Method and system for producing aviation kerosene

Abstract

The invention discloses a method and a system for producing aviation kerosene, the method comprises the following steps: (1) coal tar enters a first hydrogenation reaction zone for reaction, and reaction effluent is separated to obtain gas A, a liquid phase material A, a liquid phase material B, a liquid phase material C and a liquid phase material D; (2) enabling the liquid-phase material D to enter a second hydrogenation reaction zone for reaction; (3) enabling the liquid-phase material A, the liquid-phase material C and a reaction effluent of the second hydrogenation reaction zone to enter a third hydrogenation reaction zone for reaction, and separating the reaction effluent to obtain a gas B, a liquid-phase material E, a liquid-phase material F and a liquid-phase material G; and (4) mixing the liquid-phase material B and the liquid-phase material F to obtain the aviation kerosene. The invention further provides a system for producing aviation kerosene. The method for producing the aviation kerosene is simple in process, the high-quality aviation kerosene product meeting the GJB1603 # 6 jet fuel standard is obtained with the full-fraction coal tar as the raw material, the density can reach 0.840 g / cm < 3 > or above, and the freezing point is smaller than-50 DEG C.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemical industry, and mainly relates to a method and system for producing aviation kerosene. Background Art

[0002] High-density jet fuel is a type of liquid hydrocarbon fuel with high density, high volume calorific value and high performance. Compared with ordinary jet fuel, it effectively improves the calorific value of fuel per unit volume. The use of this fuel on aircraft can effectively increase the unit volume heat of the fuel carried by the aircraft, thereby meeting the requirements of high speed and long range of the aircraft. With the development of the industry, the demand for high-density, high-performance high-density jet fuel is becoming more and more urgent. However, the jet fuel used in my country is mainly RP-3, and its density (20°C) can only reach a maximum of 830kg / m 3 Therefore, it is of great significance to develop high-density and low-cost jet fuel.

[0003] 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.

[0004] US4875992A discloses a method for producing high-density aviation kerosene from condensed aromatic hydrocarbons and hydrogenated aromatic hydrocarbons. In this method, the raw material is a raw oil rich in dicyclic aromatic hydrocarbons and dicyclic hydrogenated aromatic hydrocarbons, including light catalytic cycle oil, fuel oil, etc. The raw material first enters the first stage reaction for desulfurization and denitrogenation. The product after desulfurization and denitrogenation enters the second stage reaction for hydrogenation, and selectively hydrogenates saturated dicyclic aromatic hydrocarbons and dicyclic hydrogenated aromatic hydrocarbons to generate cycloalkanes while generating as few low molecular hydrocarbons as possible. The gravity index (API°) of the obtained high-density aviation kerosene is between 25°-35°, and the aromatic content is below 50wt%. This method requires the raw material fraction range to be between 350-700℃, and requires the raw material to contain 85-100wt% of dicyclic aromatic hydrocarbons and dicyclic hydrogenated aromatic hydrocarbons, and the requirements for the raw material are relatively stringent.

[0005] 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.

[0006] Based on the above analysis, it can be seen that the existing process route for producing high-density aviation kerosene has defects such as complex process route, product properties that do not meet the GJB1603 high-density jet fuel use standards, and a significant impact on the environment. Summary of the invention

[0007] In view of the problems existing in the existing methods for producing aviation kerosene, the present invention provides a method and system for producing aviation kerosene. The production method has a simple process and can achieve high-quality aviation kerosene products that meet the GJB1603 No. 6 jet fuel standard by simply adjusting the existing device using full-fraction coal tar as raw material, with a density of up to 0.840 g / cm 3 Above, the freezing point is less than -50℃.

[0008] The technical solution of the present invention includes the following aspects:

[0009] The present invention first provides a method for producing aviation kerosene, comprising the following steps:

[0010] (1) In the presence of hydrogen, coal tar enters the first hydrogenation reaction zone for reaction, and the reaction effluent is separated to obtain gas A, liquid material A, liquid material B, liquid material C and liquid material D;

[0011] (2) Liquid phase material D enters the second hydrogenation reaction zone for reaction;

[0012] (3) liquid material A, liquid material C, and the reaction effluent of the second hydrogenation reaction zone enter the third hydrogenation reaction zone for reaction, and the reaction effluent is separated to obtain gas B, liquid material E, liquid material F, and liquid material G;

[0013] (4) The liquid material B and the liquid material F are mixed to obtain aviation kerosene.

