Method and system for producing aviation kerosene

Abstract

The present invention discloses a method and system for producing aviation kerosene, wherein the method comprises the following steps: (1) coal tar enters a 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 material D enters a second hydrogenation reaction zone for reaction; (3) liquid material A, liquid material C, and the reaction effluent of the second hydrogenation reaction zone enter a 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. A system for producing aviation kerosene is also provided. The method for producing aviation kerosene of the present invention has a simple process, and uses full-fraction coal tar as a raw material to obtain a high-quality aviation kerosene product that meets the GJB1603 No. 6 jet fuel standard, with a density of up to 0.840 g / cm 3 Above, the freezing point is less than ‑50℃.

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 of heat 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℃) can only reach a maximum of 830kg / m 3 Therefore, it is of great significance to develop high-density, low-cost jet fuel.

[0003] CN107057779A discloses a high-density jet fuel, including RP-3 jet fuel and a high-density fuel blending component. The high-density fuel blending component is made from low-quality heavy oil, which is hydro-refined to obtain cycloalkanes and aromatics with a distillation range of 180-300°C and a tail oil portion. 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 reaches 960-980 kg / m 3 However, its distillation range and aromatic content and other indicators do not meet the GJB1603 high-density jet fuel standards.

[0004] US Patent No. 4,875,992A discloses a method for producing high-density aviation kerosene from condensed-ring aromatics and hydroaromatic feedstocks. The feedstock is a crude oil rich in dicyclic aromatics and dicyclic hydroaromatics, including light catalytic cycle oil and fuel oil. The feedstock first enters a first-stage reaction for desulfurization and denitrogenation. The desulfurized and denitrogenated product enters a second-stage reaction for hydrogenation, where saturated dicyclic aromatics and dicyclic hydroaromatics are selectively hydrogenated to produce cycloalkanes while minimizing the production of low-molecular-weight hydrocarbons. The resulting high-density aviation kerosene has an API (gravity index) between 25° and 35° and an aromatics content below 50 wt%. This method requires a feedstock fraction range of 350-700°C and a dicyclic aromatic and hydroaromatic content of 85-100 wt%, placing stringent demands on the feedstock.

[0005] CN105694970A discloses a method for producing high-density jet fuel by hydrogenating low-temperature coal tar. This method involves heating a mixture of medium- and low-temperature coal tar and hydrogen, sequentially conducting a hydrogenation reaction over a hydrogenation protection catalyst and a hydrorefining catalyst. The hydrogenation product is fractionated to obtain naphtha, crude jet fuel, and tail oil. The crude jet fuel is then refined with clay to produce high-density No. 6 jet fuel. Although this method has a relatively simple process flow, it requires the use of 8wt% clay for refining. The refined clay is a solid waste that is currently difficult to regenerate. Clay solid waste is generally disposed of by incineration and landfill, causing significant environmental damage and making industrial production difficult 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 response to the problems existing in existing methods for producing aviation kerosene, the present invention provides a method and system for producing aviation kerosene. The production process is simple. By simply adjusting existing equipment, high-quality aviation kerosene products that meet the GJB1603 No. 6 jet fuel standard can be obtained using full-fraction coal tar as a 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) Liquid material B and liquid material F are mixed to obtain aviation kerosene.

[0014] Preferably, in the above-mentioned 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 blended with anthracene oil, 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 with anthracene oil.

[0015] Preferably, in the above-mentioned method for producing aviation kerosene, the first hydrogenation reaction zone is filled with a hydrogenation protection catalyst and a hydrorefining catalyst. Preferably, the hydrogenation protection catalyst and the hydrorefining 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 hydrorefining catalyst is 5:60 to 75:90.

