Production process and production system of aviation kerosene

Abstract

The invention discloses a production process and a production system of aviation kerosene. The production system of the aviation kerosene comprises a first hydrogenation reaction zone, a second hydrogenation reaction zone, a first gas-liquid separator, a second gas-liquid separator, a first fractionating tower, a second fractionating tower and a mixing unit. Meanwhile, the invention further provides an aviation fuel production process adopting the aviation fuel production system, part of material flow obtained by dividing the coal tar fraction subjected to moderate hydrofining treatment is mainly used as a large-specific-gravity aviation fuel component, and the product yield can be improved while an ideal large-specific-gravity aviation fuel product with all qualified indexes can be obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of coal tar processing, and in particular relates to a method for producing aviation kerosene using coal tar as raw material. Background Art

[0002] Heavy jet fuel is a type of fuel with high density (generally 0.835g / cm 3 Above), high volume calorific value (generally 35.8MJ / m 3 Compared with ordinary aviation fuel (density 0.77-0.81g / cm 3 Compared with jet fuel, high-density jet fuel can increase the calorific value of the fuel per unit volume. When the fuel tank volume is constant, it can effectively increase the energy of the fuel carried by the fuel tank, which is an important guarantee for the high-speed and long-range flight of aerospace vehicles. 3 (The volume calorific value is about 36×10 3 MJ / m 3 ) with a fuel density of 780 kg / m 3 (The volume calorific value is about 33×10 3 MJ / m 3 Compared with fuel of the same fuel volume, the aircraft can carry about 8% more energy. Therefore, the development of high-density jet fuel production technology has become one of the hot research directions in the field.

[0003] CN102304387A discloses a method for producing a coal-based high-density jet fuel, which comprises the following steps: coal chemical light oil and liquefied distillate oil from a coal direct liquefaction process enter an expanded bed hydroprocessing reactor with a forced internal circulation, contact with hydrogen and a hydroprocessing catalyst, and obtain light distillate oil, medium distillate oil and heavy distillate oil after separation and fractionation of the outlet flow of the expanded bed hydroprocessing reactor; the light distillate oil and the medium distillate oil are mixed and enter a deep hydrorefining fixed bed reactor, contact with hydrogen and a hydrorefining catalyst, and react; the outlet flow of the deep hydrorefining fixed bed reactor is separated and fractionated to obtain a high-density jet fuel; wherein a liquid collecting cup is arranged above the inside of the hydroprocessing reactor, and the collected liquid is transported through a pipeline and pressurized by a forced circulation pump and then sent to the bottom of the hydroprocessing reactor. The inventive method adopts an expanded bed reactor with forced internal circulation. The liquid in the collection cup on the upper part of the reactor needs to be returned to the reactor through a forced circulation pump for further hydrogenation, which correspondingly increases the investment in the device and energy consumption. In addition, the inventive method adopts two sets of separation and distillation systems, and the operation process is complicated, the investment in the device and the operating cost are high, and its atmospheric distillation range index does not meet the GJB1603 high-density jet fuel standard.

[0004] CN107057779A discloses a high-density jet fuel, including RP-3 jet fuel and a high-density fuel blending component, wherein the high-density fuel blending component is a cycloalkane and aromatic hydrocarbon with a distillation range of 180-300°C and a tail oil portion obtained by hydrofining with inferior heavy oil as raw material, and the physical and chemical properties of the high-density fuel blending component meet the standards of No. 3 jet fuel. Although the jet fuel density obtained reaches 960-980kg / m 3 However, its distillation range and aromatic content do not meet the GJB1603 high-density jet fuel standards.

[0005] US4401837 discloses a method for producing high-density fuel, which mainly involves thermal polymerization of cross-dicyclopentadiene, separation of trimer fractions from the thermal polymerization product, and subsequent hydrogenation and isomerization of the trimer fractions. This method not only has a complex process flow, but also has a high cost of raw materials.

[0006] CN105694970A discloses a method for producing high-density jet fuel by hydrogenating low-temperature coal tar, wherein the method mixes and heats medium-low temperature coal tar and hydrogen, and sequentially conducts hydrogenation reaction through a hydrogenation protection catalyst and a hydrogenation refining catalyst, and obtains naphtha, crude jet fuel and tail oil after fractionation of the hydrogenation product, and the crude jet fuel is refined by kaolin to obtain high-density No. 6 jet fuel. Although the process flow of this method is relatively simple, the method requires the use of 8wt% kaolin for refining, and the refined kaolin is a solid waste, which is currently difficult to regenerate. The kaolin solid waste is generally treated by incineration and landfill, which causes great damage to the environment. It is difficult to carry out industrial production under the current increasingly stringent environmental protection requirements.