[0014] Preferably, in the above method for producing aviation kerosene, the coal tar in step (1) is preferably first dehydrated and treated to remove mechanical impurities, and the treated coal tar raw material has a moisture content of no more than 0.15wt%, a metal content of no more than 20μg / g, and an ash content of no more than 0.01wt%. The coal tar 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 at the same time, and 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.

[0015] Preferably, in the above-mentioned method for producing aviation kerosene, 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.

[0016] Preferably, in the above-mentioned method for producing aviation kerosene, the hydrogenation protection catalyst can be produced by using a commercial hydrogenation protection catalyst or by a 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, and other various additives such as P, Si, F, B, etc. 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.

[0017] Preferably, in the above-mentioned method for producing aviation kerosene, 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 5wt% to 30wt% based on the weight of the catalyst as metal oxide, preferably 10wt% to 25wt%; and Group VIII metal oxides such as Co and / or Ni, with a content of 0.8wt% to 6wt% based on metal oxide, preferably 1wt% to 5wt%. The catalyst should be sulfurized before use to ensure that the hydrogenation active metal is in a sulfurized state during the reaction. The carrier is generally an inorganic refractory oxide, and specifically can be selected from one or more of alumina, amorphous silica-alumina, silicon oxide, titanium oxide, etc. The hydrotreating catalyst can be a commercial catalyst available in the market, or can be prepared according to general knowledge in the field. Commercial catalysts that can be selected include 3936, 3996, FF-22 and other hydrotreating catalysts developed and produced by Sinopec (Dalian) Research Institute of Petrochemicals Co., Ltd. (FRIPP).

[0018] Preferably, in the above method for producing aviation kerosene, the operating conditions of the first hydrogenation reaction zone in step (1) are:

[0019] The reaction pressure is 5.0 to 20.0 MPa, preferably 12.0 to 15.0 MPa;

[0020] The reaction temperature is 250-420°C, preferably 330-400°C;

[0021] The volume ratio of hydrogen to oil is 500:1 to 1500:1, preferably 800:1 to 1200:1;

[0022] Volume space velocity is 0.1~1.2h -1 , preferably 0.3 to 0.8h -1 .

[0023] Preferably, in the above-mentioned method for producing aviation kerosene, the cutting temperature of liquid material A and liquid material B in step (1) is 195-210°C, preferably 195-200°C; the cutting temperature of liquid material B and liquid material C is 205-220°C, preferably 205-215°C; the cutting temperature of liquid material C and liquid material D is 240-280°C, preferably 250-270°C.

[0024] Preferably, in the above-mentioned method for producing aviation kerosene, the first hydrogenation reaction zone, the second hydrogenation reaction zone, and the third hydrogenation reaction zone are each 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] Preferably, in the above method for producing aviation kerosene, the operating conditions of the second hydrogenation reaction zone are:

[0026] The reaction pressure is 5.0 to 20.0 MPa, preferably 12.0 to 15.0 MPa;

[0027] The reaction temperature is 250-420°C, preferably 330-390°C;

[0028] The volume ratio of hydrogen to oil is 500:1 to 1500:1, preferably 800:1 to 1200:1;

[0029] Volume space velocity is 0.1~1.5h -1 , preferably 0.6~1.2h -1 .

[0030] Preferably, in the above method for producing aviation kerosene, the operating conditions of the third hydrogenation reaction zone are:

[0031] The reaction pressure is 5.0 to 20.0 MPa, preferably 12.0 to 15.0 MPa;

[0032] The reaction temperature is 250-420°C, preferably 330-380°C;

[0033] The volume ratio of hydrogen to oil is 500:1 to 1500:1, preferably 800:1 to 1000:1;

[0034] Volume space velocity is 0.1~1.2h -1 , preferably 0.4~1.0h -1 .