[0016] Preferably, in the method for producing aviation kerosene, the hydrogenation protected catalyst can be produced by commercially available hydrogenation protected catalyst or by methods disclosed in the prior art. For example, the FZC series hydrogenation protected catalyst developed and produced by Sinopec (Dalian) Petrochemical Research Institute Co., Ltd. (FRIPP) can be used. Hydrogenation protected catalysts are generally based on porous refractory inorganic oxides (such as aluminum oxide, etc.), and oxides of Group VIB and / or Group VIII metals such as W, Mo, Co, Ni, etc. are active components. Other various auxiliary agents such as P, Si, F, B, etc. can also be selectively added. Hydrogenation protected catalysts are generally pre-sulfurized before use to ensure that the hydrogenation active metal is in a sulfide 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 series of catalysts having functions such as hydrodemetallization, hydrodesulfurization, hydrodeoxygenation, and hydrodenitrogenation. Generally, the hydrorefining catalyst comprises a carrier and a hydrogenation metal component, which, based on the weight of the catalyst, comprises an active metal component of Group VIB of the periodic table, such as W and / or Mo, in a content of 5 wt% to 30 wt% (preferably 10 wt% to 25 wt%) as metal oxide, and a Group VIII metal oxide, such as Co and / or Ni, in a content of 0.8 wt% to 6 wt% (preferably 1 wt% to 5 wt%) as metal oxide. 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, and titanium oxide can be selected. The hydrotreating catalyst can be a commercial catalyst available in the market or 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-mentioned 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 0.8 h -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; and 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 to 1.2 hours -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 to 1.0 h -1 .

[0035] Preferably, in the above-mentioned method for producing aviation kerosene, the second hydrogenation reaction zone is filled with a hydrogenation reforming catalyst, preferably a hydrogenation reforming catalyst containing amorphous silica-alumina and modified Y zeolite. Furthermore, the hydrogenation reforming 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 reforming catalyst may also contain components such as aluminum oxide, zirconium oxide, and titanium oxide. The specific surface area of ​​the hydrogenation reforming catalyst is 220 to 300 m2 The present invention relates to a kind of hydro-reforming catalyst of the present invention.The hydro-reforming catalyst of the present invention comprises the following: 1) a kind of hydro-reforming catalyst of the present invention, wherein said hydro-reforming catalyst comprises the following: 1) a kind of hydro-reforming catalyst of the present invention, wherein said hydro-reforming catalyst comprises the following: 2) a kind of hydro-reforming catalyst of the present invention, wherein said hydro-reforming catalyst comprises the following: 3) a kind of hydro-reforming catalyst of the present invention, wherein said hydro-reforming catalyst comprises the following: 4) a kind of hydro-reforming catalyst of the present invention, wherein said hydro-reforming catalyst comprises the following: 5) a kind of hydro-reforming catalyst of the present invention, wherein said hydro-reforming catalyst comprises the following:

[0036] Preferably, in the above-mentioned method for producing aviation kerosene, the second hydrogenation reaction zone is also loaded with a hydroreforming pre-refining catalyst, which is primarily used for denitrogenation and saturation of condensed-ring aromatics, thereby better utilizing the ring-opening performance of the hydroreforming catalyst, reducing the deactivation rate of the hydroreforming catalyst, and extending the operating cycle of the entire device. The hydroreforming pre-refining catalyst is positioned above the hydroreforming catalyst in the direction of liquid material flow, with the loading volume ratio of the hydroreforming pre-refining catalyst to the hydroreforming catalyst being 5:75 to 60:40.

