CN111676057B

CN111676057B - Residual oil hydrogenation reactor with multiple independent reaction units, residual oil hydrogenation system containing reactor and residual oil hydrogenation process

Info

Publication number: CN111676057B
Application number: CN202010565529.3A
Authority: CN
Inventors: 王红令; 张留明; 张红勤; 张俊; 宋现玺
Original assignee: Zhongnai Engineering Technology Co ltd
Current assignee: Zhongnai Engineering Technology Co ltd
Priority date: 2020-06-19
Filing date: 2020-06-19
Publication date: 2022-04-15
Anticipated expiration: 2040-06-19
Also published as: CN111676057A

Abstract

The invention discloses a residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units, a residual oil hydrogenation system containing the reactor and a residual oil hydrogenation process thereof, wherein the reactor comprises N independent reaction units which are connected in parallel along the longitudinal direction of the reactor, wherein N is more than or equal to 2, the independent reaction units are provided with independent reaction material feeding systems and independent reaction product discharging systems, the reaction products of each reaction unit are collected and converged by a reaction product collecting system which is arranged in the reactor and communicated with each reaction unit, and are discharged out of the reactor from a discharging port at the lower part of the reactor, the system and the related process thereof integrally improve the utilization rate of active resources of the catalyst, under the condition of not increasing the filling amount of the catalyst, the contact area of a fresh oil gas raw material and the catalyst is increased by a plurality of times, and the service cycle of a catalyst bed layer can be obviously prolonged, the pressure drop of the catalyst bed layer is relieved, so that the raw oil can stably run for a long time at the optimal reaction temperature.

Description

Residual oil hydrogenation reactor with multiple independent reaction units, residual oil hydrogenation system containing reactor and residual oil hydrogenation process

Technical Field

The invention relates to the technical field of residue hydrogenation, in particular to a residue hydrogenation reactor with a plurality of independent reaction units, a residue hydrogenation system containing the reactor and a residue hydrogenation process thereof.

Background

The residue (atmospheric residue, vacuum residue) is the heaviest fraction remaining after the primary processing (atmospheric, vacuum distillation) of the crude oil. Compared with light distillate oil, the residual oil has complex composition, large average relative molecular mass, high viscosity, large density, low hydrogen-carbon ratio, high carbon residue value, and contains a large amount of harmful elements and non-ideal components such as metal, sulfur, nitrogen, colloid, asphaltene and the like.

Hydrogenation of residual oil is one of the main technical approaches for heavy oil upgrading. At present, the hydrogenation technology methods of fixed bed, moving bed, boiling bed, suspension bed and the like are developed for the residue hydrogenation. The fixed bed hydrogenation technology is developed rapidly by taking the main technical advantage of simple and stable reaction process operation as the main technical advantage, and becomes the most mature mainstream technology of residue hydrogenation, more and more oil refining enterprises select the fixed bed residue hydrogenation and residue catalytic cracking combined process to realize the purpose of producing high-quality gasoline, kerosene and diesel oil to the maximum extent, and the economic benefit and the social benefit are obvious.

But the fixed bed has higher hydrotreating difficulty and is easy to generate coke in the reaction process. Fixed bed hydroprocessing units are typically operated under severe conditions of high temperature, high pressure and low volumetric space velocity to achieve the desired reaction objectives. In the hydrotreating process, more solids such as carbon deposit, metal sulfide and the like are generated in residual oil, the deposition rate and the deposition amount of the solids on a catalyst bed layer must be effectively controlled, otherwise, the pressure drop of a reactor is rapidly increased or the activity of a catalyst is rapidly reduced until the design limit is reached, the device is forced to be shut down, the operation and operation period of the device is greatly shortened, and the economic benefit of the process is influenced. Therefore, reducing the number of shutdowns and extending the operation period are important factors for improving the economic efficiency of the residue fixed bed hydrotreater.