[0035] Preferably, in the above-mentioned method for producing aviation kerosene, the second hydrogenation reaction zone 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 300m2 / 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.

[0036] Preferably, in the above-mentioned method for producing aviation kerosene, the second hydrogenation reaction zone is also loaded with a hydro-reforming pre-refining catalyst, which is mainly used for denitrogenation and saturation of condensed 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.

[0037] Preferably, in the above-mentioned method for producing aviation kerosene, the hydrorefining pre-refining catalyst at the top of the second hydrogenation reaction zone generally 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 Mo, calculated as 10wt% to 40wt% in terms of metal oxides, preferably 15wt% to 35wt%; and Group VIII metal oxides such as Co and Ni, calculated as 1wt% to 10wt% in terms of metal oxides, preferably 1.5wt% to 8wt%. 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 hydrorefining catalyst is an inorganic refractory oxide, such as alumina, amorphous silica-alumina, silicon oxide, titanium oxide, etc. The hydrorefining pre-refining catalyst and the supplementary refining catalyst can be selected from ordinary commercial catalysts in this field, or 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.

[0038] Preferably, in the above-mentioned method for producing aviation kerosene, the third hydrogenation reaction zone is filled with a hydrorefining catalyst, and the hydrorefining catalyst refers to a single catalyst or a series of catalysts having functions such as 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, based on the weight of the catalyst, the content is 10wt% to 35wt% in terms of metal oxide, preferably 15wt% to 30wt%; and Group VIII metal oxides such as Co and / or Ni, the content is 1wt% to 8wt% in terms of metal oxide, preferably 1.5wt% to 7wt%, and the catalyst should be sulfurized before use to ensure that the hydrogenation active metal is in a sulfurized 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 can be prepared according to general knowledge in the field. Commercial catalysts that can be selected include FF-16, FF-26 and other hydrotreating catalysts developed and produced by Sinopec (Dalian) Research Institute of Petrochemicals Co., Ltd. (FRIPP).

[0039] Preferably, in the above method for producing aviation kerosene, the cutting temperature of liquid material E and liquid material F is 195-210°C, preferably 195-200°C; the cutting temperature of liquid material F and liquid material G is 250-315°C, preferably 260-290°C.

[0040] Preferably, in the above-mentioned method for producing aviation kerosene, the liquid material E can be used as a gasoline blending component, or the liquid material E 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.

[0041] Preferably, in the above-mentioned method for producing aviation kerosene, the liquid material G can be processed in one or more of the following ways: circulating back to the first hydrogenation reaction zone for treatment, circulating back to the second hydrogenation reaction zone for treatment, and discarding as a diesel blending component; when part of the liquid material G is discarded, the amount of the discarded liquid material G can be dynamically adjusted according to the load of the entire reaction system.

[0042] A second aspect of the present invention provides a system for producing aviation kerosene, the system comprising:

[0043] The first hydrogenation reaction zone is used to receive coal tar and hydrogen. The coal tar and hydrogen enter the first hydrogenation reaction zone and contact with the hydrogenation protection catalyst and the hydrorefining catalyst to react;

[0044] A first gas-liquid separator, which is used to receive the reaction effluent obtained from the first hydrogenation reaction zone, and obtain gas A and a first liquid phase stream after separation;

[0045] A first fractionation tower, which is used to receive the liquid phase material flow from the first gas-liquid separator, and obtain liquid phase material A, liquid phase material B, liquid phase material C and liquid phase material D after separation;

[0046] The second hydrogenation reaction zone is used to receive the liquid material D and hydrogen from the first fractionation tower. The liquid material D and hydrogen enter the second hydrogenation reaction zone and contact with the hydrorefining catalyst therein to react;

[0047] The third hydrogenation reaction zone is used to receive the liquid material A and the liquid material C from the first fractionation tower, the reaction effluent from the second hydrogenation reaction zone, and the hydrogen. The liquid material A, the liquid material C, the reaction effluent from the second hydrogenation reaction zone, and the hydrogen enter the second hydrogenation reaction zone and contact with the catalyst therein to react;

[0048] A second gas-liquid separator, which is used to receive the reaction effluent obtained from the third hydrogenation reaction zone, and obtain gas B and a second liquid phase stream after separation;

[0049] A second fractionation tower, which is used to receive the second liquid phase stream from the second gas-liquid separator, and obtain liquid phase material E, liquid phase material F and liquid phase material G after separation;

[0050] The mixing tank is used to receive the liquid material B from the first fractionation tower and the liquid material F from the second fractionation tower, and obtain the aviation kerosene product after mixing.