[0037] Preferably, in the above-mentioned method for producing aviation kerosene, the hydrorefining catalyst above the second hydrogenation reaction zone generally comprises a carrier and a hydrogenation metal component. Based on the weight of the catalyst, the catalyst comprises a Group VIB active metal component such as W and Mo, calculated as metal oxide, in an amount of 10 wt% to 40 wt%, preferably 15 wt% to 35 wt%; and a Group VIII metal oxide such as Co and Ni, calculated as metal oxide, in an amount of 1 wt% to 10 wt%, preferably 1.5 wt% to 8 wt%. The catalyst should be presulfided before use to ensure that the hydrogenation active metal remains 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 catalyst and the supplemental refining catalyst can be selected from common commercial catalysts in the field or prepared according to general knowledge in the art. 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 loaded with a hydrorefining catalyst, which refers to a single catalyst or a series of catalysts having functions such as hydrodesulfurization, hydrodeoxygenation, and hydrodenitrogenation. Generally, the hydrorefining catalyst comprises a carrier and a hydrogenation metal component. Based on the weight of the catalyst, the carrier includes an active metal component from Group VIB of the Periodic Table, such as W and / or Mo, in an amount of 10 wt% to 35 wt% (preferably 15 wt% to 30 wt%) as metal oxide, and a Group VIII metal oxide, such as Co and / or Ni, in an amount of 1 wt% to 8 wt% (preferably 1.5 wt% to 7 wt%) as metal oxide. The catalyst should be sulfurized before use to ensure that the hydrogenation active metal remains sulfurized during the reaction. The carrier is generally an inorganic refractory oxide, specifically one or more of alumina, amorphous silica-alumina, silicon oxide, and titanium oxide. The hydrorefining catalyst can be a commercial catalyst available in the market or prepared according to general knowledge in the field. Commercial catalysts that can be selected include hydrorefining catalysts such as FF-16 and FF-26 developed and produced by Sinopec (Dalian) Research Institute of Petrochemicals Co., Ltd. (FRIPP).

[0039] Preferably, in the above-mentioned 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 fractionation temperature is any temperature between 130 and 145°C. The light component after fractionation can be used as a catalytic reforming feedstock, and the heavy component after fractionation 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, or 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] The first fractionating tower is used to receive the liquid phase stream 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 fractionating tower 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 discharged for use as a gasoline blending component, or the liquid material E is fractionated to obtain a light component and a heavy component, the fractionation temperature being any temperature between 130°C and 145°C, the light component after fractionation being used as a catalytic reforming feedstock, and the heavy component after fractionation being 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 via 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; 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.

[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 devices capable of performing gas-liquid two-phase separation. Those skilled in the art may select the appropriate one based on actual needs and knowledge.

[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 existing fractionation towers in the art, such as a packed tower, a plate tower, etc.

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

[0057] During research into high-density jet fuel production methods, it was discovered that the properties of high-density jet fuel require numerous control parameters, such as density, freezing point, aromatics content, sulfur content, and viscosity. These parameters are interrelated and mutually influential, with some even experiencing incompatibilities. Furthermore, high-density jet fuel has a narrower distillation range than conventional No. 3 jet fuel and requires a higher initial boiling point temperature, making it even more difficult to balance these various parameters. While controlling density alone can be achieved in a variety of ways, achieving acceptable density control can impact various factors, such as smoke point, freezing point, product composition, and calorific value by weight. Among these contradictions, the primary one is between density, freezing point, smoke point, and aromatics composition. The goal of this field has long been to simultaneously achieve an ideal high-density jet fuel product that meets all of these parameters. 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 divided, and different schemes and conditions are adopted for hydrogenation according to the properties of the fractions in different distillation ranges after division. The generated oils after hydrogenation are 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, first, the full-fraction coal tar is subjected to a moderate hydrorefining treatment, and then fractionated to obtain liquid material A, liquid material B, liquid material C, and liquid material D. The fractions of different distillation ranges are utilized in a cascade manner, 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 hydrocarbons. When mixed with liquid material F, it can significantly increase the density of the high-density aviation kerosene product; the cutting temperature of liquid material C is within the standard temperature of high-density aviation kerosene. After deep refining in the third hydrogenation reaction zone, the dicyclic aromatic hydrocarbons in the fraction can be saturated into cycloalkanes, which can effectively lower the freezing point of the high-density aviation kerosene product; the heavy components in liquid material D can be modified in the second hydrogenation reaction zone and then enter the third hydrogenation reaction zone for additional refining, which can significantly shift the fraction forward and improve the yield of high-density aviation kerosene. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 This is a schematic flow chart of the method and system for producing aviation kerosene according to 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 circulating hydrogen

[0070] 19: Second hydrogenation reaction zone 20: Second hydrogenation reaction zone effluent

[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 are not intended to limit the present invention.

