Background
The hydrocracking technology has the characteristics of high production flexibility, strong raw material adaptability and high product quality, and plays a role of a medium-flow column in the aspect of adjusting the production balance of a whole plant. The products of the hydrocracking process include natural gas, liquefied gas, naphtha, jet fuel, diesel, and tail oil. The traditional hydrocracking technology mainly produces naphtha or middle distillate according to market change.
Along with the reduction of diesel oil demand in China, the automobile holding capacity is increased, and the diesel-gasoline ratio is continuously reduced. In order to adapt to the drastic change of the oil market, the development of hydrocracking technology for producing heavy naphtha in large quantity is urgent. The hydrocracking heavy naphtha has the characteristics of high naphthene, aromatic hydrocarbon and aromatic hydrocarbon potential, and is suitable for being used as a catalytic reforming feed. After catalytic reforming dehydrogenation, the generated oil can be used as a chemical raw material and also can be used as a high-quality gasoline blending component. The higher the content of monocyclic aromatics in the heavy naphtha is, the higher the octane number of the reformed gasoline is. It should be noted that a part of monocyclic aromatic hydrocarbons with side chains is converted from heavy components, and the content of monocyclic aromatic hydrocarbons in the effluent of a hydrofining reactor (hereinafter referred to as refined oil) is closely related to the refining depth. In view of the above problems, it is necessary to develop a corresponding hydrogenation process technology to retain monocyclic aromatic hydrocarbons in heavy naphtha to the maximum extent, so as to achieve the purpose of increasing the yield and aromatic hydrocarbon potential of heavy naphtha.
In hydrocracking technology, there are many reports on hydrocracking processes and technologies, but there are few hydrocracking processes for increasing heavy naphtha aromatics potential. CN 1955257A discloses a hydrocracking method for producing chemical raw materials, mixing poor quality catalytic cracking diesel oil and heavy hydrocracking raw materials in proportion, then carrying out hydrotreating and hydrocracking, and controlling the operation conditions to make the yield of heavy naphtha reach about 40wt%. The heavy naphtha can be used as a high quality catalytic reforming feedstock. However, after the inferior diesel oil is doped, the smoke point of the aviation kerosene and the cetane number of the diesel oil are reduced, and even the diesel oil is unqualified.
CN 104560169A discloses a hydrocracking process for producing heavy naphtha from a high nitrogen feedstock. The high-nitrogen raw oil and the hydrogen-rich gas are mixed and then heated to carry out the hydrofining reaction, the hydrocracking tail oil fraction is pressurized and then mixed with the recycle hydrogen to enter the hydrocracking reaction, and the tail oil fraction which is difficult to convert can be completely converted into the naphtha fraction. However, when the hydrocracking tail oil is recycled, the processing load is reduced due to the load limitation of a feed pump.
CN 104611062A discloses a method for producing high-octane gasoline. The method is used for processing catalytic diesel oil to produce high-octane gasoline fraction, fully utilizes the characteristics of hydrocracking and reactive distillation processes, reduces secondary cracking reaction of light fraction, and improves the liquid yield, wherein the gasoline fraction yield is more than 90%. The gasoline product has high octane number, simple process and energy saving. This process is limited by the nature of the feedstock and does not significantly increase the aromatic potential of the heavy naphtha when the aromatics content in the feedstock is low.
Disclosure of Invention
The invention aims to realize the purposes of retaining monocyclic aromatic hydrocarbon to the maximum extent and improving the yield and the aromatic hydrocarbon potential of heavy naphtha by accurately controlling the hydrorefining reaction of wax oil and feeding the cut refined oil in sections according to the distribution characteristics of the nitrogen content of the refined oil.
After research, the inventor of the invention finds that the content of monocyclic aromatic hydrocarbon in the refined oil is the highest when the temperature of hydrofining reaction is between 340 and 350 ℃ under the reaction conditions of no matter what pressure, space velocity and hydrogen-oil ratio by taking the conventional straight-run wax oil as a raw material. However, in this temperature range, the nitrogen content of the refined oil is greater than 100ppm, which cannot meet the nitrogen content requirement of the refined oil and can cause basic nitrogen poisoning to the hydrocracking catalyst. After the refined oil is cut, the nitrogen content in the light component is low, and the nitrogen content in the heavy component is high. By controlling a proper cut point, the nitrogen content of the light component is not more than 10ppm, and the light component can be used as a direct feed of a hydrocracking reactor. The heavy components need to be refined additionally and can be used as the feed of the hydrocracking reactor. Therefore, the hydrofinishing reaction conditions can be precisely controlled so that the maximum amount of monocyclic aromatic hydrocarbons in the refined oil is retained. After the refined oil is subjected to hydrocracking reaction, a large amount of monocyclic aromatic hydrocarbon in the refined oil can be converted into heavy naphtha fraction, so that the aromatic hydrocarbon potential of the heavy naphtha is effectively improved.