[0051] Preferably, in the above-mentioned system for producing aviation kerosene, the liquid material E is discarded and used as a gasoline blending component, or the liquid material E is 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 is used as a catalytic reforming raw material, and the heavy component after cutting is used as a high-quality No. 3 jet fuel blending component.

[0052] Preferably, in the above-mentioned system for producing aviation kerosene, the liquid material G can be connected to the first hydrogenation reaction zone and the second hydrogenation reaction zone respectively through pipelines; the liquid material G can be circulated back to the first hydrogenation reaction zone for treatment, circulated back to the second hydrogenation reaction zone for treatment, and thrown out as a diesel blending component, and one or more of the following treatment methods can be selected; when part of the liquid material G is thrown out, the amount of the thrown out liquid material G can be dynamically adjusted according to the load of the entire reaction system.

[0053] Preferably, in the above-mentioned system for producing aviation kerosene, the first hydrogenation reaction zone, the second hydrogenation reaction zone, and the third hydrogenation reaction zone are each 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.

[0054] Preferably, in the above-mentioned system for producing aviation kerosene, the first gas-liquid separator and the second gas-liquid separator are any of the devices capable of realizing the gas-liquid two-phase separation function. Those skilled in the art can select them according to actual needs and the knowledge they have mastered.

[0055] Preferably, in the above-mentioned system for producing aviation kerosene, the first fractionation tower and the second fractionation tower can be any of the fractionation towers currently available in the art, such as a packed tower, a plate tower, and the like.

[0056] Compared with the prior art, the method and system for producing aviation kerosene provided by the present invention have the following advantages:

[0057] In the process of studying the production method of high-density aviation kerosene, it was found that there are many indicators that need to be controlled for the properties of high-density aviation kerosene products, such as density, freezing point, aromatic content, sulfur content, viscosity, etc., and the various indicators are interrelated and affect each other, and some indicators are incompatible. Compared with ordinary No. 3 aviation kerosene, high-density aviation kerosene 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 indicator is regulated, there are many operating methods that can be achieved, but when the density regulation is qualified, 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 aviation kerosene 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 and refining treatment is divided, and different schemes and conditions are adopted for hydrogenation according to the properties of the fractions in different distillation ranges after the division. The generated oil after hydrogenation is mixed to obtain the aviation kerosene fraction. While meeting various indicators of high-density aviation kerosene, the product yield is also improved.

[0058] In the aviation kerosene production process provided by the present invention, firstly, the whole fraction coal tar is subjected to moderate hydrogenation refining treatment, and then fractionation is performed to obtain liquid material A, liquid material B, liquid material C and liquid material D, and fractions of different distillation ranges are utilized in stages, different catalyst schemes are designed and more suitable reaction conditions are formulated. Among them, liquid material B contains a large amount of cycloalkanes and monocyclic aromatic compounds, which can significantly improve the density of high-density aviation kerosene products when mixed with liquid material F; the cutting temperature of liquid material C is within the standard temperature of high-density aviation kerosene, and after deep refining in the third hydrogenation reaction zone, the dicyclic aromatic hydrocarbons in the fraction can be saturated into cycloalkanes, which can effectively reduce the freezing point of high-density aviation kerosene products; the heavy components in liquid material D can be significantly moved forward after being modified in the second hydrogenation reaction zone and then entering the third hydrogenation reaction zone for supplementary refining, thereby improving the yield of high-density aviation kerosene. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 It is a schematic diagram of the process and system for producing aviation kerosene of the present invention;

[0060] in,

[0061] 1: Coal tar 2: First cycle hydrogen

[0062] 3: New hydrogen 4: First hydrogenation reaction zone

[0063] 5: Effluent from the first hydrogenation reaction zone 6: First gas-liquid separator