[0078] Unless expressly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising” will be understood to include the stated elements or components but not to exclude other elements or components.

[0079] In this document, for ease of description, spatially relative terms such as "below," "beneath," "down," "above," "above," etc. may be used to describe the relationship of one element or feature to another element or feature in the accompanying drawings. It should be understood that the spatially relative terms are intended to encompass different orientations of an object in use or operation in addition to the orientation depicted in the drawings. 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 directions. Objects may also have other orientations (rotated 90 degrees or other orientations) and the spatially relative terms used herein 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 specific positions or relative relationships. In other words, in some embodiments, the terms "first", "second", etc. can also be interchangeable with each other.

[0081]

[0046] 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 precedes 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 they can be prepared according to the knowledge in this field. As the hydroprotection catalyst, FZC-100, FZC-102A, and FZC-103 hydroprotection agents developed and produced by Sinopec (Dalian) Research Institute of Petrochemical Industry Co., Ltd. can be selected; as the hydrorefining catalyst, 3936, 3996, FF-16, FF-22, FF-26 and other hydrorefining catalysts developed and produced by Sinopec (Dalian) Research Institute of Petrochemical Industry Co., Ltd. can be selected; as the hydrorefining catalyst, FF-66, FF-76 and other hydrorefining catalysts developed and produced by Sinopec (Dalian) Research Institute of Petrochemical Industry Co., Ltd. can be selected as the hydrorefining catalyst for the upper part of the hydroreforming reaction zone and the supplementary hydrorefining catalyst for the lower part can be selected; as the hydrorefining catalyst, 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) Research Institute of Petrochemical Industry Co., Ltd. can be selected.

[0084] according to Figure 1As shown, the process flow of the method for producing aviation kerosene of the present invention is as follows: coal tar 1 after dehydration and impurity removal and new hydrogen 3 enter the first hydrogenation reaction zone 4, contact the catalyst therein to carry out a hydrogenation reaction, and the resulting first hydrogenation reaction zone effluent 5 enters the first gas-liquid separator 6 and is separated to obtain gas A7 and a first liquid phase stream 10; gas A7 enters the first purification unit 8 to remove impurities (such as hydrogen sulfide and non-condensable gases) therein. The first purified hydrogen after impurity removal is mixed with the new hydrogen 3 as the first circulating hydrogen 2 and returned to the first hydrogenation reaction zone 4. The separated first liquid stream 10 enters a first fractionation tower 11, where it undergoes fractional distillation to produce liquid material A12, liquid material B13, liquid material C14, and liquid material D15, respectively. Liquid material D15 is mixed with fresh hydrogen 3 and then enters a second hydrogenation zone 19, where it contacts the catalyst for a reaction. The second hydrogenation zone effluent 20, liquid material A12, and liquid material C14 are mixed with fresh hydrogen 3 and then enter a third hydrogenation zone 17, where they contact the catalyst for a hydrogenation reaction. The third hydrogenation zone effluent 21, produced in the third hydrogenation zone 17, enters a second gas-liquid separator 22 for separation, producing gas B23 and a second liquid stream 26. Gas B23 enters a second purification unit 24 for impurity removal. The purified second hydrogen 25, after impurity removal, is then mixed with fresh hydrogen 3 as the second recycle hydrogen 18 and third recycle hydrogen 16, which are then fed into the second and third hydrogenation zones 19 and 17, respectively. Second liquid stream 26 enters second fractionation tower 27, where it undergoes fractionation to yield liquid material E28, liquid material F29, and liquid material G30. Liquid material F29 and liquid material B13 are then mixed in mixing tank 31 to yield high-gravity aviation kerosene product 32. Liquid material G30 can be split into multiple streams, one of which is used as the product and the other recycled to the first and / or second hydrogenation reaction zones.

