260 to 290°C.

[0032] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the 201 liquid phase stream obtained in step (4) can be used as a gasoline blending component, or the 201 liquid phase stream is subjected to fraction cutting to obtain light components and heavy components, and the cutting temperature point is any one of 130-145℃, the light components after cutting can be used as catalytic reforming raw materials, and the heavy components after cutting can be used as high-quality No. 3 jet fuel blending components.

[0033] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the 203 liquid phase stream in step (4) can be selected from one or more of the following treatment modes: being recycled back to the first hydrogenation reaction zone for treatment, being recycled back to the second hydrogenation reaction zone for treatment, and being discharged as a diesel blending component; when part of it is discharged, the amount of the discharged 203 liquid phase stream can be dynamically adjusted according to the load of the entire reaction system.

[0034] The second aspect of the present application provides an aviation kerosene production system, which comprises:

[0035] a first hydrogenation reaction zone for receiving a coal tar raw material and hydrogen, the coal tar raw material and hydrogen entering the first hydrogenation reaction zone to react with a hydrogenation protection catalyst and a hydrofining catalyst;

[0036] a first gas-liquid separator for receiving a reaction effluent obtained from the first hydrogenation reaction zone, and obtaining a first gas and a first liquid phase stream after separation;

[0037] a first fractionating column for receiving the first liquid phase stream from the first gas-liquid separator, and obtaining a 101 liquid phase stream, a 102 liquid phase stream and a 103 liquid phase stream after separation;

[0038] a second hydrogenation reaction zone for receiving the 103 liquid phase stream from the first fractionating column and hydrogen, the 103 liquid phase stream and hydrogen entering the second hydrogenation reaction zone to react with a hydro-upgrading catalyst therein;

[0039] a second gas-liquid separator for receiving a reaction effluent obtained from the second hydrogenation reaction zone, and obtaining a second gas and a second liquid phase stream after separation;

[0040] a second fractionating column for receiving the second liquid phase stream from the second gas-liquid separator, and obtaining a 201 liquid phase stream, a 202 liquid phase stream and a 203 liquid phase stream after separation;

[0041] a mixing unit for receiving the 102 liquid phase stream from the first fractionating column and the 202 liquid phase stream from the second fractionating column, and obtaining an aviation kerosene product after mixing.

[0042] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the first 101 liquid phase stream is communicated with the second hydrogenation reaction zone through a pipeline.

[0043] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the first 201 liquid phase stream can be discharged as a gasoline blending component, or the first 201 liquid phase stream is subjected to fraction cutting to obtain light components and heavy components, and the cutting temperature point is any one of 130-145 DEG C; the cut light components can be used as catalytic reforming raw materials, and the cut heavy components can be used as high-quality No. 3 jet fuel blending components.

[0044] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the first 203 liquid phase stream can be communicated with the first hydrogenation reaction zone and the second hydrogenation reaction zone through a pipeline, respectively; the first 203 liquid phase stream can be subjected to any one or more of the following treatments: being circulated back to the first hydrogenation reaction zone for treatment, being circulated back to the second hydrogenation reaction zone for treatment, and being discharged as a diesel blending component; when part of the first 203 liquid phase stream is discharged, the amount of the discharged first 203 liquid phase stream can be dynamically adjusted according to the load of the entire reaction system.

[0045] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the first hydrogenation reaction zone is provided with at least one hydrogenation reactor, and the hydrogenation reactor can be selected from at least one of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

[0046] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the second hydrogenation reaction zone is provided with at least one hydrogenation reactor, and the hydrogenation reactor can be selected from at least one of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

[0047] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the first gas-liquid separator and the second gas-liquid separator are any one of devices capable of realizing gas-liquid two-phase separation function. Those skilled in the art can select according to actual needs and knowledge.

[0048] Further, in the above-mentioned aviation kerosene production system, as a specific embodiment, the first fractionating column and the second fractionating column can be any one of existing fractionating columns in the art, such as a packed column and a tray column.