[0007] Based on the analysis of the above content, it can be seen that the existing process route for producing large-scale aviation kerosene has defects such as complex process route, product properties that do not meet the usage standards, and a significant impact on the environment. Summary of the invention

[0008] In the process of studying the production process of high-density jet fuel, it was found that there are many indicators that need to be controlled for high-density jet fuel, such as density, freezing point, aromatic content, sulfur content, viscosity, etc., and the various indicators are interrelated and influence each other, and some indicators are incompatible. Compared with ordinary No. 3 jet fuel, high-density jet fuel has a narrower distillation range and a higher initial distillation point temperature requirement, so it is more difficult to balance the various indicators. If only the density is regulated, there are many operating methods that can be achieved, but when the density is regulated, the smoke point, freezing point, product composition, weight calorific value, etc. will be affected to varying degrees. Among these contradictions, the main contradiction is between density, freezing point, smoke point and aromatic composition. The goal that has been pursued in this field is to obtain an ideal high-density jet fuel product with all indicators qualified at the same time. The technical solution of the present invention is proposed based on solving the above-mentioned technical problems. The coal tar fraction after moderate hydrogenation refining treatment is split, and a certain distillation range fraction after the split is blended with another part of the split fraction after hydrogenation reforming treatment to obtain high-density aviation kerosene. While meeting various indicators of high-density aviation kerosene, the product yield is also improved.

[0009] The purpose of the present invention is to overcome the technical problems of the existing method for producing high-density aviation fuel, such as high equipment requirements, complex process flow, low density, unqualified product freezing point, low product yield, etc., and to provide an aviation fuel production process and production system. The production process is simple and does not require major changes to the device. Relying on the existing production device, it is possible to obtain high-quality aviation fuel products that meet the GJB1603 No. 6 jet fuel standard with inferior raw materials such as full-fraction coal tar, and the density can reach 0.840g / cm 3 Above, the freezing point is less than -50℃.

[0010] A first aspect of the present invention provides a process for producing aviation fuel, the process comprising the following steps:

[0011] (1) Under contact conditions, coal tar feedstock and hydrogen enter the first hydrogenation reaction zone for reaction;

[0012] (2) the reaction effluent obtained in the first hydrogenation reaction zone in step (1) is separated to obtain gas, a 101st liquid phase stream, a 102nd liquid phase stream and a 103rd liquid phase stream;

[0013] (3) the 103rd liquid phase stream obtained in step (2) and hydrogen enter the second hydrogenation reaction zone for reaction;

[0014] (4) the reaction effluent obtained in the second hydrogenation reaction zone in step (3) is separated to obtain gas, a 201st liquid phase stream, a 202nd liquid phase stream and a 203rd liquid phase stream;

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

[0016] Furthermore, in the above-mentioned aviation kerosene production process, as a specific implementation method, 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 anthracene oil can be blended at the same time, specifically, it 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 with anthracene oil.

[0017] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the coal tar raw material in step (1) is preferably first dehydrated and treated to remove mechanical impurities, and the moisture content of the treated coal tar raw material is not more than 0.15wt%, the metal content is not more than 20μg / g, and the ash content is not more than 0.01wt%.

[0018] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the first hydrogenation reaction zone in step (1) 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, an ebullating bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

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

[0020] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the hydrogenation protection catalyst can be produced using a commercial hydrogenation protection catalyst or according to the method disclosed in the prior art. For example, the FZC series hydrogenation protection catalyst developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd. (FRIPP) can be used. The hydrogenation protection catalyst generally uses a porous refractory inorganic oxide (such as alumina, etc.) as a carrier, and oxides of Group VIB and / or Group VIII metals such as W, Mo, Co, Ni, etc. as active components. Various other additives such as P, Si, F, B and other elements can also be selectively added. The hydrogenation protection catalyst is generally pre-sulfurized before use to ensure that the hydrogenation active metal is in a sulfided state during the reaction.

[0021] Furthermore, in the above-mentioned jet fuel production process, as a specific embodiment, the hydrorefining catalyst in step (1) refers to a single catalyst or a catalyst series having functions such as hydrodemetallization, hydrodesulfurization, hydrodeoxygenation, and hydrodenitrogenation. Generally, the hydrorefining catalyst includes a carrier and a hydrogenation metal component, based on the weight of the catalyst, including active metal components of Group VIB in the periodic table such as W and / or Mo, with a content of 10wt% to 35wt% based on the weight of the catalyst, preferably 15wt% to 30wt% in terms of metal oxide; and Group VIII metal oxides such as Co and / or Ni, with a content of 1wt% to 7wt% based on the weight of the catalyst, preferably 1.5wt% to 6wt%. 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, and specifically one or more of alumina, amorphous silica-alumina, silicon oxide, titanium oxide, etc. can be selected. The hydrotreating catalyst can be a commercial catalyst available in the market, or it can be prepared according to general knowledge in the field. Commercial catalysts that can be selected include 3936, 3996, FF-16, FF-22, FF-26 and other hydrotreating catalysts developed and produced by Sinopec (Dalian) Research Institute of Petrochemicals Co., Ltd. (FRIPP).