The fixed bed residual oil hydrotreating catalyst has multiple functions of removing a small amount of solid particles, Hydrodemetallization (HDM), Hydrodesulfurization (HDS), Hydrodenitrogenation (HDN), Hydrodecarbonization (HDCCR), partial Hydrogenation Conversion (HC) and the like. Obviously, it is difficult to develop a single type of catalyst that integrates the above functions. The main varieties of the fixed bed residual oil hydrogenation catalysts of various families at present can be generally divided into: the four main types of hydrogenation protective agent (HG), hydrogenation demetallization agent (HDM), hydrogenation desulfurizing agent (HDS) and hydrogenation denitrogenation agent (HDN) are separately placed in different reactors.

The fixed bed residual oil hydrogenation technology is characterized in that the problem that asphaltene, metal and the like in residual oil can be removed and can be tolerated is solved on the premise of achieving the main reaction purposes of desulfurization, conversion and the like. Namely, the uniform distribution of solid deposits in each bed layer of the reactor in the whole operation period is realized through the reasonable adjustment of the bed layer void ratio and the catalytic activity, and the activity and the stability of the catalyst reach the optimal balance.

The fixed bed residual oil hydrogenation technology generally adopts various catalysts with different main functions to be combined and filled in different or same hydrogenation reactors according to the reaction mechanism and sequence of removing mechanical impurities, hydrodemetallization, desulfurization, denitrification/carbon residue removal, and generally adopts a preposed position with lower catalyst activity, larger granularity and pore diameter and a postpositioned position with higher activity and smaller granularity and pore diameter according to the sequence of contacting reaction materials; according to the type of the catalyst, the protective agent, the demetallization agent, the desulfurizer and the denitrogenation/carbon residue removal agent are sequentially filled from front to back. Typical technologies such as CHEVRON (CHEVRON) company residual oil hydrogenation series patent technology, chinese petrochemical FRIPP and RIPP residual oil hydrogenation series patent technology all have the common technical characteristics.

The reaction material flow of the present fixed bed residual oil hydrogenation technology is divided into mechanical impurity removal, hydrodemetallization, desulfurization, denitrification/carbon residue removal reaction according to the flow direction, the mechanical impurity and metal impurity in the residual oil are removed and then deposited on a catalyst bed layer in a solid form, the deposition is firstly carried out on a front bed layer, the deposition is increased and saturated along with the increase of the residual oil treatment capacity, and the deposition gradually extends to a rear bed layer; the saturation of the deposit can gradually lose the activity of the catalyst on one hand and gradually increase the pressure drop of the catalyst bed on the other hand, and as a result, the reaction conversion effect is more and more far away from the expected index, meanwhile, the production safety of the hydrogenation device is lower and lower, the removal rate of the hydrogenation impurities is reduced, the pressure drop of the catalyst bed is increased, one of the two reaches the design limit value of the process and the device, and the production period of the device is finished.

In the initial operation stage of the existing fixed bed residual oil hydrogenation device, the reactions of mechanical impurity removal, hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and residual carbon removal are relatively balanced, and as the operation time increases, the preposed catalyst bed layer of the mechanical impurity removal and metal is gradually inactivated due to sediment saturation, so that the hydrodesulfurization, hydrodenitrogenation and residual carbon removal catalysts gradually bear more demetallization reaction loads, and the inactivation rate is increased. In order to compensate activity loss, the existing fixed bed residual oil hydrogenation technology needs to gradually increase the reaction temperature of a catalyst bed layer in the middle and later period of the operation of a device. However, the residue hydrogenation process is a complex reaction system, and has an optimal reaction temperature corresponding to a specific residue type and a catalyst grading system. When the reaction temperature is increased, the activity of the catalyst is improved, the coking and other side reaction rates on the surface of the catalyst are increased, and hot spots are easy to appear on a catalyst bed layer, wherein one is to further increase the inactivation rate, and the other is to further increase the pressure drop of the bed layer. Furthermore, both the catalyst and the apparatus have a limit operating temperature, and the reaction temperature must not exceed one of these two limits.

