CN109777483B - Method for stabilizing quality of hydrocracking product - Google Patents
Method for stabilizing quality of hydrocracking product Download PDFInfo
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- CN109777483B CN109777483B CN201711118880.2A CN201711118880A CN109777483B CN 109777483 B CN109777483 B CN 109777483B CN 201711118880 A CN201711118880 A CN 201711118880A CN 109777483 B CN109777483 B CN 109777483B
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Abstract
The invention discloses a method for stabilizing quality of a hydrocracking product, which comprises the following steps: the hydrocracking raw material and hydrogen are mixed and then enter a hydrocracking pretreatment reactor for refining reaction, the reaction effluent enters a hydrocracking reactor for hydrocracking reaction, four hydrocracking catalyst beds are arranged in the hydrocracking reactor, a hydrogenation post-treatment catalyst bed is arranged at the bottom of the hydrocracking reactor, when the conversion rate of fractions at the temperature of more than 350 ℃ in the hydrocracking raw material is 80-89%, arranging hydrogenation post-treatment catalyst beds among the hydrocracking catalyst beds, wherein the volume ratio of the hydrogenation post-treatment catalysts filled among the beds and at the bottom of the reactor along the material flow direction is 5-15:10-30:20-40:30-50, and the volume ratio of the hydrogenation post-treatment catalysts (total) filled in the hydrocracking reactor to the hydrocracking catalysts (total) filled in the hydrocracking reactor is 1: 6-8, separating the hydrocracking product to obtain various products. The method can obviously improve the stability of the quality of the hydrocracking product.
Description
Technical Field
The invention relates to a method for stabilizing quality of a hydrocracking product, in particular to a method for stabilizing quality of a heavy naphtha product in a hydrocracking product at the middle and later stages in a long-period operation process.
Background
The hydrocracking process is a process for converting heavy distillate oil (VGO, CGO and DAO) into target products such as light oil, middle distillate oil and the like by hydrodesulfurization, hydrodenitrogenation, polycyclic aromatic hydrocarbon hydrosaturation and ring-opening cracking under the conditions of hydrogen presence, high temperature and high pressure and under the action of a catalyst, has the characteristics of flexible operation, good product quality and environmental friendliness, is one of the main processes for deep processing of the heavy distillate oil, not only is an important means for producing light oil products in the oil refining industry, but also becomes a key technology of petrochemical enterprises, exerts the irreplaceable effect of other processes, has become the standard configuration of various current large oil refining enterprises, and plays a key role in combination of oil, chemical and fiber and flow optimization configuration of the whole plant.
The hydrocracking device is used as a standard preparation device of an oil refining enterprise, plays a key linking transition role between oil refining-oil refining and oil refining-chemical engineering, the liquid product of the hydrocracking device can be used as a gasoline blending component to produce high-quality gasoline, the heavy naphtha can be used as a catalytic reforming unit to feed and produce reformed gasoline or aromatic hydrocarbon products, the kerosene can be used as aviation kerosene or low-freezing diesel oil products, the diesel oil can be used as high-quality fuel oil, and the tail oil can be used as lubricating oil base stock or an ethylene cracking raw material.
At present, when the domestic hydrocracking device is in actual use, according to the difference of oil product balance of enterprises, target products or production modes of the domestic hydrocracking device are different, but in order to meet the market demand, higher economic benefit is pursued, and the adjustment mode of the domestic hydrocracking device is stronger in consistency on the whole. At present, diesel oil products in domestic markets are excessive and are blocked in sales, so that the improvement of the diesel oil-gas ratio and the reduction of the diesel oil yield become the fundamental targets of optimization and upgrading of oil refining enterprises at present and even in recent years. The diesel-gasoline ratio is reduced, although the way and the method are not single, on the whole, the yield of diesel oil needs to be reduced, on the other hand, the yield of gasoline needs to be increased, for a hydrocracking device, the two modes of producing gasoline and producing diesel oil can be flexibly switched through the change of the process, the operation condition and the catalyst, and for the selected catalyst, the improvement of the yield of gasoline becomes a main production target on the premise of ensuring the qualification of other products under the current production working condition, so that the conversion depth of the reaction process is increased, the operation severity is increased, and the reaction temperature and the conversion rate are higher.