[0049] Compared with the prior art, the aviation kerosene production process and production system provided by the present application have the following technical effects and advantages:

[0050] The application provides a production process of marine coal, which comprises the following steps: subjecting full-range coal tar to moderate hydrorefining treatment, and then subjecting a 102 liquid phase stream obtained by fractionation to mixing with a 202 liquid phase stream obtained by subsequent hydro-upgrading treatment to obtain a high-specific-gravity marine coal product. The 102 liquid phase stream contains a large amount of naphthenes and monocyclic aromatic compounds, and the mixing with the 202 liquid phase stream can obviously improve the density of the high-specific-gravity marine coal, so that the index of the high-specific-gravity marine coal can reach 0.840 g / cm 3 At the same time, the freezing point of the high-specific-gravity marine coal fraction can be obviously reduced, so that the index of the high-specific-gravity marine coal is less than -50 ℃, and the problem that the important indexes of the high-specific-gravity marine coal are incompatible is solved. At the same time, the refined coal tar fraction is cut, the 102 liquid phase stream does not enter the hydro-upgrading reaction zone for hydrogenation treatment, and the problem of excessive hydrogenation and the consequent advance of the distillation range in the subsequent hydro-upgrading treatment can be avoided, so that the yield of the high-specific-gravity marine coal fraction can be improved. In the method, the 101 liquid phase stream enters the second hydrogenation reaction zone, on the one hand, the properties of the product can be further improved, and on the other hand, the temperature of the second hydrogenation reaction zone can be effectively controlled, so that the operation flexibility of the second hydrogenation reaction zone and the service life of the catalyst can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 is a schematic diagram of a production process and a production system of marine coal of the application;

[0052] Among them,

[0053] 1: coal tar raw material 2: first circulating hydrogen

[0054] 3: new hydrogen 4: first hydrogenation reaction zone

[0055] 5: first hydrogenation reaction zone effluent 6: first gas-liquid separator

[0056] 7: first gas 8: first purification unit

[0057] 9: first purified hydrogen 10: first liquid phase stream

[0058] 11: first fractionating column 12: 101 liquid phase stream

[0059] 13: 102 liquid phase stream 14: 103 liquid phase stream

[0060] 15: second circulating hydrogen 16: second hydrogenation reaction zone

[0061] 17: second hydrogenation reaction zone effluent 18: second gas-liquid separator

[0062] 19: second gas 20: second purification unit

[0063] 21: second purified hydrogen 22: second liquid phase stream

[0064] 23: second fractionation column 24: 201st liquid phase stream

[0065] 25: 202nd liquid phase stream 26: 203rd liquid phase stream

[0066] 27: mixing unit 28: heavy naphtha product DETAILED DESCRIPTION

[0067] The technical features of the present application will be further described below by specific examples in conjunction with the accompanying drawings, but these examples cannot limit the present application.

[0068] Unless otherwise clearly indicated, throughout the specification and claims, the terms "comprise" or variations such as "comprises" or "comprising" will be understood to imply the inclusion of a stated element or group of elements but not the exclusion of any other element or group of elements.

[0069] In this document, spatially relative terms, such as "beneath", "below", "lower", "above", "upper", "on", "directly on", "indirectly on", and the like, can be used to describe one element's or feature's relationship to another element or feature as illustrated in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientations depicted in the figures. For example, if the device in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the exemplary term "below" can encompass both an orientation of above and below. The device can be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

[0070] In this document, the terms "first", "second", etc. are used to distinguish between two different elements or portions, and are not used to define a particular position or relative relationship. In other words, in some embodiments, the terms "first", "second", etc. can be interchanged with each other.

[0071] In this document, all numerical values of parameters (e.g., quantities or conditions) should be understood to be modified in all instances by the term "about" unless otherwise indicated in the specific context.

[0072] In this document, the naphtha yield is the weight percentage of the heavy naphtha product to the raw oil.

[0073] In this article, the various catalysts involved can be selected from commercial catalysts according to their properties, or can be prepared according to the knowledge in the art. The hydrogenation protection catalyst can be selected from FZC-100, FZC-102A, FZC-103 hydrogenation protection catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute Co., Ltd.; the hydrofining catalyst can be selected from 3936, 3996, FF-16, FF-22, FF-26, etc. hydrofining catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute Co., Ltd.; the hydro-upgrading pre-fining catalyst in the upper part of the hydro-upgrading reaction zone and the supplemental hydrofining catalyst in the lower part can be selected from FF-66, FF-76, etc. hydrofining catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute Co., Ltd.; the hydro-upgrading catalyst can be selected from 3824, 3903, 3971, 3976, FC-12, FC-28, FC-32, FC-36, FC-46, FC-50, FC-60, FC-66, FC-76, etc. hydro-upgrading catalysts developed and produced by Sinopec (Dalian) Petroleum Chemical Research Institute Co., Ltd.