When processing inferior residual oil, the protection and demetalization reactor (i.e. the first reactor) often causes the problems of shortened operation period of the device or low utilization efficiency of the main catalyst due to bed layer blockage or the deactivation of the main catalyst of desulfurization conversion prior to the activity of the catalyst. In order to solve the above problems, some have improved the process flow, and one solution is to add a section of moving bed reactor or upflow reactor (UFR) in front of the fixed bed reactor. By utilizing the characteristic that the catalyst of the moving bed reactor can be replaced on line, the problem of bed layer blockage is solved, and the problem of activity matching with the main catalyst is also solved. The representative processes are Chevron's OCR technology and Shell's HYCON technology, but the technology has high investment and unstable operation, and thus cannot be widely applied in industry. The UFR process is an up-flow fixed bed hydrogenation technology, reactant flows slightly expand a catalyst bed layer from bottom to top, so that the problem of large pressure drop change in the initial and final stages of a conventional fixed bed reactor is solved, and industrialization is realized for the first time in 2000.

Another solution is to use a pre-reactor in front of the reactor train that can be cut off or switched, which represents the Hyvahl technology where the process is IFP. The method adopts the technology of a removable reactor, has low investment, simple and convenient operation and high safety, but only slightly improves the long-period operation of the system. The device investment of the switchable reactor technology is not increased much, the operation is simpler, and the method is a very effective improvement scheme of the fixed bed residual oil hydrogenation technology, and can be applied to inferior residual oil raw materials, especially occasions with increased metal content. The technical advantages are as follows: flexible operation, long period and low cost. The operation mode is as follows: multiple series are shared, and the cost is reduced. Therefore, the trend of industrial application is relatively fast in recent years. However, the technology still adopts a fixed bed reactor, and has the same inherent property as the fixed bed, the adaptability of the technology is also greatly limited, and the technology is difficult to adapt to the larger change of the property of the residual oil raw material, which is the objective reality that most refineries must face nowadays, and the next research focuses on how to enhance the adaptability of the technology to the large fluctuation of the raw material.

The fixed bed hydrogenation technology of UOP company adds a bypass between the protective reactor and the main reactor, and a valve on the bypass can control the flow of the protective reactor to ensure that the temperature is higher than the embrittlement temperature. UOP company uses two bed guard reactors for fixed bed hydroprocessing techniques for high impurity content feedstocks; the internal gas bypass can utilize the catalyst of the protective bed layer to the maximum extent and reduce the increase of pressure drop to the maximum extent; more efficient and economical than a protected reactor catalyst replacement system.

In order to solve the problem that the pressure drop of a catalyst bed layer is increased too fast due to solid deposition, various special-shaped catalysts are developed by different catalyst research units in a competitive mode so as to improve the void ratio of the catalyst bed layer and uniformly contain solid deposition as much as possible. Such as CN97116251.4, CN99225199.0, cn99225198, CN99225197.4, CN03213520.3, CN 03284728.9.

Meanwhile, each catalyst research unit also carries out matched research on a plurality of series of catalyst grading methods so as to adapt to the processing requirements of different raw oil, delay the pressure difference accumulation of the catalyst bed layer as much as possible and prolong the running period. Such as CN201010519221.1, CN201010519224.5 and CN00807042.

For example, CN1144860C and CN208824452U adopt a side-opening feeding mode, in which one or more feed ports are added in the first reactor in the heavy and residual oil hydrogenation reaction system, the feeding direction is an up-in-down-out mode, when the pressure drop of the catalyst bed in the reactor is 0.4-0.8 times of the designed maximum pressure drop value, the next feed port is sequentially used, and the original feed port can be fed with cycle oil or a mixture of cycle oil and raw oil.

In the related patent technologies, no matter the special-shaped catalyst is adopted to increase the bed voidage, or the upflow reactor is adopted, or the raw material oil-gas feeding mode is changed, the reactant flows flow along the axial direction of the reactor, the ratio of the flow area to the material flow stroke is small, solid sediments are firstly coalesced on the front catalyst bed layer and gradually extend towards the rear catalyst bed layer, the problems of synchronous inactivation of the catalyst, large pressure drop of the catalyst bed layer and the like cannot be fundamentally solved, and the problem of large waste of active resources of the rear catalyst always exists.