The hydrocracking process simultaneously carries out a plurality of reactions. Cracking reactions typically involve the cleavage of carbon-carbon single bonds to lower molecular weight compounds, including olefins, and the cleavage of aromatic side chains of higher molecular weight compounds. Hydrogenation reactions also occur in the hydrocracking unit, including the hydrogenation of double bonds of aromatic and olefinic compounds. Therefore, in the reaction process, the existing hydrogenation process is accompanied by the dehydrogenation process, the two processes have certain difference in equilibrium constants under different reaction conditions, and the olefin generated in the reaction process is not beneficial to the stability of subsequent products, so that a certain amount of refined catalyst is always added to the bottommost part of a cracking reactor in the general hydrocracking process, namely, the refined catalyst is a post-treatment catalyst, and the function of the refined catalyst can be used for carrying out hydrogenation saturation on the olefin generated in the reaction process, so that the stability of the subsequent products is improved, and the trend of generating mercaptan is reduced, for example, the excessive standard of mercaptan in heavy naphtha and aviation kerosene products can be avoided, so that the quality of the products is ensured to be qualified, or the excessive standard of the olefin of the heavy naphtha, namely the excessive bromine index is avoided, so that the deactivation rate.
CN200610047864.4 describes a one-stage serial hydrocracking method, in which a one-stage serial hydrocracking pretreatment reactor is filled with a pretreatment catalyst and a hydrocracking catalyst, and in the hydrocracking reactor is filled with a hydrocracking catalyst and a post-hydrogenation treatment catalyst. Compared with the prior art, the method can improve the overall activity of the hydrocracking unit, increase the processing capacity of the unit or prolong the operation period, and simultaneously improve the product quality. CN200780020520.7 introduces a hydrocracking method for producing low-sulfur diesel, which can realize the production of low-sulfur diesel after the reaction is carried out in single-stage or two-stage hydrocracking and the optimized promotion of a catalyst and the proper treatment of the reaction process. However, both of them involve the phenomena that the temperature of the reaction zone of the post-treatment of hydrocracking is too high, the activity of the catalyst is not matched very well, the product quality is not stable, and the problems are more serious especially in the middle and later stages of the reaction.
CN201510604895.4 introduces a preparation method of a post-treatment type hydrocracking catalyst, which can realize the production of products with higher hydrogenation activity and selectivity by optimizing and limiting the preparation process of the catalyst, and the selectivity of middle distillate oil of the products is higher, thus being suitable for treating hydrocracking catalysts consisting of various metals. But still belongs to the hydrocracking catalyst category in principle, if used for hydrogenation after-treatment, the stability of product quality is difficult to guarantee, and after short-term operation, the problem that the content of olefin in a liquid phase product exceeds the standard or mercaptan exceeds the standard can occur.
CN02144950.3 introduces a hydrocracking post-treatment catalyst and a preparation method thereof, and the catalyst can realize the characteristics of hydrodemercaptan removal, high olefin saturation activity and good stability by improving the preparation of the catalyst, and is particularly suitable for the process of producing low-sulfur alcohol products by hydrocracking post-treatment. Although the preparation process of the catalyst is improved, the preparation process is not adapted to the actual reaction condition of aftertreatment, the characteristic that the product quality is difficult to stabilize in the middle and later stages of the reaction still exists, in addition, key indexes such as acidity of the catalyst are not explained, the improvement of hydrogenation performance and cracking performance is not involved, and the like, and the problem still exists in the practical application.