[0074] As Figure 1As shown, the coal tar feed 1 after dewatering and removal of impurities is mixed with fresh hydrogen 3 to obtain the hydrogenation feed of the first hydrogenation reaction zone, which enters the first hydrogenation reaction zone 4 and is in contact with the catalyst therein to perform hydrogenation reaction, and the first hydrogenation reaction zone effluent 5 obtained is separated in the first gas-liquid separator 6, and the first gas 7 and the first liquid phase stream 10 are obtained by separation; the first gas 7 enters the first purification unit 8 to remove impurities (such as hydrogen sulfide, non-condensable gas, etc.) therein, and the first purified hydrogen after removal of impurities is mixed with fresh hydrogen 3 to return to the first hydrogenation reaction zone 4 as the first recycle hydrogen 2. The first liquid phase stream 10 obtained by separation enters the first fractionation column 11, and after fractionation, the 101st liquid phase stream 12, the 102nd liquid phase stream 13 and the 103rd liquid phase stream 14 are obtained, wherein the 101st liquid phase stream 12 and the 103rd liquid phase stream 14 are mixed with fresh hydrogen 3 and then enter the second hydrogenation reaction zone 16 to be in contact with the catalyst therein to perform hydro-upgrading reaction, wherein the 101st liquid phase stream 12 enters the second hydrogenation reaction zone 16 through the feed port on the reactor shell above the hydrogenation-upgrading catalyst bed in the second hydrogenation reaction zone; the second hydrogenation reaction zone effluent 17 obtained by reaction enters the second gas-liquid separator 18 to be separated, and the second gas 19 and the second liquid phase stream 22 are obtained by separation; wherein the second gas 19 enters the second purification unit 20 to remove impurities therein, and the second purified hydrogen 21 after removal of impurities is mixed with fresh hydrogen 3 to enter the second hydrogenation reaction zone 16 as the second recycle hydrogen 15, and the second liquid phase stream 22 separated is introduced into the second fractionation column 23, and after fractionation, the 201st liquid phase stream 24, the 202nd liquid phase stream 25 and the 203rd liquid phase stream 26 are obtained, and the 202nd liquid phase stream 25 and the 102nd liquid phase stream 12 are mixed in the mixing unit 27 to obtain the heavy coal product 28 with large specific gravity. The 203rd liquid phase stream 26 can be divided into multiple streams, one of which is used as a product, and one of which is recycled back to the first hydrogenation reaction zone and / or the second hydrogenation reaction zone.

[0075] In the present text, the coal tar feed used includes two kinds, and the specific feed properties are shown in Table 1.

[0076] Table 1 Coal tar feed properties

[0077]

[0078]

[0079] Example 1

[0080] The feed A is used as the raw material, and the feed properties are shown in Table 1. The hydrogenation process is as follows: Figure 1The production process flow is as follows: the 101st liquid phase feed stream entirely enters the second hydrogenation reaction zone, while the 203rd feed stream is recycled back to the second hydrogenation reaction zone at a ratio of 1:1 to the external flow. The first hydrogenation reaction zone is filled with hydrogenation protection agent FZC-103 and hydrogenation refining catalyst FF-22, with a volume ratio of 1:5. The 102nd liquid phase feed stream has a boiling range of 195–210℃, and its properties are shown in Table 2. The second hydrogenation reaction zone is filled sequentially according to the liquid phase feed flow direction with FF-66 hydrogenation pre-refining catalyst, FC-50 hydrogenation catalyst, and FF-76 supplementary refining catalyst, with a volume ratio of 2:10:1. The 202nd liquid phase feed stream has a boiling range of 195–280℃. The hydrogenation process conditions for the first and second hydrogenation reaction zones are shown in Table 3, and the reaction results are shown in Table 5.