Disclosure of Invention

In view of the above-mentioned deficiencies in the prior art, the present invention provides a residuum hydrogenation reactor having a plurality of independent reaction units, a residuum hydrogenation system containing the same, and a residuum hydrogenation process thereof. In the invention, the pressure drop of the catalyst bed layer is reduced, and the utilization rate of active resources of the catalyst is improved. Under the condition of not increasing the loading of the catalyst, the contact area of the fresh raw material oil gas and the catalyst is increased by several times, so that the service life of a catalyst bed layer is obviously prolonged.

The residue hydrogenation fixed bed reactor with a plurality of independent reaction units comprises: the reactor comprises N independent reaction units which are connected in parallel along the longitudinal direction of the reactor, wherein N is more than or equal to 2, each independent reaction unit is provided with an independent reaction material sampling system and an independent reaction product discharging system, and the reaction products of each reaction unit are collected and gathered by a reaction product collecting system which is communicated with each reaction unit in the reactor and are discharged out of the reactor from a discharge port at the lower part of the reactor.

In the invention, the hydrogenation reaction conditions are as follows: the reaction temperature is 320-430 ℃, the reaction pressure is 10-25 MPa, and the space velocity is 0.1-1.0 h^-1The volume ratio of hydrogen to oil is 200-2000, the preferable reaction temperature is 350-400 ℃, the reaction pressure is 14-18 MPa, and the space velocity is 0.2-0.5 h^-1The volume ratio of hydrogen to oil is 400-1000.

In the invention, the raw oil is atmospheric residue oil and vacuum residue oil obtained by primary processing or secondary processing of crude oil, or the mixture of the atmospheric residue oil and the vacuum residue oil in any proportion, or the mixture of the atmospheric residue oil or the vacuum residue oil and wax oil obtained by primary processing or secondary processing in any proportion. The density (20 ℃) of the nano-particles is 0.895 to 1.150g/cm³In the above-mentioned manner,the viscosity (100 ℃) is 25-5000 mm²The content of carbon residue is between 5.0 and 20.0m percent, the content of sulfur is between 0.5 and 5.0m percent, the content of nitrogen is between 0.1 and 1.0m percent, and the content of metal (Ni + V) is between 30.0 and 250.0 microgram/g.

In the present invention, the residual oil hydrogenation catalyst refers to a single catalyst or a plurality of catalysts having functions of heavy oil and/or residual oil hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, and hydrocracking. These catalysts are generally based on porous refractory inorganic oxides, such as alumina or crystalline aluminosilicates, such as zeolites, as the active component, oxides of metals of group VIB and/or group VIII. Other auxiliary agents such as P, Si, F, B and other elements can also be added selectively. For example, CEN and FZC series catalysts produced by the institute of petrochemical engineering.

According to the invention, through skillful improvement of the reactor structure, the contact area of fresh raw material oil gas and a catalyst is increased by several times, so that the service cycle of a catalyst bed layer is correspondingly and obviously prolonged, the ratio of the raw material oil flow area to the reaction stroke of the raw material oil flow area is also increased, and the pressure drop is in direct proportion to resistance and in inverse proportion to the stroke. After the protective agent and the hydrodemetallization catalyst in the pre-reactor are partially deactivated, the hydrodesulfurization catalyst and the hydrodenitrogenation/carbon residue removal catalyst in the post-reactor can also continue to normally exert the main functional activity, so that the utilization rate of the active resources of the catalyst is maximized.

The invention has short residual oil reaction stroke and pressure transmission, uniform sediment distribution, no need of excessively increasing bed voidage of a protective agent and a hydrodemetallization catalyst, no need of adopting a grading method of excessive catalyst varieties to balance reaction performance, effectively reducing the variety and specification of the catalyst, enabling raw oil to stably run for a long time at the optimal reaction temperature, no need of temperature raising operation for compensating the activity of the catalyst, and capability of adopting a dense phase method to fill the catalyst, thereby improving the space utilization rate of the reactor.

Drawings

FIG. 1: flow chart of conventional residual oil hydrogenation process

FIG. 2: the invention relates to a process flow chart I of residual oil hydrogenation, wherein a reaction material flows from bottom to top.