[0064] 7: Gas A 8: First purification unit

[0065] 9: First purified hydrogen 10: First liquid phase stream

[0066] 11: First fractionation tower 12: Liquid phase material A

[0067] 13: Liquid material B 14: Liquid material C

[0068] 15: Liquid phase material D 16: Third cycle hydrogen

[0069] 17: The third hydrogenation reaction zone 18: The second cycle hydrogen

[0070] 19: Second hydrogenation reaction zone 20: Effluent from the second hydrogenation reaction zone

[0071] 21: Effluent from the third hydrogenation reaction zone 22: Second gas-liquid separator

[0072] 23: Gas B 24: Second purification unit

[0073] 25: Second purified hydrogen 26: Second liquid phase stream

[0074] 27: Second fractionation tower 28: Liquid phase material E

[0075] 29: Liquid material F 30: Liquid material G

[0076] 31: Mixing tank 32: Aviation kerosene products DETAILED DESCRIPTION

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081]

[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.

[0082] In this article, the aviation kerosene yield is the weight percentage of the aviation kerosene product to the feedstock oil.

[0083] 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.

[0084] according to Figure 1As shown, the process flow of the method for producing aviation kerosene of the present invention is as follows: the coal tar 1 after dehydration and impurity removal and the new hydrogen 3 enter the first hydrogenation reaction zone 4, contact with the catalyst therein for hydrogenation reaction, and the obtained first hydrogenation reaction zone effluent 5 enters the first gas-liquid separator 6 and is separated to obtain gas A7 and the first liquid phase stream 10; the gas A7 enters the first purification unit 8 to remove impurities (such as hydrogen sulfide, non-condensable gas, etc.) therein, and the first purified hydrogen after 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 fractionation tower 11, and after fractionation, liquid materials A12, liquid materials B13, liquid materials C14 and liquid materials D15 are obtained respectively; wherein the liquid material D15 is mixed with the new hydrogen 3 and enters the second hydrogenation reaction zone 19 to contact with the catalyst therein for reaction, and the second hydrogenation reaction zone effluent 20, liquid materials A12 and liquid materials C14 obtained after the reaction are mixed with the new hydrogen 3 and enter the third hydrogenation reaction zone 17 to contact with the catalyst therein for hydrogenation reaction. The third hydrogenation reaction zone effluent 21 obtained by the reaction of the third hydrogenation reaction zone 17 enters the second gas-liquid separator 22 for separation, and gas B23 and the second liquid stream 26 are separated; wherein the gas B23 enters the second purification unit 24 to remove impurities therein, and the second purified hydrogen 25 after impurities are removed is mixed with the new hydrogen 3 as the second circulating hydrogen 18 and the third circulating hydrogen 16 to enter the second hydrogenation reaction zone 19 and the third hydrogenation reaction zone 17 for use. The second liquid phase stream 26 enters the second fractionation tower 27, and after fractionation, liquid phase material E28, liquid phase material F29 and liquid phase material G30 are obtained respectively, wherein liquid phase material F29 and liquid phase material B13 enter the mixing tank 31 and are mixed to obtain high specific gravity aviation kerosene product 32. Liquid phase material G30 can be divided into multiple streams, one of which is used as a product, and one is recycled to the first hydrogenation reaction zone and / or the second hydrogenation reaction zone.

[0085] In this paper, the raw materials coal tar used include two types, and the specific raw material properties are shown in Table 1.

[0086] Table 1 Coal tar raw material properties

[0087]

[0088]

[0089] Example 1

[0090] The raw material used is coal tar A in Table 1, and its properties are shown in Table 1. Figure 1The process of the invention relates to a process in which the liquid material G is divided into two streams, wherein the ratio of the liquid material G recycled to the second hydrogenation reaction zone to the liquid material G thrown out is 1:1. 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 FZC-103 and FF-22 is 1:5. Among them, the cutting temperature point of liquid material A and liquid material B is 195°C; the cutting temperature point of liquid material B and liquid material C is 210°C; the cutting temperature point of liquid material C and liquid material D is 255°C. The second hydrogenation reaction zone is sequentially filled with hydrogenation reforming pre-refining catalyst FF-66 and hydrogenation reforming catalyst FC-50 according to the flow direction of the liquid material, and the filling volume ratio of FF-66 and FC-50 is 1:5. The third hydrogenation reaction zone is filled with hydrogenation refining catalyst FF-26. The distillation range of liquid material F is 195-280°C. The hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are shown in Table 2, and the reaction results are shown in Table 4.