[0081] Example 2

[0082] Raw material B was used as the raw material, and its properties are shown in Table 1. [The following is a description of the process:] ...using... Figure 1 The production process flow is as follows: the 101st liquid phase stream entirely enters the second hydrogenation reaction zone, and the 203rd stream entirely recycles back to the second hydrogenation reaction zone. The first hydrogenation reaction zone is filled with hydrogenation protection agent FZC-103 and hydrogenation refining catalyst FF-22, with a volume ratio of 1:6. The 102nd liquid phase stream has a boiling range of 200–215°C, and its properties are shown in Table 2. The second hydrogenation reaction zone is filled sequentially according to the liquid phase flow direction with FF-66 hydrogenation pre-refining catalyst, FC-50 hydrogenation catalyst, and FF-76 supplementary refining catalyst, with a volume ratio of 1:10:1. The 202nd liquid phase stream has a boiling range of 200–275°C. The hydrogenation process conditions for the first and second hydrogenation reaction zones are shown in Table 3, and the reaction results are shown in Table 5.

[0083] Example 3

[0084] The process is basically the same as in Example 1, except that the hydrogenation process conditions in the first hydrogenation reaction zone and the second hydrogenation reaction zone are different. The hydrogenation process conditions in the first hydrogenation reaction zone and the second hydrogenation reaction zone are shown in Table 3, and the reaction results are shown in Table 5.

[0085] Example 4

[0086] The process is basically the same as in Example 1, except that the 101st liquid phase feed stream does not enter the second hydrogenation reaction zone. The hydrogenation process conditions of the first and second hydrogenation reaction zones are shown in Table 3, and the reaction results are shown in Table 5.

[0087] Comparative Example 1

[0088] The same as example 1 except that the first liquid phase stream in Comparative Example 1 was divided into two liquid phase streams, a first stream and a second stream, after fractionation, wherein the distillation range of the first stream was equivalent to the 101st liquid phase stream in example 1 and the second stream was fed into the second hydrogenation reaction zone. The hydrogenation process conditions of the first hydrogenation reaction zone and the second hydrogenation reaction zone were shown in Table 4 and the reaction results were shown in Table 6.

[0089] Comparative Example 2

[0090] The same as example 2 except that the first liquid phase stream in Comparative Example 2 was divided into two liquid phase streams, a first stream and a second stream, after fractionation, wherein the distillation range of the first stream was equivalent to the 101st liquid phase stream in example 2 and the second stream was fed into the second hydrogenation reaction zone. The hydrogenation process conditions of the first hydrogenation reaction zone and the second hydrogenation reaction zone were shown in Table 4 and the reaction results were shown in Table 6.

[0091] Comparative Example 3

[0092] The same as example 1 except that the first liquid phase stream in Comparative Example 3 was directly fed into the second hydrogenation reaction zone without fractionation. The hydrogenation process conditions of the first hydrogenation reaction zone and the second hydrogenation reaction zone were shown in Table 4 and the reaction results were shown in Table 6.

[0093] Table 2 Properties of the 102nd liquid phase stream obtained in Examples 1-4

[0094]

[0095]

[0096] Table 3 Hydrogenation process conditions of Examples 1-4

[0097] Test No. Example 1 Example 2 Example 3 Example 4 First hydrogenation reaction zone Reaction pressure, MPa 15.0 15.0 12.0 15.0 Reaction temperature, °C 360 340 390 360 volume space velocity, h -1 ]]> 0.45 0.30 0.7 0.45 Hydrogen to oil volume ratio 1000 800 1200 1000 Second hydrogenation reaction zone Reaction pressure, MPa 15.0 15.0 12.0 15.0 Reaction temperature, °C 360 340 380 360 volume space velocity, h -1 ]] 0.8 0.4 1.2 0.8 Hydrogen to oil volume ratio 1000 800 1200 1000

[0098] Table 4 Hydrogenation process conditions of Comparative Examples 1-3

[0099]

[0100]

[0101] Table 5 Reaction results of Examples 1-4

[0102]

[0103]