FIG. 3: the second flow chart of the residual oil hydrogenation process of the invention, wherein the reaction material flows from top to bottom.

Detailed Description

The technical scheme and the effect of the invention are further explained by combining the drawings and the embodiment.

The invention provides a residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units, which comprises: the reactor comprises N independent reaction units which are connected in parallel along the longitudinal direction of the reactor, wherein N is more than or equal to 2, each independent reaction unit is provided with an independent reaction material sampling system and an independent reaction product discharging system, and the reaction products of each reaction unit are collected and gathered by a reaction product collecting system which is communicated with each reaction unit in the reactor and are discharged out of the reactor from a discharge port at the lower part of the reactor.

Preferably, in the residue hydrogenation fixed bed reactor with a plurality of independent reaction units, N is 3 or 4.

Also preferably, each individual reaction unit in the above reactor of the present invention has an individual feed line for the reaction material and/or a feed valve with adjustable amount and flow rate, which are disposed outside the reactor, wherein the catalyst-to-oil ratio is optimized by adjusting the feed valve according to the operating state of the reactor.

In general, in the above-mentioned residue hydrogenation fixed bed reactor of the present invention, each of the independent reaction units has an independent (slag) oil (hydrogen) gas dispersing and distributing device, so that the (slag) oil (hydrogen) gas is uniformly distributed in the reactor and the reaction unit and the reaction materials are fully contacted with the catalyst.

Optionally, in the above-mentioned residue hydrogenation fixed bed reactor of the present invention, the flow direction of the reaction material of each of the independent reaction units is an upflow or downflow, or the flow direction of a part of the reaction material of the independent reaction unit is an upflow and the flow direction of the reaction material of the other part of the independent reaction unit is a downflow.

In general, in the above-mentioned residue hydrogenation fixed bed reactor of the present invention, a reaction product discharge port is provided at the top or bottom of each of the individual reaction units, and the reaction product flows into the reaction product collecting system through the discharge port to be collected and collected.

As shown in fig. 2 and fig. 3, preferably, the number of the independent reaction units in the residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units of the present invention is 4, wherein fig. 2 shows the residual oil hydrogenation reactor with the reaction material flowing from bottom to top, and the system and the process flow thereof; FIG. 3 shows a residuum hydrogenation reactor of the present invention with the reaction mass flowing from top to bottom, and its system and process flow.

The residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units can be used as a pre-reactor of a residual oil hydrogenation reaction system. In particular as protectant reactors and/or demetallization reactors. The reactor can be connected with any type of residual oil hydrogenation fixed bed reactor in series and/or in parallel to form a complete residual oil hydrogenation reaction system.

In the above-mentioned fixed-bed reactor for residual oil hydrogenation having a plurality of independent reaction units according to the present invention, raw oil and reaction gas enter each reaction unit from the upper feed inlet or the lower feed inlet of each independent reaction unit, and after reaction of the catalyst bed layer in each reaction unit, a reaction product (product oil) flows into the reaction product collection system from the lower discharge outlet or the upper discharge outlet of each reaction unit.

The residue hydrogenation fixed bed reactor with a plurality of independent reaction units comprises: the reactor comprises a cylinder body, an upper end enclosure, a lower end enclosure, upper and/or lower feed inlets of each reaction unit, upper and/or lower discharge outlets of each reaction unit, feed pipes and discharge pipes communicated with each reaction unit, and catalyst beds of each reaction unit, wherein (slag) oil (hydrogen) gas distribution discs at the upper and lower ends of each catalyst bed, a reaction gas collecting area near the upper end enclosure, and a reaction product (generated oil) collecting area near the lower end enclosure.

The invention also provides a residual oil hydrogenation reaction system which comprises the residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units as a pre-reactor of the residual oil hydrogenation reaction system, in particular as a protective agent reactor and/or a demetallization reactor. In addition, the residual oil hydrogenation reaction system can also comprise a hydrodesulfurization reactor, a hydrodenitrogenation reactor, a carbon residue removal reactor and/or a partial hydrogenation reactor.