[0091] Example 2

[0092] The raw material is coal tar B in Table 1, and its properties are shown in Table 1. Figure 1 The process of the invention relates to a process in which the liquid material G is divided into two streams, wherein the ratio of the liquid material G recycled to the second hydrogenation reaction zone to the liquid material G thrown out is 2:1. 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 FZC-103 and FF-22 is 1:10. Among them, the cutting temperature point of liquid material A and liquid material B is 200°C; the cutting temperature point of liquid material B and liquid material C is 215°C; the cutting temperature point of liquid material C and liquid material D is 265°C. The second hydrogenation reaction zone is sequentially filled with hydrogenation reforming pre-refining catalyst FF-66 and hydrogenation reforming catalyst FC-50 according to the flow direction of the liquid material, and the filling volume ratio of FF-66 and FC-50 is 1:10. The third hydrogenation reaction zone is filled with hydrogenation refining catalyst FF-26. The distillation range of liquid material F is 200-275°C. The hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are shown in Table 2, and the reaction results are shown in Table 4.

[0093] Example 3

[0094] It is basically the same as Example 1, except that the hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are different. The hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are shown in Table 2, and the reaction results are shown in Table 4.

[0095] Example 4

[0096] It is basically the same as Example 2, except that the hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are different. The hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are shown in Table 2, and the reaction results are shown in Table 4.

[0097] Comparative Example 1

[0098] The method is basically the same as Example 1, except that the first liquid phase stream in Comparative Example 1 is not fractionated, but the first liquid phase stream enters the second hydrogenation reaction zone, and the effluent of the second hydrogenation reaction zone enters the second fractionation tower for fractionation. 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.

[0099] Comparative Example 2

[0100] The method is basically the same as Example 1, except that the first liquid phase stream in Comparative Example 2 is not fractionated, but the first liquid phase stream enters the third hydrogenation reaction zone, and the effluent of the third hydrogenation reaction zone enters the second fractionation tower for fractionation. The hydrogenation process conditions of the first hydrogenation reaction zone and the third hydrogenation reaction zone are shown in Table 3, and the reaction results are shown in Table 5.

[0101] Comparative Example 3

[0102] It is basically the same as Example 1, except that the first liquid phase stream in Comparative Example 3 is not fractionated, but the first liquid phase stream first enters the second hydrogenation reaction zone, the effluent of the second hydrogenation reaction zone then enters the third hydrogenation reaction zone, and the effluent of the third hydrogenation reaction zone enters the second fractionation tower for fractionation. The hydrogenation process conditions of the first hydrogenation reaction zone, the second hydrogenation reaction zone and the third hydrogenation reaction zone are shown in Table 3, and the reaction results are shown in Table 5.

[0103] Table 2 Hydrogenation process conditions of Examples 1-4

[0104]

[0105]

[0106] Table 3 Comparative Examples 1-3 Hydrogenation Process Conditions

[0107]

[0108]

[0109] Table 4 Reaction results of Examples 1-4

[0110] Test No. Example 1 Example 2 Example 3 Example 4 <![CDATA[Density (20 °C), g·cm -3 > 0.8422 0.8417 0.8431 0.8411 Distillation range (ASTM D86), ℃ IBP / 10% 195 / 209 200 / 209 195 / 208 200 / 210 30％ / 50％ 219 / 234 219 / 231 218 / 233 220 / 233 70％ / 90％ 246 / 258 245 / 256 243 / 256 247 / 257 95% / FBP 270 / 280 265 / 275 267 / 280 266 / 275 <![CDATA[逆流 viscosity (20 °C) / mm 2 ·s -1 > 2.764 2.745 2.832 2.836 <![CDATA[Reverse viscosity (-40 °C) / mm 2 ·s -1 > 20.86 20.33 21.64 21.76 Freezing point / ℃ -53 -52 -52 -50 Flash point (closed cup) / ℃ 82 81 83 82 Jet fuel yield, wt% 57.5 55.7 56.8 54.6