[0104] Table 6 Reaction results of Comparative Examples 1-3

[0105] Test No. Comparative Example 1 Comparative Example 2 Comparative Example 3 Density (20°C), g-cm -3 ]] 0.829 0.830 0.828 Distillation range (ASTM D86), °C IBP / 10% 195 / 211 200 / 211 195 / 210 30％ / 50％ 222 / 237 222 / 233 221 / 235 70％ / 90％ 248 / 260 248 / 255 246 / 260 95% / FBP 267 / 280 265 / 275 265 / 280 2 -1 ]]> ​​ 2.779 2.732 2.744 2 ·s -1 ]]> ​ 20.73 20.88 20.62 Freezing point / °C -45 -46 -43 Flash point (closed cup) / °C 82 81 83 Marine gas oil yield, wt% 47.2 43.6 47.7

[0106] It can be seen from the product properties of Example 1 and Comparative Example 1 that the large specific gravity aviation kerosene prepared without separating the large specific gravity kerosene refined light component after hydrofining of the raw material cannot meet the requirements of the GJB1603 No. 6 jet fuel standard.

[0107] It can be seen from the product properties of the aviation kerosene obtained by the example that the density of the large specific gravity aviation kerosene produced by the method reaches 0.840 g / cm 3 The above, and the freezing point is less than -50℃, meets the requirements of the GJB1603 No. 6 jet fuel standard. And can expand the raw material source of large specific gravity aviation kerosene, also enriches the deep utilization of coal tar resources, has great economic benefit and social benefit.

Claims

1. A process for producing marine gas oil, the process comprising the following steps: (1) under contact conditions, a coal tar feedstock and hydrogen are introduced into a first hydrogenation reaction zone for reaction; the first hydrogenation reaction zone is packed with a hydrogenation guard catalyst and a hydrofining catalyst, the hydrogenation guard catalyst and the hydrofining catalyst are sequentially packed in the order of liquid phase material flow direction, and the ratio of the hydrogenation guard catalyst to the hydrofining catalyst is 5:60-75:90 based on the volume ratio of packing; (2) the reaction effluent obtained in the first hydrogenation reaction zone in step (1) is separated to obtain a gas, a first 101 liquid phase stream, a second 102 liquid phase stream and a third 103 liquid phase stream; the cutting temperature of the first 101 liquid phase stream and the second 102 liquid phase stream is 195-210°C, and the cutting temperature of the second 102 liquid phase stream and the third 103 liquid phase stream is 205-220°C; (3) the third 103 liquid phase stream obtained in step (2) and hydrogen are introduced into a second hydrogenation reaction zone for reaction; the second hydrogenation reaction zone is packed with a hydro-upgrading catalyst, and the hydro-upgrading catalyst comprises amorphous silicon aluminum and modified Y zeolite; the second hydrogenation reaction zone is packed with a hydro-upgrading pre-hydrofining catalyst, and the hydro-upgrading pre-hydrofining catalyst is arranged above the hydro-upgrading catalyst in the order of liquid phase material flow direction, and the volume ratio of the hydro-upgrading pre-hydrofining catalyst to the hydro-upgrading catalyst is 5:75-60:40; the second hydrogenation reaction zone is packed with a supplemental hydrofining catalyst, and the supplemental hydrofining catalyst is arranged below the hydro-upgrading catalyst in the order of liquid phase material flow direction, and the volume ratio of the hydro-upgrading catalyst to the supplemental hydrofining catalyst is 25:50-100:5; (4) the reaction effluent obtained in the second hydrogenation reaction zone in step (3) is separated to obtain a gas, a first 201 liquid phase stream, a second 202 liquid phase stream and a third 203 liquid phase stream; the cutting temperature of the first 201 liquid phase stream and the second 202 liquid phase stream is 195-210°C, and the cutting temperature of the second 202 liquid phase stream and the third 203 liquid phase stream is 250-315°C; (5) the second 102 liquid phase stream obtained in step (2) and the second 202 liquid phase stream obtained in step (4) are mixed to obtain a marine gas oil product.

2. The marine gas oil production process according to claim 1, characterized in that: The coal tar feedstock in step (1) is first subjected to dehydration and removal of mechanical impurities, and the treated coal tar feedstock has a water content of not more than 0.15wt%, a metal content of not more than 20ug / g and an ash content of not more than 0.01wt%.