The invention also provides a residual oil hydrogenation process, which uses the residual oil hydrogenation reaction system and the residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units.

The residual oil hydrogenation process flow of the invention is as follows: raw oil mixed with dissolved hydrogen enters each independent reaction unit from the upper part or the lower part of each independent reaction unit of the reactor through an independent feeding system of each independent reaction unit of the reactor, flows into a catalyst bed layer of the reaction unit through small holes on an oil gas distributor of each reaction unit, and supplemental hydrogen uniformly distributed through a hydrogen distribution disc of the independent reaction unit upwards passes through the catalyst bed layer, is mixed with the raw oil and then reacts on the catalyst bed layer. Raw oil and hydrogen sequentially pass through the protective agent layer and/or the hydrodemetallization catalyst layer in the catalyst bed layer of each independent reaction unit in the reactor from top to bottom or from bottom to top along the axial direction of each independent reaction unit. The final reaction product oil flows into the reaction product collecting system through a lower discharge port or an upper discharge port of each reaction unit, is discharged from a collecting area at the lower part of the reactor through a reactor outlet, and further flows through a subsequent fixed bed reactor with a hydrodesulfurization catalyst bed layer, a reactor with a hydrodenitrogenation and/or carbon residue removal catalyst bed layer and a reactor with a partial hydroconversion catalyst bed layer. In the pre-reactor of the invention, the removed mechanical impurities and easily removed iron and calcium impurities are deposited on a protective agent catalyst bed layer, metal impurities such as nickel, vanadium and the like are mainly deposited on a hydrogenation demetalization catalyst bed layer, the obtained hydrogenation produced oil is collected by a produced oil collecting area and then discharged out of the reactor, and the obtained gas-phase product and the reaction residual hydrogen are collected by a reaction gas collecting area at the upper part of the reactor and then discharged out of the reactor.

The invention is further explained and illustrated below by means of specific embodiments, without however being limited to the scope of protection of the invention as described in the examples below.

Example 1

The same raw material, catalyst species and grading and loading method thereof as in comparative example 1 below were used to perform a comparison of the process operations of the residue hydrogenation fixed bed reactor having a plurality of independent reaction units, system and process thereof according to the present invention as shown in fig. 2 and the conventional residue hydrogenation fixed bed reactor, system and process thereof as shown in fig. 1.

As shown in fig. 2, the residual hydrogenation reactor having a plurality of independent reaction units according to the present invention is used as a protecting agent and/or demetallization reactor, i.e., a first reactor. The number of independent reaction units in the residual oil hydrogenation fixed bed reactor is 4, and oil gas reaction materials flow from bottom to top.

In this example 1, a self-developed and produced ZRH-102SP catalyst is used, the hydrodemetallization catalyst is ZRH-114AS, the hydrodemetallization/hydrodesulfurization transition catalyst is ZRH-215AS, the hydrodesulfurization catalyst is ZRH-302AS, and the hydrodenitrogenation catalyst is ZRH-402AS, and in each reactor, the grading loading ratio of each functional catalyst is ZRH-102 SP: ZRH-114 AS: ZRH-215 AS: ZRH-302 AS: ZRH-402AS ═ 10: 30: 5: 20: 35. the raw oil is middle east atmospheric residue, and the impurity content is as follows: 2.78w% of S, 0.29w% of N, 12.1w% of CCR and 110 [ mu ] g/g of Ni + V. The reaction conditions are as follows: the reaction pressure is 15.7MPa, the reaction temperature is 370 ℃, the volume ratio of hydrogen to oil is 700, and the oil inlet amount is 0.2h based on the space velocity of the existing fixed bed^-1For reference, the removal rate of various impurities was taken from the data at 500h of hydrogenation. The reaction results are shown in table 1.

TABLE 1

Comparative example 1

The same raw materials, functional catalysts, catalyst grading, filling ratio and reaction conditions as those in example 1 are adopted, and a conventional residue hydrogenation fixed bed reactor, a system and a process thereof are shown in fig. 1, wherein the volume of the first reactor is equal to that in example 1. The reaction results are shown in table 2.