The prior hydrocracking technology only has nitrogen content requirement on hydrofined oil, and does not directionally control the composition of the hydrofined oil, so that the product quality cannot be obviously improved. In order to overcome the defects in the prior art, the invention provides a hydrocracking process for producing high-quality reforming raw materials.
The hydrocracking process for producing the high-quality reforming raw material comprises the following steps of:
(1) Providing a hydrofining reaction zone, wherein the hydrofining reaction zone comprises hydrofining catalysts; providing a hydrocracking reaction zone, wherein the hydrocracking reaction zone sequentially comprises a hydrofining catalyst bed layer and a plurality of hydrocracking catalyst bed layers which are connected in series;
(2) Feeding the nitrogen-containing raw oil and hydrogen into a hydrofining reaction zone, and carrying out contact reaction with a hydrofining catalyst under the conditions that the average reaction temperature is 330 to 350 ℃, and preferably 335 to 345 ℃;
(3) Carrying out gas-liquid separation on the hydrofining effluent obtained in the step (2), and enabling the obtained liquid phase to enter a fractionating tower to obtain a hydrofining light component and a hydrofining heavy component; the cutting temperature of the light component and the heavy component is 420 to 500 ℃, and preferably 440 to 480 ℃;
(4) Allowing the heavy components obtained in the step (3) and hydrogen to enter a hydrocracking reaction zone, and sequentially contacting and reacting with a hydrofining catalyst and a hydrocracking catalyst;
(5) The light component obtained in the step (3) and optional hydrogen enter a middle bed layer of a hydrocracking reaction zone to contact and react with a hydrocracking catalyst;
(6) And separating and fractionating reaction effluent obtained by hydrocracking to obtain a gas product and a liquid product containing a heavy naphtha component.
In the invention, the nitrogen-containing raw material is a low-nitrogen wax oil raw material, the initial boiling point of the low-nitrogen wax oil raw material is generally 260-320 ℃, the final boiling point of the low-nitrogen wax oil raw material is generally 400-530 ℃, and the nitrogen content is less than 1200 mu g/g. When processing inferior nitrogenous raw materials, a protective agent is generally filled before a hydrofining agent, and the protective agent comprises a demetallizing agent, a carbon residue removing agent, a silicon catching agent and the like.
In the step (1), 1 to 6 hydrofining catalyst bed layers are generally arranged in a hydrofining reaction zone along the material flow direction, and preferably 2 to 4 hydrofining catalyst bed layers are arranged; the hydrocracking reaction zone is generally provided with 1 refined catalyst bed and 2 to 6 cracking catalyst beds along the material flow direction.
The hydrofinishing catalyst, which is generally comprised of a support and a metal. The metal is non-noble metal, the main active metal is the VIB metal component in the periodic table of elements, such as tungsten or/and molybdenum, and the weight of the metal oxide is 5 to 50wt%, preferably 10 to 40wt%. The auxiliary agent is mainly a metal component in the VIIIB (fourth B) in the periodic table of elements, such as cobalt or/and molybdenum, and the auxiliary agent is 2 to 30wt% and preferably 3 to 15wt% based on the weight of the metal oxide. The carrier can be a single carrier or a mixture of alumina, amorphous silica-alumina and a molecular sieve, and the carrier accounts for 60 to 90wt%, preferably 60 to 85wt%. The above carrier may be used to carry an active metal and prepare a hydrorefining catalyst, or an industrial catalyst such as FF-46, FF-56, and FF-66 from the institute of petrochemical engineering may be used.
In the step (2), the average reaction temperature in the hydrogenation refining reaction zone is preferably 335 to 345 ℃.
The cutting point of the light and heavy components in the step (3) is 420 to 500 ℃, and preferably 440 to 480 ℃. Or the nitrogen content in the light component after cutting is controlled to be not more than 20ppm, preferably not more than 10ppm, based on the nitrogen content in the light and heavy components.
The hydrocracking catalyst generally comprises a cracking component, a hydrogenation component and a binder. The cracking component typically comprises amorphous silica-alumina and/or molecular sieves, typically molecular sieves such as Y-type or β -type molecular sieves. The binder is typically alumina or silica. The hydrogenation component is a metal, a metal oxide or a metal sulfide of a metal in a VI group, a VII group or a VIII group, and more preferably one or more of iron, chromium, molybdenum, tungsten, cobalt, nickel or sulfides or oxides thereof. The content of the hydrogenation component is usually 10 to 35wt% based on the weight of the catalyst. Specifically, the existing hydrocracking catalyst may be selected, or a specific hydrocracking catalyst may be prepared as required. Commercial hydrocracking catalysts are mainly: FC-12, FC-16, FC-24, FC-32, FC-46, FC-52 and the like developed by FRIPP.