CN02144949.X introduces a hydrotreating catalyst and its preparation method, and the improvement of the catalyst preparation process can realize the features of high hydrogenation sweetening and olefin saturation activity, especially suitable for the sweetening process after hydrocracking. The method still belongs to a patent related to a catalyst in principle, a process is not limited and modified, the aim of completely and uniformly controlling the preparation and process application of the catalyst is not achieved, the optimization of the product quality cannot be thoroughly realized, in addition, the preparation method is not optimized for some key parameters, and after the reaction temperature is overhigh during application, the inactivation rate of the catalyst is accelerated, and the severity is increased, so that the condition that the quality of individual products does not reach the standard is caused.
Disclosure of Invention
Aiming at the problems that in the prior art, the olefins are overproof, namely the bromine index of heavy naphtha is higher, mercaptan is higher, the sulfur content of aviation kerosene products is overproof and the like, which commonly exist in the later stage of a hydrocracking reaction process using a post-treatment catalyst, the invention provides a method for improving the quality stability of hydrocracking products through the grading use and temperature control of the catalyst.
A method for improving the quality of a hydrocracked product, comprising: the hydrocracking raw material and hydrogen are mixed and then enter a hydrocracking pretreatment reactor for refining reaction, the reaction effluent enters a hydrocracking reactor for hydrocracking reaction, four hydrocracking catalyst beds are arranged in the hydrocracking reactor, a hydrogenation post-treatment catalyst bed is arranged at the bottom of the hydrocracking reactor, when the conversion rate of fractions at the temperature of more than 350 ℃ in the hydrocracking raw material is 80-89%, arranging hydrogenation post-treatment catalyst beds among the hydrocracking catalyst beds, wherein the volume ratio of the hydrogenation post-treatment catalysts filled among the beds and at the bottom of the reactor along the material flow direction is 5-15:10-30:20-40:30-50, and the volume ratio of the hydrogenation post-treatment catalysts (total) filled in the hydrocracking reactor to the hydrocracking catalysts (total) filled in the hydrocracking reactor is 1: 6-8, separating the hydrocracking product to obtain various products.
In the method of the present invention, it is preferable to control the hydrotreating reaction temperature of any one hydrocracking catalyst filled between beds to be lower than the reaction temperature of the adjacent previous hydrocracking catalyst bed by 7 to 20 ℃, preferably 8 to 19 ℃, at least at the middle and later stages of the operation of the apparatus (the middle and later stages of the operation of the apparatus generally refer to the time difference between the types of the hydrocracking catalysts used and the time after the operation of the apparatus is started for 18 months).
According to the method, the temperature control of the inter-bed hydrogenation post-treatment catalyst is realized by injecting cold hydrogen, so that the reaction product flowing down from the upper part contacts the hydrogenation post-treatment catalyst with the reduced temperature firstly in the bed, the olefin content in the reactant can be further reduced to the maximum extent, and the hydrogenation pressure of the subsequent post-treatment catalyst is reduced. The amplitude of the temperature reduction control is different according to the mass content of the molecular sieve in the hydrocracking catalyst. Generally, when the mass content of the molecular sieve is less than 20%, the temperature reduction range of a hydrocracking post-treatment catalyst bed layer filled along the material flow direction can be 8-12 ℃, 8-12 ℃ and 9-13 ℃; when the mass content of the molecular sieve is 20-50%, the temperature reduction range of a hydrocracking post-treatment catalyst bed layer filled along the material flow direction can be 11-14 ℃, 11-14 ℃ and 13-16 ℃; when the content of the molecular sieve is more than 50 percent, the temperature reduction range of the hydrocracking post-treatment catalyst bed layer filled along the material flow direction can be 13-16 ℃, 13-16 ℃ and 16-19 ℃.