[0085] In this paper, the raw materials used include two types of coal tar, 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 is coal tar A in Table 1, and its properties are shown in Table 1. Figure 1The process involves splitting liquid feed G into two streams, with the ratio of liquid feed G recycled to the second hydrogenation reaction zone to that discarded being 1:1. The first hydrogenation reaction zone is loaded with hydrogenation protectant FZC-103 and hydrorefining catalyst FF-22, with the loading volume ratio of FZC-103 to FF-22 being 1:5. The cutoff temperature between liquid feed A and liquid feed B is 195°C; the cutoff temperature between liquid feed B and liquid feed C is 210°C; and the cutoff temperature between liquid feed C and liquid feed D is 255°C. The second hydrogenation reaction zone is loaded with hydrorefining catalyst FF-66 and hydrorefining catalyst FC-50, sequentially along the direction of liquid feed flow, with the loading volume ratio of FF-66 to FC-50 being 1:5. The third hydrogenation reaction zone is loaded with hydrorefining catalyst FF-26. The distillation range of liquid feed 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 involves splitting liquid feed G into two streams, with the ratio of liquid feed G recycled to the second hydrogenation reaction zone to that discarded being 2:1. The first hydrogenation reaction zone is loaded with hydrogenation protectant FZC-103 and hydrorefining catalyst FF-22, with the loading volume ratio of FZC-103 to FF-22 being 1:10. The cutoff temperature between liquid feed A and liquid feed B is 200°C; the cutoff temperature between liquid feed B and liquid feed C is 215°C; and the cutoff temperature between liquid feed C and liquid feed D is 265°C. The second hydrogenation reaction zone is loaded with hydrorefining catalyst FF-66 and hydrorefining catalyst FC-50, sequentially along the liquid feed flow direction, with the loading volume ratio of FF-66 to FC-50 being 1:10. The third hydrogenation reaction zone is loaded with hydrorefining catalyst FF-26. The distillation range of liquid feed 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] The results are basically the same as those in Example 1, except that the hydrogenation process conditions in the first hydrogenation reaction zone, the second hydrogenation reaction zone, and the third hydrogenation reaction zone are different. The hydrogenation process conditions in 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 process was essentially the same as Example 1, except that the first liquid stream in Comparative Example 1 was not fractionated. Instead, the entire first liquid stream entered the second hydrogenation reaction zone, and the effluent from the second hydrogenation reaction zone entered the second fractionation tower for fractionation. The hydrogenation process conditions for the first and second hydrogenation reaction zones are shown in Table 3, and the reaction results are shown in Table 5.

[0099] Comparative Example 2

[0100] The process was essentially the same as Example 1, except that the first liquid stream in Comparative Example 2 was not fractionated. Instead, the entire first liquid stream entered the third hydrogenation reaction zone, and the effluent from the third hydrogenation reaction zone entered the second fractionation tower for fractionation. The hydrogenation process conditions for the first and third hydrogenation reaction zones are shown in Table 3, and the reaction results are shown in Table 5.

[0101] Comparative Example 3

[0102] This process is essentially the same as Example 1, except that in Comparative Example 3, the first liquid stream is not fractionated. Instead, the first liquid stream first enters the second hydrogenation reaction zone, the effluent from the second hydrogenation reaction zone then enters the third hydrogenation reaction zone, and the resulting effluent from the third hydrogenation reaction zone enters the second fractionation tower for fractionation. The hydrogenation process conditions for the first, second, and third hydrogenation reaction zones are shown in Table 3, and the reaction results are shown in Table 5.