[0022] Furthermore, 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: reaction pressure is 5.0-20.0 MPa, preferably 12.0-15.0 MPa; reaction temperature is 250-420°C, preferably 330-400°C; hydrogen-oil volume ratio is 500:1-1500:1, preferably 800:1-1200:1; volume space velocity is 0.1-1.2 h -1 , preferably 0.3~0.7h -1 .

[0023] Furthermore, in the above-mentioned jet fuel production process, as a specific embodiment, the cutting temperature of the 101st liquid phase stream and the 102nd liquid phase stream in step (2) is 195-210°C, preferably 195-200°C; the cutting temperature of the 102nd liquid phase stream and the 103rd liquid phase stream is 205-220°C, preferably 205-215°C. After adopting the above-mentioned cutting scheme, the initial distillation point of the 102nd liquid phase stream is 195-210°C, preferably 195-200°C; the final distillation point is 205-220°C, preferably 205-215°C.

[0024] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the second hydrogenation reaction zone in step (3) 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, an ebullating bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

[0025] Furthermore, in the above-mentioned jet fuel production process, as a specific embodiment, the second hydrogenation reaction zone in step (3) is filled with a hydrogenation catalyst, preferably a hydrogenation catalyst containing amorphous silica-alumina and modified Y zeolite. Furthermore, the hydrogenation catalyst contains 20wt% to 60wt% amorphous silica-alumina, 5wt% to 25wt% modified Y zeolite, 10wt% to 30wt% of Group VIB metals (in terms of oxides) and 4wt% to 10wt% of Group VIII metals (in terms of oxides). The catalyst should be pre-sulfurized before use to ensure that the hydrogenation active metal is in a sulfurized state during the reaction. The hydrogenation catalyst may also contain components such as aluminum oxide, zirconium oxide, and titanium oxide. The specific surface area of ​​the hydrogenation catalyst is 220 to 300m 2 / g, pore volume is 0.3~0.6mL / g, pore volume of pore diameter 3~10nm accounts for 75%~95% of total pore volume, preferably 85%~95%, infrared acidity is 0.3~0.5mmol / g. The described hydro-reforming catalyst can select common commercial catalysts in this field, or can be prepared according to general knowledge in this 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 and other hydro-reforming catalysts developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.

[0026] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the second hydrogenation reaction zone in step (3) is also loaded with a hydro-reforming pre-refining catalyst, which is mainly used for denitrogenation and saturation of polycyclic aromatic hydrocarbons, so as to better exert the ring-opening performance of the hydro-reforming catalyst, reduce the deactivation rate of the hydro-reforming catalyst, and extend the operation cycle of the entire device. According to the flow direction of the liquid phase material, the hydro-reforming pre-refining catalyst is arranged above the hydro-reforming catalyst, and the loading volume ratio of the hydro-reforming pre-refining catalyst to the hydro-reforming catalyst is 5:75 to 60:40.

[0027] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the second hydrogenation reaction zone in step (3) is also filled with a supplementary hydrorefining catalyst, which is mainly used to saturate some of the olefins produced by the ring-opening and chain-breaking of the hydroreforming catalyst, and improve the quality of the oil generated in the reforming reaction zone. According to the flow direction of the liquid phase material, the supplementary hydrorefining catalyst is arranged at the lower part of the hydroreforming catalyst, and the filling volume ratio of the hydroreforming catalyst to the supplementary hydrorefining catalyst is 25:50 to 100:5.

[0028] Further, in the above-mentioned aviation kerosene production process, as a specific embodiment, the hydro-refining pre-refining catalyst at the top of the second hydro-reaction zone and the supplementary hydro-refining catalyst at the bottom of the second hydro-reaction zone generally include a carrier and a hydrogenation metal component, based on the weight of the catalyst, including active metal components of Group VIB in the periodic table such as W and Mo, calculated as metal oxides at 10wt% to 40wt%, preferably 15wt% to 35wt%; and Group VIII metal oxides such as Co and Ni, calculated as metal oxides at 1wt% to 10wt%, preferably 1.5wt% to 8wt%, and the catalyst should be pre-sulfurized before use to ensure that the hydrogenation active metal is in a sulfurized state during the reaction. The carrier used for the hydro-refining catalyst is an inorganic refractory oxide, such as alumina, amorphous silica-alumina, silicon oxide, titanium oxide, etc. The hydro-refining pre-refining catalyst and the supplementary refining catalyst can be selected from ordinary commercial catalysts in this field, or they can be prepared according to general knowledge in this field. Commercial catalysts that can be selected include hydrogenation catalysts such as FF-66 and FF-76 developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.