It should be further noted that, when hydrocracking catalysts with different molecular sieve mass contents are used and the same reaction depth is controlled, the average reaction temperature is different, when the molecular sieve mass content is lower (< 20%), the temperature reduction means and the temperature reduction amplitude are most preferred, and when the molecular sieve mass content is higher (> 50%), the space velocity and the proportion of the hydrocracking reactor bottom hydrogenation post-treatment are most preferred.
In the method of the invention, the position relation of the catalyst bed layers is defined according to the flow direction of the material flow in the hydrocracking reactor, namely the catalyst bed layer which is firstly contacted with the material flow is called as a first catalyst bed layer.
In the process of the present invention, the hydrocracking feedstock may be a wax oil feedstock or a diesel oil feedstock, as long as it can be used as a conventional feedstock for a hydrocracking apparatus, but a wax oil feedstock, particularly a heavy wax oil feedstock, is preferred. The distillation range is generally 250-600 ℃, the dry point is generally 500-600 ℃, the preferred temperature is 510-590 ℃, the nitrogen content is below 2500 mu g/g, generally 500 mu g/g-2000 mu g/g, the sulfur content is not strictly limited, and the content of other impurities can meet the conventional requirements. The crude oil may be various straight run or secondary processed wax oils obtained by processing naphthenic base crude oil, intermediate base crude oil or paraffin base crude oil, preferably straight run wax oil components or deasphalted oil of the primarily processed paraffin base crude oil, and may be selected from various Vacuum Gas Oils (VGO) and deasphalted oils (DAO) obtained by processing paraffin base crude oil, such as one or more of Daqing VGO, DAO, Changqing VGO and DAO. The hydrogen is the common feeding material with the impurity content meeting the requirement in the industry.
In the method, the hydrocracking pretreatment reaction conditions are as follows: the reaction temperature is 300-420 ℃, preferably 310-405 ℃, and the pressure of a reaction inlet is 6-16 MPa, preferably 8-14 MPa; the space velocity is 0.5h-1～3.0h-1Preferably 0.6h-1～2.5h-1(ii) a The volume ratio of hydrogen to oil at the reaction inlet is 400-1200, preferably 500-1100.
In the process of the invention, hydrogenation is carried outThe cracking reaction conditions were as follows: the reaction temperature is 370-430 ℃, preferably 380-425 ℃, and the hydrocracking reaction temperature in the middle and later operation periods is 390-425 ℃; the pressure of a reaction inlet is 6MPa to 16MPa, and preferably 8MPa to 14 MPa; the space velocity is 0.5h-1～3.0h-1Preferably 0.8h-1～2.8h-1(ii) a The volume ratio of hydrogen to oil at the reaction inlet is 400-1200, preferably 500-1100.
In the method, the hydrocracking catalyst comprises a cracking component and a hydrogenation component. The cracking component typically comprises amorphous silica-alumina and/or a molecular sieve, such as a Y-type, beta-type or USY molecular sieve. The binder is typically alumina or silica. The hydrogenation component is selected from metals, metal oxides or metal sulfides in groups VI, VII or VIII, 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 5-40%, preferably 10-35% based on the weight of the catalyst, the content of the molecular sieve is not strictly limited, but the controlled temperature reduction amplitude is different according to the content of the molecular sieve. The conventional hydrocracking catalyst can be selected from various commercial catalysts, such as FC-14, FC-32, FC-46 and other catalysts developed by FRIPP. The specific hydrocracking catalyst may also be prepared as required according to common general knowledge in the art.