3. The marine gas oil production process according to claim 1, characterized in that: The operating conditions of the first hydroprocessing reaction zone in step (1) are as follows: reaction pressure is 5.0-20.0 MPa, reaction temperature is 250-420°C, hydrogen / oil volume ratio is 500:1-1500:1, and volume space velocity is 0.1-1.2 h -1 .

4. The marine gas oil production process according to claim 1, characterized in that: The operating conditions of the first hydroprocessing reaction zone in step (1) are as follows: reaction pressure is 12.0-15.0 MPa, reaction temperature is 330-400°C, hydrogen / oil volume ratio is 800:1-1200:1, and volume space velocity is 0.3-0.7 h -1 .

5. The marine gas oil production process according to claim 1, characterized in that: The operating conditions of the hydro-upgrading reaction zone in step (3) are as follows: reaction pressure 5.0-20.0 MPa, reaction temperature 250-420°C, hydrogen / oil volume ratio 500:1-1500:1, and volume space velocity 0.1-1.5 h -1 .

6. The marine gas oil production process according to claim 1, characterized in that: The operating conditions of the hydro-upgrading reaction zone in step (3) are as follows: reaction pressure is 12.0-15.0 MPa; reaction temperature is 330-380°C; hydrogen / oil volume ratio is 800:1-1200:1; volume space velocity is 0.4-1.2 h -1 .

7. The marine gas oil production process according to claim 1, characterized in that: The first 101 liquid phase stream in step (2) is introduced into the second hydrogenation reaction zone for treatment.

8. The marine gas oil production process according to claim 1, characterized in that: The cutting temperature of the first 201 liquid phase stream and the second 202 liquid phase stream in step (4) is 195-200°C, and the cutting temperature of the second 202 liquid phase stream and the third 203 liquid phase stream is 260-290°C.

9. The marine gas oil production process according to claim 1, characterized in that: The third 203 liquid phase stream in step (4) is selected from one or more of the following treatment modes: recycling to the first hydrogenation reaction zone for treatment, recycling to the second hydrogenation reaction zone for treatment, and being discharged as a diesel blending component.

10. A marine gas oil production system for implementing the process of claim 1, the production system comprising: a first hydrogenation reaction zone for receiving the coal tar feedstock and hydrogen, the coal tar feedstock and hydrogen entering the first hydrogenation reaction zone and being reacted with a hydroprotection catalyst and a hydrofining catalyst; a first gas-liquid separator for receiving a reaction effluent from the first hydrogenation reaction zone, and separating the reaction effluent to obtain a first gas and a first liquid phase stream; a first fractionating column for receiving the first liquid phase stream from the first gas-liquid separator, and separating the first liquid phase stream to obtain a first 101 liquid phase stream, a first 102 liquid phase stream, and a first 103 liquid phase stream; a second hydrogenation reaction zone for receiving the first 103 liquid phase stream from the first fractionating column and hydrogen, the first 103 liquid phase stream and hydrogen entering the second hydrogenation reaction zone and being reacted with a hydro-upgrading catalyst therein; a second gas-liquid separator for receiving a reaction effluent from the second hydrogenation reaction zone, and separating the reaction effluent to obtain a second gas and a second liquid phase stream; a second fractionating column for receiving the second liquid phase stream from the second gas-liquid separator, and separating the second liquid phase stream to obtain a second 201 liquid phase stream, a second 202 liquid phase stream, and a second 203 liquid phase stream; a mixing unit for receiving the first 102 liquid phase stream from the first fractionating column and the second 202 liquid phase stream from the second fractionating column, and mixing the first 102 liquid phase stream and the second 202 liquid phase stream to obtain a jet fuel product.

11. The marine fuel production system according to claim 10, characterized in that: The first 101 liquid phase stream is communicated to the second hydrogenation reaction zone via a pipeline.

12. The marine fuel production system according to claim 10, characterized in that: The second 203 liquid phase stream is communicated to the first hydrogenation reaction zone and the second hydrogenation reaction zone via pipelines, respectively.

13. The marine fuel production system according to claim 10, characterized in that: The first hydrogenation reaction zone is provided with at least one hydrogenation reactor selected from at least one of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

14. The marine fuel production system according to claim 10, characterized in that: The second hydrogenation reaction zone is provided with at least one hydrogenation reactor selected from at least one of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

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