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

[0030] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation method, the 101st liquid-phase feed stream in step (2) enters the second hydrogenation reaction zone for treatment, preferably entering through the inlet on the reactor shell above the hydrogenation reforming catalyst bed in the second hydrogenation reaction zone. When the hydrogenation reforming catalyst is arranged in multiple layers, the 101st liquid-phase feed stream can also be divided into multiple feeds to enter the second hydrogenation reaction zone.

[0031] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the cutting temperature of the 201st liquid phase stream and the 202nd liquid phase stream in step (4) is 195-210°C, preferably 195-200°C; the cutting temperature of the 202nd liquid phase stream and the 203rd liquid phase stream is 250-315°C, preferably 260-290°C.

[0032] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation, the 201st liquid stream obtained in step (4) can be used as a gasoline blending component, or the 201st liquid stream can be fractionated to obtain a light component and a heavy component, and the cutting temperature point is any temperature between 130 and 145°C. The light component after cutting can be used as a catalytic reforming raw material, and the heavy component after cutting can be used as a high-quality No. 3 jet fuel blending component.

[0033] Furthermore, in the above-mentioned jet fuel production process, as a specific implementation method, the 203rd liquid phase stream in step (4) can be recycled back to the first hydrogenation reaction zone for treatment, recycled back to the second hydrogenation reaction zone for treatment, and discarded as a diesel blending component. One or more of the following treatment methods are selected; when part of the 203rd liquid phase stream is discarded, the amount of the discarded 203rd liquid phase stream can be dynamically adjusted according to the load of the entire reaction system.

[0034] A second aspect of the present invention provides an aviation fuel production system, the production system comprising:

[0035] The first hydrogenation reaction zone is used to receive the coal tar feedstock and hydrogen. The coal tar feedstock and hydrogen enter the first hydrogenation reaction zone and contact with the hydrogenation protection catalyst and the hydrorefining catalyst to react;

[0036] A first gas-liquid separator, which is used to receive the reaction effluent obtained from the first hydrogenation reaction zone and obtain a first gas and a first liquid phase stream after separation;

[0037] A first fractionation tower, which is used to receive the first liquid phase stream from the first gas-liquid separator, and obtain a 101st liquid phase stream, a 102nd liquid phase stream and a 103rd liquid phase stream after separation;

[0038] The second hydrogenation reaction zone is used to receive the 103rd liquid phase stream and hydrogen from the first fractionation tower. The 103rd liquid phase stream and hydrogen enter the second hydrogenation reaction zone and contact with the hydroreforming catalyst therein to react;

[0039] A second gas-liquid separator, which is used to receive the reaction effluent obtained from the second hydrogenation reaction zone and obtain a second gas and a second liquid phase stream after separation;

[0040] A second fractionation tower, which is used to receive the second liquid phase stream from the second gas-liquid separator, and obtain a 201st liquid phase stream, a 202nd liquid phase stream and a 203rd liquid phase stream after separation;

[0041] The mixing unit is used for receiving the 102nd liquid phase material flow from the first fractionation tower and the 202nd liquid phase material flow from the second fractionation tower, and obtaining the aviation kerosene product after mixing.

[0042] Furthermore, in the above-mentioned jet fuel production system, as a specific implementation, the 101st liquid phase stream is connected to the second hydrogenation reaction zone through a pipeline.

[0043] Furthermore, in the above-mentioned jet fuel production system, as a specific implementation, the 201st liquid stream can be discharged and used as a gasoline blending component, or the 201st liquid stream can be fractionated and cut to obtain a light component and a heavy component, and the cutting temperature point is any temperature between 130 and 145°C. The light component after cutting can be used as a catalytic reforming raw material, and the heavy component after cutting can be used as a high-quality No. 3 jet fuel blending component.

[0044] Furthermore, in the above-mentioned jet fuel production system, as a specific implementation method, the 203rd liquid-phase feed stream can be connected to the first hydrogenation reaction zone and the second hydrogenation reaction zone respectively through pipelines; the 203rd liquid-phase feed stream can be circulated back to the first hydrogenation reaction zone for treatment, circulated back to the second hydrogenation reaction zone for treatment, and externally discharged as a diesel blending component, and one or more of the following treatment methods can be selected; when part of the liquid-phase feed stream is externally discharged, the amount of the externally discharged 203rd liquid-phase feed stream can be dynamically adjusted according to the load of the entire reaction system.

[0045] Furthermore, in the above-mentioned jet fuel production system, as a specific embodiment, at least one hydrogenation reactor is provided in the first hydrogenation reaction zone, and the hydrogenation reactor can be selected from at least one of a fixed bed hydrogenation reactor, an ebullating bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

[0046] Furthermore, in the above-mentioned jet fuel 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, an ebullating bed hydrogenation reactor, and a suspended bed hydrogenation reactor.