In the hydrocracking reaction zone in the step (2), the volume space velocity of the fresh feed relative to the hydrofining catalyst is 4.0 to 16 h -1 Preferably 6.0 to 14.0 hours -1 . The volume space velocity of the fresh feed relative to the hydrocracking catalyst is 0.5 to 3 hours -1 Preferably 1.0 to 2.5 hours -1 。
And (3) the feeding position of the light component obtained in the step (5) is an intermediate cracking catalyst bed layer of a hydrocracking reaction zone. The middle cracking catalyst bed layer of the hydrocracking reaction zone refers to the second cracking catalyst bed layer of the hydrocracking catalyst bed layers and any subsequent catalyst bed layer, and preferably refers to any one of the 2 nd to 4 th cracking catalyst bed layers.
In step (6), the liquid product obtained by hydrocracking usually comprises at least one of light naphtha, aviation kerosene, diesel oil and tail oil fraction, preferably aviation kerosene or diesel oil, in addition to heavy naphtha. Further, the obtained tail oil or/and diesel oil can be taken out of the device as a product, and can also be recycled to the inlet of a hydrofining reactor or a hydrocracking reactor, so that the yield of the obtained heavy naphtha is increased.
The hydrocracking process of the present invention can be used in any hydrocracking field.
Compared with the prior art, the method has the following beneficial effects:
1. the inventor of the application researches and discovers that at a proper hydrofining temperature, the monocyclic aromatic hydrocarbon content in the refined oil has a highest value, and the monocyclic aromatic hydrocarbon content is only related to the refining temperature and is not related to conditions such as space velocity, pressure, hydrogen-oil ratio and the like. Moreover, the monocyclic aromatic components in the refined oil are mainly distributed among the light components. Based on the discovery, the invention provides the technical scheme. And determining the proper reaction temperature of the hydrofining device and the cutting scheme of the refined oil according to the aromatic saturation characteristics of the hydrofining reaction and the nitrogen content distribution of the refined oil. The refined oil is divided into light components and heavy components which are enriched in monocyclic aromatic hydrocarbon and then enter a hydrocracking reactor in a segmented mode, the monocyclic aromatic hydrocarbon components can be reserved to the maximum extent, and after the monocyclic aromatic hydrocarbon components are converted into heavy naphtha, the yield and the aromatic hydrocarbon potential of the heavy naphtha can be effectively improved. Meanwhile, the heavy component of the refined oil passes through a refined catalyst bed layer of the hydrocracking reaction zone, so that the nitrogen content of the heavy component is further reduced, the contained aromatic hydrocarbon with more than two rings can be further subjected to hydrogenation saturation and is continuously converted into monocyclic aromatic hydrocarbon, and the potential aromatic hydrocarbon content of the obtained heavy naphtha component is also improved after passing through a hydrocracking catalyst.
2. And (3) performing light-weight segmentation on refined oil liquid, and allowing light components obtained by hydrofining to enter 2 to 4 catalyst bed layers of a middle cracking catalyst bed layer of a hydrocracking reaction zone, wherein the light components can also be used as cold oil to play a role in heat extraction and reduce the outlet temperature of the hydrocracking catalyst bed layer.
3. The invention separates the refined oil into light and heavy components, and the heavy component is further hydrofined at higher temperature in the cracking reaction zone, which is also beneficial to deeply removing nitrogen-containing compounds in the heavy component, and can inhibit the over-saturation of aromatic hydrocarbon and avoid the potential loss of heavy stone aromatic hydrocarbon.
Detailed Description
The process of the present invention will be further described with reference to the accompanying drawings, in which many of the equipment such as pumps, heat exchangers, compressors, furnaces, stripping section water wash and dehydration columns, etc., are omitted, but are well known to those skilled in the art.
The process of the method provided by the invention is described in detail as follows: raw oil 1 and mixed hydrogen 2 are mixed and then enter a hydrofining reactor 3, sequentially pass through a hydrofining catalyst bed layer from top to bottom, refined oil 4 enters a fractionating tower 5 to be divided into light components and heavy components, the light components 6 obtained at the upper part enter the middle part of a hydrocracking reactor 7, the heavy components 8 enter the inlet of the hydrocracking reactor to be supplemented and refined, hydrocracking generated oil 9 enters a separator 10, gas 11 discharged at the upper part passes through a desulfurizing tower 12, the obtained circulating hydrogen 13 is pressurized by a circulating hydrogen compressor 14 and then is mixed with new hydrogen 15, liquid phase 16 obtained at the middle lower part of the separator enters a subsequent fractionating tower 17, and fractionating tower top gas 18, light naphtha 19, heavy naphtha 20, aviation kerosene 21, diesel 22 and tail oil 23 are obtained.