In the method, the hydrocracking pretreatment reactor is filled with a hydrocracking pretreatment catalyst. The hydrocracking pretreatment catalyst comprises a carrier and hydrogenation metal loaded on the carrier, and generally comprises a metal component in the VIB group of the periodic table of elements, such as tungsten and/or molybdenum, accounting for 10-35% of oxide, and preferably 15-30% of oxide, based on the weight of the catalyst; group VIII metals such as nickel and/or cobalt, in terms of oxides, are in the range of 1% to 7%, preferably 1.5% to 6%. The carrier is inorganic refractory oxide, and is generally selected from alumina, amorphous silica-alumina, silica, titanium oxide and the like. The catalyst has the preferable metal of Mo-Ni and the specific surface area of not less than 160m2/g-1Not less than 0.3ml/g-1Infrared total acid 0.4-0.7 mmol/g, and the conventional hydrocracking catalyst may be selected from available commercial catalyst, such as Nashu petrochemical research instituteFRIPP) developed hydrotreating catalysts such as 3936, 3996, FF-16, FF-26, FF-36, FF-46 and the like; it can also be prepared according to the common knowledge in the field, if necessary. The refining reaction is a process of removing impurities such as desulfurization, denitrification, aromatic saturation and the like.
In the method, the hydrogenation post-treatment catalyst between bed layers in the hydrocracking reactor is an improved hydrocracking pretreatment catalyst and can be prepared by adding an auxiliary agent for modification, the components mainly comprise a carrier and loaded hydrogenation metal, and the catalyst generally comprises a VIB group metal component in the periodic table of elements by taking the weight of the catalyst as a reference, wherein the content of tungsten and/or molybdenum is 5-25 percent, preferably 10-20 percent, calculated by oxide; group VIII metals such as nickel and/or cobalt, in terms of oxides, are in the range of 1% to 5%, preferably 1.5% to 4%. The carrier is inorganic refractory oxide, and is generally selected from alumina, amorphous silica-alumina, silica, titanium oxide and the like. The preferable metal of the catalyst is Mo-Co, and the specific surface area is not less than 180m2/g-1Not less than 0.4ml/g-1The infrared total acid is less than 0.2mmol/g, and the mass content of the hydrogenation active component and the infrared acid content are respectively 5-85%, 50-95%, preferably 10-65% and 55-85% lower than those of the hydrocracking pretreatment catalyst. The hydrogenation post-treatment catalyst at the bottom of the hydrocracking reactor can use the hydrocracking pretreatment catalyst or the modified hydrocracking pretreatment catalyst.
The subsequent product separation, fractionation, and various acceptable products according to the control method of the present invention are within the routine knowledge of those skilled in the art and will not be described herein in a comprehensive manner.
Compared with the prior art, the hydrocracking fluidized bed uses the hydrogenation post-treatment catalyst, compared with the conventional hydrocracking pretreatment catalyst, due to the difference of the use position and the reaction purpose, the catalyst does not need to pursue overhigh denitrification performance, so the acidity and the hydrogenation performance of the catalyst are reduced, the coking and inactivation tendency of the catalyst in the operation process is delayed, especially the inactivation rate in a high-temperature reaction section, the stability of the hydrogenation performance is kept, unsaturated hydrocarbons such as olefin and the like generated in the reaction process can be reduced to the maximum extent, the unsaturated hydrocarbons such as olefin and the like can be converted to the greatest extent from the reaction angle, the generation of mercaptan sulfur by the subsequent reaction with hydrogen sulfide or the direct entering of the mercaptan sulfur into a product is avoided, and the hydrocracking fluidized bed has great effect on improving and stabilizing the product quality.
The invention utilizes the temperature difference of different reaction zones in the hydrocracking process and the fusion of cooling means to optimize and adjust the temperature of the reaction conditions of the hydrogenation post-treatment catalyst between beds, and transfers the hydrogenation post-treatment high-temperature section of the raw material to the low-temperature reaction section with controllable temperature, so that on one hand, a large amount of olefin generated in the upper reaction process is saturated and added in the low-temperature zone to be removed, the reaction severity of the bottom post-treatment catalyst is reduced, on the other hand, the coking tendency and the inactivation rate of the reaction process are delayed, the operation stability of the hydrocracking device is enhanced, particularly the quality stability of heavy naphtha and aviation kerosene products in the middle and later periods, the operation period of the device can be further prolonged, and the loss caused by unplanned shutdown of enterprises is reduced.