[0047] Furthermore, in the above-mentioned aviation kerosene production system, as a specific implementation, the first gas-liquid separator and the second gas-liquid separator are any of the devices that can realize the gas-liquid two-phase separation function. Those skilled in the art can select according to actual needs and the knowledge they have mastered.

[0048] Furthermore, in the above-mentioned aviation fuel production system, as a specific implementation, the first distillation tower and the second distillation tower can adopt any of the existing distillation towers in the art, such as a packed tower, a plate tower, and the like.

[0049] Compared with the prior art, the technical effects and advantages of the aviation fuel production process and production system provided by the present invention are as follows:

[0050] In the jet fuel production process provided by the present invention, firstly, the whole fraction coal tar is subjected to appropriate hydrogenation refining treatment, and then the 102nd liquid stream obtained by fractionation is mixed with the 202nd liquid stream obtained after subsequent hydrogenation reforming treatment to obtain a high-density jet fuel product. Among them, the 102nd liquid stream contains a large amount of cycloalkanes and monocyclic aromatic hydrocarbons, which can be significantly improved by mixing with the 202nd liquid stream to increase the density of the high-density jet fuel, so that its index can reach 0.840g / cm 3 The above can significantly reduce the freezing point of the heavy jet fuel fraction, making its index less than -50°C, solving the problem of incompatibility of various important indicators of heavy jet fuel. At the same time, by cutting the refined coal tar fraction, wherein the 102nd liquid phase stream does not enter the hydrogenation reforming reaction zone for hydrogenation treatment, it can be avoided that excessive hydrogenation is performed during the subsequent hydrogenation reforming treatment, resulting in an advance in the distillation range, thereby increasing the yield of the heavy jet fuel fraction. In the method of the present invention, the 101st liquid phase stream enters the second hydrogenation reaction zone, which can further improve the product properties on the one hand, and effectively regulate the temperature of the second hydrogenation reaction zone on the other hand, thereby improving the operating flexibility of the second hydrogenation reaction zone and the service life of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a schematic diagram of the aviation fuel production process and production system of the present invention;

[0052] in,

[0053] 1: Coal tar raw material 2: First cycle hydrogen

[0054] 3: New hydrogen 4: First hydrogenation reaction zone

[0055] 5: Effluent from the first hydrogenation reaction zone 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 fractionation tower 12: 101st liquid phase stream

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

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

[0061] 17: Effluent from the second hydrogenation reaction zone 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 tower 24: 201st liquid phase stream

[0065] 25: No. 202 liquid phase stream 26: No. 203 liquid phase stream

[0066] 27: Mixing unit 28 heavy jet fuel products DETAILED DESCRIPTION

[0067] The technical features of the present invention are further described below through specific examples in conjunction with the accompanying drawings, but these embodiments cannot limit the present invention.

[0068] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0069] In this document, for the convenience of description, spatial relative terms such as "below", "below", "down", "above", "above", "upper", etc. may be used to describe the relationship between one element or feature and another element or feature in the accompanying drawings. It should be understood that the spatial relative terms are intended to include different orientations of the object in use or operation in addition to the orientation depicted in the figure. For example, if the object in the figure is turned over, the element described as being "below" or "below" other elements or features will be oriented "above" the element or feature. Therefore, the exemplary term "below" can include both below and above. Objects may also have other orientations (rotated 90 degrees or other orientations) and the spatial relative terms used in this document should be interpreted accordingly.

[0070] In this document, the terms "first", "second", etc. are used to distinguish two different elements or parts, and are not used to limit a specific position or relative relationship. In other words, in some embodiments, the terms "first", "second", etc. can also be interchangeable.

[0071]

[0043] All numerical values ​​for parameters (eg, amounts or conditions) herein are to be understood as being modified in all instances by the term "about," whether or not "about" actually appears before the numerical value.

[0072] In this article, jet fuel yield is the weight percentage of heavy jet fuel product to feedstock oil.

[0073] In this article, the various catalysts involved can be commercial catalysts selected according to their properties, or can be prepared according to the knowledge in the field. The hydrogenation protection catalyst can be selected from FZC-100, FZC-102A, and FZC-103 hydrogenation protection agents developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.; the hydrorefining catalyst can be selected from 3936, 3996, FF-16, FF-22, FF-26 and other hydrorefining catalysts developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.; the hydrorefining pre-refining catalyst at the upper part of the hydroreforming reaction zone and the supplementary hydrorefining catalyst at the lower part can be selected from FF-66, FF-76 and other hydrorefining catalysts developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.; the hydrorefining 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 and other hydrorefining catalysts developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd.