The process of the present invention will be further illustrated with reference to the following examples, but the invention is not limited thereto.
TABLE 1 Properties of the stock oils
TABLE 2 catalysts
TABLE 3 reaction conditions
The feed oil used in the following examples and comparative examples was a sand light VGO, the properties of which are shown in Table 1. The hydrocracking reactor is exemplified by typical four cracking catalyst beds, with a hydrofinishing catalyst bed disposed upstream of the uppermost cracking catalyst bed. In the hydrocracking reactor, the filling volume ratio of the hydrofining catalyst to the hydrocracking catalyst is as follows. The process flow diagram is shown in figure 1. The hydrofinishing agent FF-66 and the hydrocracking agent FC-46 used in the examples and the comparative examples were industrial agents, and the properties of both are shown in Table 2. The process evaluation conditions for all examples and comparative examples are shown in Table 3. The boiling ranges of the heavy naphtha in the examples and the comparative examples are 65 to 177 ℃.
Example 1
The average temperature of the hydrofining reactor is 335 ℃, the cut point of the light and heavy components is 470 ℃, and the airspeed of the hydrofining agent of the hydrocracking reactor is 6.0 h -1 The space velocity of the hydrocracking agent is 1.8h -1 . And the light component enters the inlet of a second reaction zone of the hydrocracking reactor, and the heavy component directly enters the inlet of the hydrocracking reactor. Other process conditions are shown in table 3.
Example 2
The average temperature of the hydrofining reactor is 335 ℃, the cutting point of the light and heavy components is 460 ℃, and the airspeed of the hydrofining agent of the hydrocracking reactor is 8.0 h -1 The airspeed of the hydrocracking agent is 1.8h -1 . And the light component enters the inlet of a second reaction zone of the hydrocracking reactor, and the heavy component directly enters the inlet of the hydrocracking reactor. Other process conditions are shown in table 3.
Example 3
The average temperature of the hydrofining reactor is 345 ℃, the cutting point of the light and heavy components is 470 ℃, and the airspeed of the hydrofining agent of the hydrocracking reactor is 6.0 h -1 HydrocrackingThe space velocity of the agent is 1.8h -1 . And the light component enters the inlet of the second reaction zone of the hydrocracking reactor, and the heavy component directly enters the inlet of the hydrocracking reactor. Other process conditions are shown in table 3.
Example 4
The average temperature of the hydrofining reactor is 345 ℃, the cutting point of the light and heavy components is 460 ℃, and the space velocity of the hydrofining agent of the hydrocracking reactor is 8.0 h -1 The space velocity of the hydrocracking agent is 1.8h -1 . And the light component enters the inlet of the third reaction zone of the hydrocracking reactor, and the heavy component directly enters the inlet of the hydrocracking reactor. Other process conditions are shown in table 3.
Comparative example 1
By adopting the conventional hydrocracking process, the effluent of the hydrofining reaction is not cut, and only a hydrocracking catalyst is filled in a hydrocracking reactor. The average temperature of the hydrofining reactor is 375 ℃, and the space velocity of hydrofining agent of the hydrocracking reactor is 8.0 h -1 The space velocity of the hydrocracking agent is 1.8h -1 . The refined oil and hydrogen directly enter the inlet of the hydrocracking reactor. Other process conditions are shown in table 3.
Comparative example 2
The procedure is as in comparative example 1. The average temperature of the hydrofining reactor is 340 ℃, and the space velocity of hydrofining agent of the hydrocracking reactor is 8.0 h -1 The airspeed of the hydrocracking agent is 1.8h -1 . The refined oil and hydrogen directly enter the inlet of the hydrocracking reactor. Other process conditions are shown in table 3.
Table 4 example test results
TABLE 5 comparative example test results
The experiment results of the comparative example and the example show that the hydrocracking process can effectively improve the heavy componentNaphtha yield and aromatic hydrocarbon. When the average hydrofining reactor is 345 ℃, the cutting point of the light and heavy components is 470 ℃, and the space velocity of hydrofining agent in the hydrocracking reactor is 6.0 h -1 The space velocity of the hydrocracking agent is 1.8h -1 When the light components enter the inlet of the second reaction zone of the hydrocracking reactor, the yield of the heavy naphtha is 47.9 percent at most, and the maximum arene potentiality is 58.0 percent at most.