The invention perfectly integrates the preparation improvement of the catalyst and the reasonable application of the process conditions, can realize the purpose of improving the product quality, especially the product quality in the middle and later periods of operation, only by the grading filling, the variety change and the condition optimization of the catalyst on the premise of not modifying a hydrocracking device, reasonably corresponds different conversion depths to the improvement of a catalyst bed layer, reduces the complexity of modification and achieves the maximum benefit by the minimum modification. The device can thoroughly solve the influence of the change of the device process condition and the change of the product requirement on the product quality and the product period under the current market requirement, enhances the response flexibility and the stability of an oil refining enterprise to the market change, can bring considerable economic benefit and social benefit on the premise of unchanged investment of manpower and material resources, and has very remarkable application advantage.
Research results show that the conventional post-treatment catalyst is filled at the bottom of a cracking catalyst bed and has the function of reducing the olefin generated in the reaction process, but because the reaction temperature is higher and basically belongs to the highest temperature position of the whole hydrogenation reaction process, the probability of dehydrogenation reaction is high in the process of olefin saturation, the reaction temperature is higher and higher along with the extension of the running period, and the problem that the bromine index of heavy naphtha exceeds the standard frequently occurs in the middle and later stages of the reaction, for some low-activity hydrocracking catalysts, the problem is more serious, and the demand of the current fuel oil market causes that no matter what kind of catalyst is used, the reaction temperature is higher even if the high-activity hydrocracking catalyst is used due to the high heavy naphtha demand, and even if the activity of the catalyst is reduced, the reaction temperature thereof is further increased, and such problems occur not only in the medium-pressure hydrocracking unit but also frequently in the high-pressure hydrocracking unit. Therefore, the heavy naphtha bromine index is higher, and the excessive mercaptan of the aviation kerosene product becomes the more serious problem in the middle and later stages of the hydrocracking device of the current oil refining enterprise, and the problem needs to be solved urgently. Aiming at the defects existing in the reaction condition of the post-treatment catalyst, particularly at the stage of lowering the hydrogenation performance and improving the dehydrogenation tendency of the catalyst in the middle and later operating periods, the method of controlling the temperature between catalyst beds is utilized to set the olefin saturation process at a lower temperature position and reasonably match with the conversion depth, so as to reduce the content of the olefin in the whole cracking reaction system, meanwhile, the hydrogenation catalysts with different properties are graded, so that the catalyst properties and the process conditions are more integrated, and the method has the characteristics of simple operation, safety, controllability, convenience and implementation, can solve the problems of high bromine index and mercaptan in the heavy naphtha in the middle and later periods of operation and over standard mercaptan in the aviation kerosene product, not only improves the stability of the product quality in the operation process of the device and prolongs the operation period, the invention can be realized only by changing the grading of the catalyst without modifying the device.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Wherein, 1 is raw oil, 2 is hydrogen, 3 is a hydrogenation pretreatment reactor, 4 is a pretreated effluent, 5 is a hydrocracking reactor, 6, 7, 8 and 9 are hydrogenation post-treatment catalysts, 10 is a hydrocracking reaction effluent, and 11 is cooling quenching hydrogen.
Detailed Description
The combined process of the present invention will be described in detail with reference to the accompanying drawings. Fig. 1 only shows the core description of the process flow, and some necessary equipment and vessels are omitted in the schematic diagram, and the process flow is as follows:
The operation and effect of the method for improving the quality of a hydrocracked product according to the present invention will be further described with reference to examples and comparative examples. The properties of the feedstock oils used in the following examples and comparative examples are shown in Table 1, and the main properties of the catalysts used in the examples and comparative examples are shown in Table 2.