[0074] like Figure 1As shown, the coal tar feedstock 1 after dehydration and removal of impurities is mixed with new hydrogen 3 to obtain the hydrogenation feed of the first hydrogenation reaction zone, which enters the first hydrogenation reaction zone 4, contacts with the catalyst therein for hydrogenation reaction, and the obtained first hydrogenation reaction zone effluent 5 enters the first gas-liquid separator 6 for separation, and the separated first gas 7 and the first liquid phase stream 10 are obtained; 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 the impurities are removed is mixed with the new hydrogen 3 as the first circulating hydrogen 2 and returned to the first hydrogenation reaction zone 4. The first liquid stream 10 obtained by separation enters the first distillation tower 11, and after fractionation, the 101st liquid stream 12, the 102nd liquid stream 13 and the 103rd liquid stream 14 are obtained respectively, wherein the 101st liquid stream 12 and the 103rd liquid stream 14 are mixed with the new hydrogen 3 and enter the second hydrogenation reaction zone 16 to contact with the catalyst therein for hydrogenation reforming reaction, wherein the 101st liquid stream 12 enters the second hydrogenation reaction zone 16 through the feed port on the reactor shell corresponding to the hydrogenation reforming catalyst bed in the second hydrogenation reaction zone; the effluent 17 of the second hydrogenation reaction zone obtained by the reaction enters the second gas The liquid separator 18 performs separation to obtain a second gas 19 and a second liquid phase stream 22; the second gas 19 enters the second purification unit 20 to remove impurities therein, the second purified hydrogen 21 after impurities are removed is mixed with the new hydrogen 3 as the second circulating hydrogen 15 to enter the second hydrogenation reaction zone 16 for use, the separated second liquid phase stream 22 enters the second fractionation tower 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 respectively, the 202nd liquid phase stream 25 and the 102nd liquid phase stream 12 enter the mixing unit 27 and are mixed to obtain a high-density aviation kerosene product 28. The 203rd liquid phase stream 26 can be divided into multiple streams, one of which is used as a product and one is recycled back to the first hydrogenation reaction zone and / or the second hydrogenation reaction zone.

[0075] In this paper, the coal tar raw materials used include two types, and the specific raw material properties are shown in Table 1.

[0076] Table 1 Coal tar raw material properties

[0077]

[0078]

[0079] Example 1

[0080] Raw material A is used as the raw material, and the properties of the raw materials are shown in Table 1. Figure 1The production process flow in which the 101st liquid phase stream all enters the second hydrogenation reaction zone, and the 203rd stream is recycled back to the second hydrogenation reaction zone with a ratio of 1:1 to the external rejection. The first hydrogenation reaction zone is filled with hydrogenation protective agent FZC-103 and hydrogenation refining catalyst FF-22, and the filling volume ratio of hydrogenation protective agent FZC-103 and hydrogenation refining catalyst FF-22 is 1:5. Among them, the distillation range of the 102nd liquid phase stream is 195-210°C, and the properties are shown in Table 2. The second hydrogenation reaction zone is sequentially filled with FF-66 hydrogenation reforming pre-refining catalyst, FC-50 hydrogenation reforming catalyst, and FF-76 supplementary refining catalyst according to the flow direction of the liquid phase material, and the filling volume ratio of hydrogenation reforming pre-refining catalyst, hydrogenation reforming catalyst and supplementary refining catalyst is 2:10:1. The distillation range of the 202nd liquid phase stream is 195-280°C. The hydrogenation process conditions of 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.

[0081] Example 2

[0082] Raw material B is used as the raw material, and the properties of the raw materials are shown in Table 1. Figure 1 The production process flow in which the 101st liquid phase stream all enters the second hydrogenation reaction zone, and the 203rd stream is all recycled back to the second hydrogenation reaction zone. The first hydrogenation reaction zone is loaded with hydrogenation protective agent FZC-103 and hydrogenation refining catalyst FF-22, and the filling volume ratio of hydrogenation protective agent FZC-103 and hydrogenation refining catalyst FF-22 is 1:6. Among them, the distillation range of the 102nd liquid phase stream is 200-215°C, and the properties are shown in Table 2. The second hydrogenation reaction zone is sequentially loaded with FF-66 hydrogenation reforming pre-refining catalyst, FC-50 hydrogenation reforming catalyst, and FF-76 supplementary refining catalyst according to the flow direction of the liquid phase material, and the filling volume ratio of hydrogenation reforming pre-refining catalyst, hydrogenation reforming catalyst and supplementary refining catalyst is 1:10:1. The distillation range of the 202nd liquid phase stream is 200-275°C. The hydrogenation process conditions of 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.

[0083] Example 3

[0084] It is basically the same as Example 1, except that the hydrogenation process conditions of the first hydrogenation reaction zone and the second hydrogenation reaction zone are different. The hydrogenation process conditions of 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] It is basically the same as Example 1, except that the 101st liquid phase stream does not enter the second hydrogenation reaction zone. The hydrogenation process conditions of 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.