[0111] Table 5 Comparative Examples 1-4 Reaction Results

[0112] Test No. Comparative Example 1 Comparative Example 2 Comparative Example 3 <![CDATA[Density (20 °C), g·cm -3 > 0.830 0.828 0.831 Distillation range (ASTM D86), ℃ IBP / 10% 195 / 210 195 / 212 195 / 211 30％ / 50％ 220 / 234 222 / 235 221 / 235 70％ / 90％ 248 / 259 249 / 262 248 / 261 95% / FBP 269 / 280 272 / 280 271 / 280 <![CDATA[Reverse viscosity (20 °C) / mm 2 ·s -1 > 2.833 2.766 2.775 <![CDATA[Countercurrent viscosity (-40 °C) / mm 2 ·s -1 > 22.35 21.75 21.54 Freezing point / ℃ -43 -40 -42 Flash point (closed cup) / ℃ 79 80 78 Jet fuel yield, wt% 46.9 44.5 47.8

[0113] It can be seen from the product properties of Example 1 and Comparative Example 1 that some indicators of the high-density aviation kerosene obtained when coal tar is directly fed into the second hydrogenation reaction zone without being cut after hydrorefining in the first hydrogenation reaction zone cannot meet the requirements of the GJB1603 No. 6 jet fuel standard.

[0114] The properties of the aviation kerosene product obtained in the example show that the density of the high-density aviation kerosene produced by the method reaches 0.840 g / cm 3 The temperature of the kerosene is above 100 °C, and the freezing point is less than -50 °C, which meets the requirements of the GJB1603 No. 6 jet fuel standard. At the same time, the method of the present invention can effectively expand the raw material source of high-density aviation kerosene, and also enrich the deep utilization of coal tar resources, which has great economic and social benefits.

Claims

1. A method for producing aviation kerosene, comprising the following steps: (1) In the presence of hydrogen, coal tar enters the first hydrogenation reaction zone for reaction, and the reaction effluent is separated to obtain gas A, liquid material A, liquid material B, liquid material C and liquid material D; (2) Liquid phase material D enters the second hydrogenation reaction zone for reaction; (3) Liquid material A, liquid material C, and the reaction effluent of the second hydrogenation reaction zone enter the third hydrogenation reaction zone for reaction, and the reaction effluent is separated to obtain gas B, liquid material E, liquid material F, and liquid material G; (4) Liquid material B and liquid material F are mixed to obtain aviation kerosene.

2. The method for producing aviation kerosene according to claim 1, wherein: The coal tar in step (1) is 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 20μg / g, and the ash content is not more than 0.01wt%.

3. The method for producing aviation kerosene according to claim 1, wherein: 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 method for producing aviation kerosene according to claim 1, wherein: The operating conditions of the first hydrogenation reaction zone in step (1) are as follows: reaction pressure of 5.0-20.0 MPa, preferably 12.0-15.0 MPa; reaction temperature of 250-420°C, preferably 330-400°C; hydrogen-to-oil volume ratio of 500:1-1500:1, preferably 800:1-1200:1; volume space velocity of 0.1-1.2 h -1 , preferably 0.3 to 0.8h -1 .

5. The method for producing aviation kerosene according to claim 1, wherein: The cutting temperature of liquid material A and liquid material B in step (1) is 195-210°C, preferably 195-200°C; the cutting temperature of liquid material B and liquid material C is 205-220°C, preferably 205-215°C; the cutting temperature of liquid material C and liquid material D is 240-280°C, preferably 250-270°C.

6. The method for producing aviation kerosene according to claim 1, wherein: The operating conditions of the second hydrogenation reaction zone are: reaction pressure of 5.0-20.0 MPa, preferably 12.0-15.0 MPa; reaction temperature of 250-420°C, preferably 330-390°C; hydrogen-oil volume ratio of 500:1-1500:1, preferably 800:1-1200:1; volume space velocity of 0.1-1.5 h -1 , preferably 0.6~1.2h -1 .