TABLE 1 Primary Properties of the base oils
TABLE 2 catalyst key Properties
The embodiment corresponds to the comparative example one by one, the hydrofining reactor and the hydrocracking reactor are not changed, the problem of product quality is solved only by the change of catalyst filling, the controlled product conversion rate is consistent, only the second, third and fourth beds of the hydrocracking reactor have differences, the filling volume is the same, and the method comprises catalyst filling, bed temperature rise (namely, the temperature reduction of temperature-reduction controllable reaction) and the like. The comparative examples show the bromine index of heavy naphtha at the mid-to late-run stage, which is generally lower for any molecular sieve content catalyst.
Example 1
The process flow shown in fig. 1 is adopted, the treatment catalysts A and B are used, the cracking catalyst C1 is used, the reaction mass conversion rate is controlled to be 85%, the operation time is 20 months, and the heavy naphtha bromine index is sampled and analyzed.
Comparative example 1
A conventional hydrocracking process flow is adopted, A and B are used as treatment catalysts, C1 is used as a cracking catalyst, the reaction mass conversion rate is controlled to be 85%, the operation time is 20 months, and the bromine index of the heavy naphtha is sampled and analyzed.
Example 2
The process flow shown in fig. 1 is adopted, the treatment catalysts A and B are used, the cracking catalyst C2 is used, the reaction mass conversion rate is controlled to be 85%, the operation time is 24 months, and the heavy naphtha bromine index is sampled and analyzed.
Comparative example 2
A conventional hydrocracking process flow is adopted, A and B are used as treatment catalysts, C2 is used as a cracking catalyst, the reaction mass conversion rate is controlled to be 85%, the operation time is 24 months, and the heavy naphtha bromine index is sampled and analyzed.
Example 3
The process flow shown in fig. 1 was adopted, the treatment catalysts a and B were used, the cracking catalyst C3 was used, the reaction mass conversion was controlled to 86%, the run time was 26 months, and the heavy naphtha bromine index was analyzed by sampling.
Comparative example 3
A conventional hydrocracking process flow is adopted, A and B are used as treatment catalysts, C3 is used as a cracking catalyst, the reaction mass conversion rate is controlled to be 86%, the operation time is 26 months, and the bromine index of the heavy naphtha is sampled and analyzed.
Comparing the effects of the above examples with those of the comparative examples, the results are given in table 3 below (only the different cracking bed parameters are listed) when controlling the same conversion depth (mass conversion 85%):
TABLE 3
The embodiment and the comparative example show that the method has the greatest characteristic that the saturation capacity of olefin is enhanced by changing the filling position of the catalyst at the middle and later periods of the operation of the hydrocracking device under a certain reaction condition so as to correspond to the lower bed inlet temperature, thereby reducing the content of olefin in the product, achieving the purposes of improving the product quality and the stability of the product quality, prolonging the operation period of the device, saving the consumption of manpower and material resources, bringing considerable economic benefit and social benefit to enterprises, and having great practical application advantages.
Claims (8)
1. A method for stabilizing quality of a hydrocracked product, characterized by: the method comprises the following steps: mixing a hydrocracking raw material and hydrogen, then feeding the mixture into a hydrocracking pretreatment reactor for refining reaction, feeding reaction effluent into the hydrocracking reactor for hydrocracking reaction, wherein four hydrocracking catalyst beds are arranged in the hydrocracking reactor, a hydrocracking post-treatment catalyst bed is arranged at the bottom of the hydrocracking reactor, a hydrocracking post-treatment catalyst bed is arranged between the hydrocracking catalyst beds when the conversion rate of fractions higher than 350 ℃ in the hydrocracking raw material is 80-89%, the volume ratio of the hydrogenation post-treatment catalysts filled between the beds and at the bottom of the reactor along the material flow direction is 5-15:10-30:20-40:30-50, and the volume ratio of the hydrogenation post-treatment catalysts filled in the hydrocracking reactor to the hydrocracking catalysts filled in the hydrocracking reactor is 1: 6-8, separating the hydrocracking product to obtain various products;
wherein, the hydrotreating reaction temperature of the hydrotreating catalyst filled between the beds of any hydrocracking catalyst is controlled to be 7-20 ℃ lower than the reaction temperature of the adjacent previous hydrocracking catalyst bed at least in the middle and later periods of the operation of the device;
the hydrogenation post-treatment catalyst between bed layers in the hydrocracking reactor is improvedThe hydrocracking pretreatment catalyst comprises a carrier and loaded hydrogenation metal, wherein the weight of the catalyst is taken as a reference, and the VIB group metal component in the periodic table of elements accounts for 5-25% by weight of oxides; the metal of the VIII family is 1-5% calculated by oxide, the carrier is inorganic refractory oxide, the specific surface area of the catalyst after hydrogenation is not less than 180m2/g-1Not less than 0.4ml/g-1The infrared total acid is less than 0.2mmol/g, and the mass content of the hydrogenation active component and the infrared acid content are respectively 5-85% and 50-95% lower than those of the hydrocracking pretreatment catalyst.