[0087] Comparative Example 1

[0088] The results are basically the same as those in Example 1, except that the first liquid phase stream in Comparative Example 1 is fractionated to obtain two liquid phase materials, namely the first material and the second material, wherein the distillation range of the first material is equivalent to the 101st liquid phase stream in Example 1, and the second material all enters the second hydrogenation reaction zone. The hydrogenation process conditions of the first hydrogenation reaction zone and the second hydrogenation reaction zone are shown in Table 4, and the reaction results are shown in Table 6.

[0089] Comparative Example 2

[0090] It is basically the same as Example 2, except that the first liquid phase stream in Comparative Example 2 is fractionated to obtain two liquid phase materials, namely the first material and the second material, wherein the distillation range of the first material is equivalent to the 101st liquid phase stream in Example 2, and the second material all enters the second hydrogenation reaction zone. The hydrogenation process conditions of the first hydrogenation reaction zone and the second hydrogenation reaction zone are shown in Table 4, and the reaction results are shown in Table 6.

[0091] Comparative Example 3

[0092] The method is basically the same as Example 1, except that the first liquid phase stream in Comparative Example 3 is 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 are shown in Table 4, and the reaction results are shown in Table 6.

[0093] Table 2 Properties of the 102nd liquid 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 The first hydrogenation reaction zone Reaction pressure, MPa 15.0 15.0 12.0 15.0 Reaction temperature, °C 360 340 390 360 <![CDATA[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 <![CDATA[Space velocity, h -1 > 0.8 0.4 1.2 0.8 Hydrogen to oil volume ratio 1000 800 1200 1000

[0098] Table 4 Comparative Examples 1-3 Hydrogenation Process Conditions

[0099]

[0100]

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

[0102]

[0103]

[0104] Table 6 Comparative Examples 1-3 Reaction Results

[0105] Test No. Comparative Example 1 Comparative Example 2 Comparative Example 3 <![CDATA[Density (20 °C), g·cm -3 > 0.829 0.830 0.828 Distillation range (ASTM D86), ℃ 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 <![CDATA[Countercurrent viscosity (20 °C) / mm 2 ·s -1 > 2.779 2.732 2.744 <![CDATA[Countercurrent viscosity (-40°C) / mm 2 ·s -1 > 20.73 20.88 20.62 Freezing point / ℃ -45 -46 -43 Flash point (closed cup) / ℃ 82 81 83 Jet fuel 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 some indicators of the heavy jet fuel obtained when the raw materials are not separated into the light components of the heavy jet fuel after hydrofining cannot meet the requirements of the GJB1603 No. 6 jet fuel standard.

[0107] The properties of the jet fuel product obtained in the example show that the density of the high-density jet fuel produced by this method reaches 0.840 g / cm 3 The temperature of the fuel oil is above 200℃, and the freezing point is less than -50℃, which meets the requirements of the GJB1603 No. 6 jet fuel standard. It can also expand the raw material source of heavy jet fuel, enrich the deep utilization of coal tar resources, and has great economic and social benefits.

Claims

1. A process for producing aviation fuel, the process comprising the following steps: (1) Under contact conditions, coal tar feedstock and hydrogen enter the first hydrogenation reaction zone for reaction; (2) The reaction effluent obtained in the first hydrogenation reaction zone in step (1) is separated to obtain gas, a 101st liquid phase stream, a 102nd liquid phase stream and a 103rd liquid phase stream; (3) The 103rd liquid phase stream obtained in step (2) and hydrogen enter the second hydrogenation reaction zone for reaction; (4) The reaction effluent obtained from the second hydrogenation reaction zone in step (3) is separated to obtain gas, a 201st liquid phase stream, a 202nd liquid phase stream and a 203rd liquid phase stream; (5) The 102nd liquid phase stream obtained in step (2) and the 202nd liquid phase stream obtained in step (4) are mixed to obtain a jet fuel product.

2. The aviation fuel production process according to claim 1, characterized in that: The coal tar raw material in step (1) is first dehydrated and treated to remove mechanical impurities. The moisture content of the treated coal tar raw material is not more than 0.15wt%, the metal content is not more than 20ug / g, and the ash content is not more than 0.01wt%.

3. The aviation fuel production process according to claim 1, characterized in that: The first hydrogenation reaction zone is filled with a hydrogenation protection catalyst and a hydrogenation refining catalyst, which are sequentially filled in the direction of liquid phase material flow. Based on the filling volume ratio, the ratio of the hydrogenation protection catalyst to the hydrogenation refining catalyst is 5:60 to 75:

90.

4. The aviation fuel production process according to claim 1, characterized in that: The operating conditions of the first hydrogenation reaction zone in step (1) are as follows: reaction pressure of 5.0 to 20.0 MPa, preferably 12.0 to 15.0 MPa; reaction temperature of 250 to 420°C, preferably 330 to 400°C; hydrogen to oil volume ratio of 500:1 to 1500:1, preferably 800:1 to 1200:1; volume space velocity of 0.1 to 1.2 h -1 , preferably 0.3~0.7h -1 .