TABLE 2

From the data analysis in tables 1 and 2, it can be seen that: by adopting the conventional residual oil hydrogenation fixed bed reactor process, when the oil inlet quantity of the residual oil is increased from the benchmark to (the benchmark is plus 30 percent), the reaction space velocity is increased from 0.20h^-1Increased to 0.26h^-1The removal rate of various impurities is reduced along with the increase of the space velocity, and the removal rate of various impurities is reduced by about 4 percent along with the increase of 10 percent of the benchmark. By adopting the residual oil hydrogenation fixed bed reactor process, the impurity removal rate is higher than that of the conventional residual oil hydrogenation fixed bed reactor process on the same reference; with the increase of the oil inlet amount benchmark, the reaction space velocity can also be increased by 0.20h^-1Increased to 0.26h^-1Because the contact mode of fresh oil gas and catalyst is changed, the contact area of unit oil gas material and catalyst is increased, although the removal rate of various impurities is reduced, the reduction speed of the removal rate of the impurities is lower than that of the conventional residue hydrogenation fixed bed reactor, and the removal rate of various impurities is reduced by about 2% when the removal rate of the various impurities is increased by 10% along with the reference.

Example 2

Comparison of the process operations of the residue hydrogenation fixed bed reactor, system and process having a plurality of independent reaction units according to the present invention as shown in fig. 3 and the conventional residue hydrogenation fixed bed reactor, system and process as shown in fig. 1 was performed using the same raw materials, functional catalysts, catalyst gradation and loading ratio and reaction conditions as in comparative example 2 below.

As shown in fig. 3, the residual hydrogenation reactor having a plurality of independent reaction units according to the present invention is used as a protecting agent and/or demetallization reactor, i.e., a first reactor. The number of independent reaction units in the residual oil hydrogenation fixed bed reactor is 4, and oil gas reaction materials flow from top to bottom.

In this example 2, a self-developed and produced ZRH-102SP catalyst is used, the protecting agent is zr h-102SP, the hydrodemetallization catalyst is zr h-116AS, the hydrodemetallization/hydrodesulfurization transition catalyst is zr h-206AS, the hydrodesulfurization catalyst is zr h-315AS, and the hydrodenitrogenation catalyst is zr h-401AS, and in each reactor, the grading loading ratio of each functional catalyst is zr h-102 SP: ZRH-116 AS: ZRH-206 AS: ZRH-315 AS: ZRH-401AS ═ 10: 30: 5: 20: 35. the raw oil is another middle east atmospheric residue, and the impurity content is as follows: 2.67w% for S, 0.31 w% for N, 13.57 w% for CCR, and 126 μ g/g for Ni + V. The reaction conditions are as follows: the reaction pressure is 15.7MPa, the reaction temperature is 375 ℃, the volume ratio of hydrogen to oil is 700, and the oil inlet amount is 0.2h at the airspeed of the prior fixed bed process^-1As a reference. The reaction results are shown in Table 3.

TABLE 3

Comparative example 2

The same raw materials, functional catalysts, catalyst grading, filling ratio and reaction conditions as those in example 2 are adopted, and a conventional residue hydrogenation fixed bed reactor, a system and a process thereof are shown in fig. 1, wherein the volume of the first reactor is equal to that in example 2. The reaction results are shown in Table 4.

TABLE 4

As can be seen from the data analysis in tables 3 and 4: under the same operation time, the residual oil hydrogenation fixed bed reactor process has higher impurity removal rate than the conventional fixed bed reactor process. Along with the prolonging of the operation time, from 500h to 750h, the removal rate of various impurities in the conventional fixed bed reactor process is reduced by about 4 percent, and from 750h to 1000h, the removal rate of various impurities is reduced by about 3.5 percent; in the residual oil hydrogenation fixed bed reactor process, fresh oil gas in a fixed bed layer of a first reactor enters a system to perform layered contact reaction with a catalyst, and accumulated impurities are dispersed in the same time to slow the deactivation speed of the catalyst in the system from 500h to 750h due to the increase of the contact area of the catalyst and the oil gas, so that the removal rate of various impurities of the fixed bed reactor process is reduced by about 3 percent, from 750h to 1000h, and the removal rate of various impurities is only reduced by about 2 percent.