2. The method of claim 1, wherein: when the mass content of the molecular sieve in the hydrocracking catalyst is less than 20%, the temperature of the hydrotreating reaction of the hydrogenation post-treatment catalyst filled between the beds of the hydrocracking catalyst along the material flow direction is respectively 8-12 ℃, 8-12 ℃ and 9-13 ℃ lower than the reaction temperature of the adjacent previous hydrocracking catalyst bed; when the mass content of the molecular sieve in the hydrocracking catalyst is 20-50%, the temperature of the hydrotreating reaction of the hydrogenated post-treatment catalyst filled between the beds of the hydrocracking catalyst along the material flow direction is respectively reduced by 11-14 ℃, 11-14 ℃ and 13-16 ℃ compared with the reaction temperature of the adjacent previous hydrocracking catalyst bed; when the mass content of the molecular sieve in the hydrocracking catalyst is more than 50%, the temperature of the hydrotreating reaction of the hydrogenation post-treatment catalyst filled between the beds of the hydrocracking catalyst along the material flow direction is respectively reduced by 13-16 ℃, 13-16 ℃ and 16-19 ℃ compared with the reaction temperature of the previous adjacent hydrocracking catalyst bed.
3. The method of claim 1, wherein: the hydrocracking raw material is a wax oil raw material or a diesel oil raw material.
4. The method of claim 1, wherein: the hydrocracking pretreatment reaction conditions were as follows: the reaction temperature is 300-420 ℃; the pressure of a reaction inlet is 6MPa to 16 MPa; the space velocity is 0.5h-1～3.0h-1(ii) a The volume ratio of hydrogen to oil at the reaction inlet is 400～1200。
5. The method of claim 1, wherein: the hydrocracking pretreatment reactor is filled with a hydrocracking pretreatment catalyst, the hydrocracking pretreatment catalyst comprises a carrier and loaded hydrogenation metal, and the VIB group metal component is 10-35% of oxide based on the weight of the catalyst; the VIII family metal accounts for 1 to 7 percent of the oxide, and the carrier is inorganic refractory oxide.
6. The method of claim 1, wherein: the hydrocracking reaction conditions were as follows: the reaction temperature is 370-430 ℃, and the hydrocracking reaction temperature in the middle and later periods of operation is 390-425 ℃; the pressure of a reaction inlet is 6MPa to 16 MPa; the space velocity is 0.5h-1～3.0h-1(ii) a The volume ratio of hydrogen to oil at the reaction inlet is 400-1200.
7. The method of claim 1, wherein: the hydrocracking catalyst comprises a cracking component and a hydrogenation component, wherein the cracking component is amorphous silica-alumina and/or a molecular sieve, and the hydrogenation component is selected from metals, metal oxides or metal sulfides in families VI, VII or VIII.
8. The method of claim 1, wherein: the temperature control of the inter-bed hydrogenation post-treatment catalyst is realized by injecting cold hydrogen.
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