7. The method for producing aviation kerosene according to claim 1, wherein: The operating conditions of the third hydrogenation reaction zone are: 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-oil volume ratio of 500:1-1500:1, preferably 800:1-1000:1; volume space velocity of 0.1-1.2 h -1 , preferably 0.4~1.0h -1 .

8. The method for producing aviation kerosene according to claim 1, wherein: The third hydrogenation reaction zone is filled with a hydrorefining catalyst, wherein the hydrorefining catalyst refers to a single catalyst or a series of catalysts having the functions of hydrodesulfurization, hydrodeoxygenation and hydrodenitrogenation.

9. The method for producing aviation kerosene according to claim 1, wherein: The second hydrogenation reaction zone is filled with a hydrogenation catalyst, and the hydrogenation catalyst containing amorphous silica-alumina and modified Y zeolite is used.

10. The method for producing aviation kerosene according to claim 1, wherein: The second hydrogenation reaction zone is also 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.

11. The method for producing aviation kerosene according to claim 1, wherein: The cutting temperature of liquid material E and liquid material F is 195-210°C, preferably 195-200°C; the cutting temperature of liquid material F and liquid material G is 250-315°C, preferably 260-290°C.

12. The method for producing aviation kerosene according to claim 1, wherein: The liquid material E is used as a gasoline blending component, or the liquid material E is fractionated to obtain a light component and a heavy component, the cutting temperature point is any temperature between 130 and 145° C. The cut light component is used as a catalytic reforming raw material, and the cut heavy component is used as a high-quality No. 3 jet fuel blending component.

13. The method for producing aviation kerosene according to claim 1, wherein: The liquid material G can be processed in one or more of the following ways: circulating back to the first hydrogenation reaction zone for treatment, circulating back to the second hydrogenation reaction zone for treatment, or being discarded as a diesel blending component.

14. A system for producing aviation kerosene, the system comprising: The first hydrogenation reaction zone is used to receive coal tar and hydrogen. The coal tar 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 gas A and a first liquid phase stream after separation; A first fractionation tower, which is used to receive the liquid phase material flow from the first gas-liquid separator, and obtain liquid phase material A, liquid phase material B, liquid phase material C and liquid phase material D after separation; The second hydrogenation reaction zone is used to receive the liquid material D and hydrogen from the first fractionation tower. The liquid material D and hydrogen enter the second hydrogenation reaction zone and contact with the hydrorefining catalyst therein to react; The third hydrogenation reaction zone is used to receive the liquid material A and the liquid material C from the first fractionation tower, the reaction effluent from the second hydrogenation reaction zone, and the hydrogen. The liquid material A, the liquid material C, the reaction effluent from the second hydrogenation reaction zone, and the hydrogen enter the second hydrogenation reaction zone and contact with the catalyst therein to react; A second gas-liquid separator, which is used to receive the reaction effluent obtained from the third hydrogenation reaction zone, and obtain gas B 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 liquid phase material E, liquid phase material F and liquid phase material G after separation; The mixing tank is used to receive the liquid material B from the first fractionation tower and the liquid material F from the second fractionation tower, and obtain the aviation kerosene product after mixing.

15. The system for producing aviation kerosene according to claim 14, wherein: The liquid material E is discarded and used as a gasoline blending component, or the liquid material E is fractionated to obtain a light component and a heavy component, the cutting temperature point is any temperature between 130 and 145° C. The light component after cutting is used as a catalytic reforming raw material, and the heavy component after cutting is used as a high-quality No. 3 jet fuel blending component.

16. The system for producing aviation kerosene according to claim 14, wherein: The liquid material G is connected to the first hydrogenation reaction zone and the second hydrogenation reaction zone through pipelines respectively; the liquid material G can be processed in one or more of the following ways: circulating back to the first hydrogenation reaction zone for treatment, circulating back to the second hydrogenation reaction zone for treatment, or being discarded as a diesel blending component.

Images