Claims

1. A residual oil hydrogenation reaction system is characterized in that: the system comprises a residual oil hydrogenation fixed bed reactor with a plurality of independent reaction units, and the residual oil hydrogenation fixed bed reactor is used as a protective agent reactor and/or a demetallization reactor of a residual oil hydrogenation reaction system, and comprises: n independent reaction units are connected in parallel along the longitudinal direction of the reactor, wherein N is more than or equal to 2, each independent reaction unit is provided with an independent reaction material feeding system and an independent reaction product discharging system, the reaction products of each reaction unit are collected and converged by a reaction product collecting system communicated with each reaction unit in the reactor and are discharged out of the reactor from a discharging port at the lower part of the reactor, each independent reaction unit is provided with an independent residual oil hydrogen dispersing and distributing device, so that residual oil hydrogen is uniformly distributed in the reactor and the reaction units and fully contacts with a catalyst, the flow direction of the reaction materials of each independent reaction unit is upflow or downflow, or the flow direction of the reaction materials of one part of the independent reaction units is upflow, and the flow direction of the reaction materials of the other part of the independent reaction units is downflow, and the top or the bottom of each independent reaction unit is provided with a reaction product discharge port, and the reaction products flow into the reaction product collecting system through the discharge ports to be collected and converged.

2. A residuum hydroprocessing reaction system as recited in claim 1, wherein: wherein N is 3 or 4.

3. A residuum hydroprocessing reaction system as recited in claim 1, wherein: each independent reaction unit in the reactor is provided with an independent reaction material feeding pipeline and/or feeding valves with adjustable quantity and flow rate, wherein the independent reaction material feeding pipelines and/or the feeding valves are arranged outside the reactor, and the catalyst-oil ratio is enabled to reach an optimal value by adjusting the feeding valves according to the running state of the reactor.

4. A residuum hydroprocessing reaction system according to any one of claims 1-3, characterized by: the reactor can be connected with any type of residual oil hydrogenation fixed bed reactor in series and/or in parallel to form a complete residual oil hydrogenation reaction system.

5. A residuum hydroprocessing reaction system according to any one of claims 1-3, characterized by: raw oil and reaction gas enter each reaction unit from an upper feed inlet or a lower feed inlet of each independent reaction unit, and after reaction of catalyst bed layers in each reaction unit, reaction products, namely product oil flow into the reaction product collecting system from a lower discharge outlet or an upper discharge outlet of each reaction unit.

6. A residuum hydroprocessing reaction system according to any one of claims 1-3, characterized by: the reactor also comprises a cylinder, an upper end enclosure, a lower end enclosure, upper and/or lower feed inlets of each reaction unit, upper and/or lower discharge outlets of each reaction unit, feed pipes and discharge pipes communicated with each reaction unit, and catalyst beds of each reaction unit, residual oil hydrogen distribution discs at the upper and lower ends of each catalyst bed, a reaction gas gathering area near the upper end enclosure, and a reaction product near the lower end enclosure, namely a generated oil gathering area.

7. A residuum hydroprocessing reaction system according to any one of claims 1-3, characterized by: wherein, the system also comprises a hydrodesulfurization reactor, a hydrodenitrogenation reactor, a carbon residue removal reactor and/or a partial hydrogenation reactor.

8. A process for hydrogenating residual oil is characterized in that: a residuum hydroprocessing reaction system as recited in any one of claims 1-7, wherein the reaction conditions are: reaction temperature: 320-430 ℃ and reaction pressure: 10-25 MPa, airspeed: 0.1 to 1.0 hour^-1Hydrogen-oil volume ratio: 200 to 2000.

9. A process for hydrogenating a residue as in claim 8, wherein: the reaction conditions are as follows: reaction temperature: 350-400 ℃ and reaction pressure: 14-18 MPa, airspeed: 0.2 to 0.5h^-1Hydrogen-oil volume ratio: 400-1000.