5. The aviation fuel production process according to claim 1, characterized in that: The initial distillation point of the 102nd liquid phase stream in step (2) is 195-210°C, preferably 195-200°C; the final distillation point is 205-220°C, preferably 205-215°C.

6. The aviation fuel production process according to claim 1, characterized in that: The second hydrogenation reaction zone in step (3) is filled with a hydrogenation catalyst, and a hydrogenation catalyst containing amorphous silica-alumina and modified Y zeolite is used.

7. The aviation fuel production process according to claim 1, characterized in that: The second hydrogenation reaction zone in step (3) is filled with a hydrogenation pre-refining catalyst. According to the flow direction of the liquid phase material, the hydrogenation pre-refining catalyst is arranged above the hydrogenation catalyst. The filling volume ratio of the hydrogenation pre-refining catalyst to the hydrogenation catalyst is 5:75 to 60:

40.

8. The aviation fuel production process according to claim 1, characterized in that: The second hydrogenation reaction zone in step (3) is filled with a supplementary hydrorefining catalyst. According to the flow direction of the liquid phase material, the supplementary hydrorefining catalyst is arranged at the lower part of the hydroreforming catalyst. The filling volume ratio of the hydroreforming catalyst to the supplementary hydrorefining catalyst is 25:50 to 100:

5.

9. The aviation fuel production process according to claim 1, characterized in that: The operating conditions of the hydro-reforming reaction zone in step (3) are as follows: reaction pressure of 5.0-20.0 MPa, preferably 12.0-15.0 MPa; reaction temperature of 250-420°C, preferably 330-380°C; hydrogen-to-oil volume ratio of 500:1-1500:1, preferably 800:1-1200:1; volume space velocity of 0.1-1.5 h -1 , preferably 0.4 to 1.2h -1 .

10. The aviation fuel production process according to claim 1, characterized in that: The 101st liquid phase feed stream in step (2) enters the second hydrogenation reaction zone for treatment.

11. The aviation fuel production process according to claim 1, characterized in that: The cutting temperature of the 201st liquid phase stream and the 202nd liquid phase stream in step (4) is 195-210°C, preferably 195-200°C; the cutting temperature of the 202nd liquid phase stream and the 203rd liquid phase stream is 250-315°C, preferably 260-290°C.

12. The aviation fuel production process according to claim 1, characterized in that: The 203rd liquid phase stream in step (4) can be processed in one or more of the following ways: recycled to the first hydrogenation reaction zone for treatment, recycled to the second hydrogenation reaction zone for treatment, or discarded as a diesel blending component.

13. A jet fuel production system, comprising: The first hydrogenation reaction zone is used to receive the coal tar feedstock and hydrogen. The coal tar feedstock and hydrogen enter the first hydrogenation reaction zone and contact with the hydrogenation protection catalyst and the hydrorefining catalyst to react; A first gas-liquid separator, which is used to receive the reaction effluent obtained from the first hydrogenation reaction zone and obtain a first gas and a first liquid phase stream after separation; A first fractionation tower, which is used to receive the first liquid phase stream from the first gas-liquid separator, and obtain a 101st liquid phase stream, a 102nd liquid phase stream and a 103rd liquid phase stream after separation; The second hydrogenation reaction zone is used to receive the 103rd liquid phase stream and hydrogen from the first fractionation tower. The 103rd liquid phase stream and hydrogen enter the second hydrogenation reaction zone and contact with the hydroreforming catalyst therein to react; A second gas-liquid separator, which is used to receive the reaction effluent obtained from the second hydrogenation reaction zone and obtain a second gas and a second liquid phase stream after separation; A second fractionation tower, which is used to receive the second liquid phase stream from the second gas-liquid separator, and obtain a 201st liquid phase stream, a 202nd liquid phase stream and a 203rd liquid phase stream after separation; The mixing unit is used for receiving the 102nd liquid phase material flow from the first fractionation tower and the 202nd liquid phase material flow from the second fractionation tower, and obtaining the aviation kerosene product after mixing.

14. The aviation fuel production system according to claim 13, characterized in that: The 101st liquid-phase stream is connected to the second hydrogenation reaction zone through a pipeline.

15. The aviation fuel production system according to claim 13, characterized in that: The 203rd liquid phase material flows through pipelines and is connected to the first hydrogenation reaction zone and the second hydrogenation reaction zone respectively.

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

17. The aviation fuel production system according to claim 13, characterized in that: The second hydrogenation reaction zone is provided with at least one hydrogenation reactor, and the hydrogenation reactor is selected from at least one of a fixed bed hydrogenation reactor, an ebullating bed hydrogenation reactor and a suspended bed hydrogenation reactor.

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