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

[0104]

[0105]

[0106] Table 3 Hydrogenation process conditions for Comparative Examples 1-3

[0107]

[0108]

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

[0110] Test number 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[Countercurrent 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 Aviation kerosene yield, wt% 57.5 55.7 56.8 54.6

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

[0112] Test number 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 Aviation kerosene yield, wt% 46.9 44.5 47.8

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

[0114] The properties of the aviation kerosene product obtained in the examples show that the density of the high-density aviation kerosene produced by this method reaches 0.840 g / cm 3 The freezing point is less than -50°C, meeting the requirements of 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, enrich the deep utilization of coal tar resources, and 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; the cutting temperature of liquid material A and liquid material B is 195-210°C, the cutting temperature of liquid material B and liquid material C is 205-220°C, and the cutting temperature of liquid material C and liquid material D is 240-280°C; the first hydrogenation reaction zone is filled with a hydrogenation protection catalyst and a hydrorefining catalyst, and the hydrogenation protection catalyst and the hydrorefining catalyst are sequentially filled in accordance with the flow direction of the liquid material, and the ratio of the hydrogenation protection catalyst to the hydrorefining catalyst is 5:60-75:90 based on the filling volume ratio; (2) The liquid phase material D enters the second hydrogenation reaction zone for reaction; the second hydrogenation reaction zone is filled with a hydrogenation catalyst containing amorphous silica-alumina and modified Y zeolite; the second hydrogenation reaction zone is also filled with a hydrogenation pre-refined catalyst. According to the flow direction of the liquid phase material, the hydrogenation pre-refined catalyst is arranged above the hydrogenation catalyst. The filling volume ratio of the hydrogenation pre-refined catalyst to the hydrogenation catalyst is 5:75 to 60:40; (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. The reaction effluent is separated to obtain gas B, liquid material E, liquid material F, and liquid material G; the third hydrogenation reaction zone is filled with a hydrorefining catalyst; the cutting temperature of liquid material E and liquid material F is 195-210°C, and the cutting temperature of liquid material F and liquid material G is 250-315°C; (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 greater than 0.15 wt%, the metal content is not greater than 20 μg / g, and the ash content is not greater than 0.01 wt%.

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

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: reaction pressure of 12.0-15.0 MPa, reaction temperature of 330-400°C, hydrogen-to-oil volume ratio of 800:1-1200:1, volume space velocity of 0.3-0.8 h -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 195-200°C, the cutting temperature of liquid material B and liquid material C is 205-215°C, and the cutting temperature of liquid material C and liquid material D is 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, reaction temperature of 250-420°C, hydrogen-to-oil volume ratio of 500:1-1500:1, and volume space velocity of 0.1-1.5 h -1 .

7. The method for producing aviation kerosene according to claim 1, wherein: The operating conditions of the second hydrogenation reaction zone are: reaction pressure of 12.0-15.0 MPa, reaction temperature of 330-390°C, hydrogen-to-oil volume ratio of 800:1-1200:1, and volume space velocity of 0.6-1.2 h -1 .

8. 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, reaction temperature of 250-420°C, hydrogen-to-oil volume ratio of 500:1-1500:1, and volume space velocity of 0.1-1.2 h -1 .

9. The method for producing aviation kerosene according to claim 1, wherein: The operating conditions of the third hydrogenation reaction zone are: reaction pressure of 12.0-15.0 MPa, reaction temperature of 330-380°C, hydrogen-to-oil volume ratio of 800:1-1000:1, and volume space velocity of 0.4-1.0 h -1 .

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

11. 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 feedstock, and the cut heavy component is used as a high-quality No. 3 jet fuel blending component.

12. 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.

13. A system for producing aviation kerosene according to the method of claim 1, 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; The first fractionating tower is used to receive the liquid phase stream 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 hydrogenation 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 hydrorefining 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 fractionating tower 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.

14. The system for producing aviation kerosene according to claim 13, 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 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.

15. The system for producing aviation kerosene according to claim 13, 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.

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