阅读说明：本技术 一种物料流向交替变化的渣油加氢反应器、含有该反应器的渣油加氢系统及其渣油加氢工艺 (Residual oil hydrogenation reactor with alternately changed material flow directions, residual oil hydrogenation system comprising reactor and residual oil hydrogenation process ) 是由 张留明 张红勤 张俊 王红令 宋现玺 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种物料流向交替变化的渣油加氢反应器、含有该反应器的渣油加氢系统及其渣油加氢工艺,该反应器内部空间具有与反应器筒体相同中心轴的圆筒状夹层,所述反应器在不改变原有反应器体积和催化剂填装量的条件下,被圆筒分割成两个截面积相等的夹层,该反应器高度为原反应器高度的1/N,其中N≥2,渣油物料在相邻被所述圆筒物理分割开且截面积相等的两个催化剂床层中的流向正好相反,当催化剂床层压降大于最大压降设计值的0.3倍时,通过外部管线的预设开关和/或阀门,改变渣油原料和加氢产物在所述反应器中的流向,实现渣油原料在反应器中的流向反向交替变化,该反应器既能通过改变原料流向分散杂质沉积的位置,当N≥3时又能通过减小反应器高度增加新鲜渣油原料与催化剂的接触截面积、从而缓解反应器整个催化剂床层压降并延长其使用周期。(The invention discloses a residual oil hydrogenation reactor with material flow direction alternating, a residual oil hydrogenation system containing the reactor and a residual oil hydrogenation process thereof, wherein the inner space of the reactor is provided with a cylindrical interlayer with the same central shaft as a reactor cylinder, the reactor is divided into two interlayers with the same cross section area by a cylinder under the condition of not changing the original reactor volume and catalyst filling amount, the height of the reactor is 1/N of the original reactor height, wherein N is more than or equal to 2, the flow directions of residual oil materials in two adjacent catalyst bed layers which are physically divided by the cylinder and have the same cross section area are just opposite, when the pressure drop of the catalyst bed layers is more than 0.3 times of the maximum pressure drop design value, the flow directions of the residual oil raw material and hydrogenation products in the reactor are changed through a preset switch and/or a valve of an external pipeline, and the reverse alternating change of the flow direction of the residual oil raw material in the reactor is realized, the reactor can not only change the flow direction of the raw material to disperse the deposition position of impurities, but also increase the contact sectional area of the fresh residual oil raw material and the catalyst by reducing the height of the reactor when N is more than or equal to 3, thereby relieving the pressure drop of the whole catalyst bed layer of the reactor and prolonging the service cycle of the reactor.)

1. A residual oil hydrogenation fixed bed reactor with material flow direction alternating is characterized in that: the reactor has an inner space provided with 2 cylindrical interlayers with the same central axis and the same cross section area as the reactor cylinder, the height of the reactor is 1/N of the original height, wherein N is more than or equal to 2, the catalyst bed layer in the reactor is physically divided into 2 parts with the same cross section area by the cylinder, the flow directions of residual oil in two adjacent catalyst bed layers physically divided by the cylinder are opposite, and when the pressure drop of the catalyst bed layer of the reactor is more than 0.3 times of the maximum pressure drop design value of the catalyst bed layer of the reactor, the flow direction of the residual oil raw material in the reactor is changed through a preset switch and/or valve of an external pipeline, so that the reverse alternating change of the flow direction of the residual oil raw material in the reactor is realized.

2. A residual oil hydrogenation fixed bed reactor as claimed in claim 1, wherein, residual oil and hydrogen raw material are injected into the reactor from the central axis of the reactor cylinder or the position near to the central axis, and sequentially pass through the 2 catalyst beds with equal cross-sectional area physically divided by the cylinder, so as to carry out hydrogenation reaction, and the hydrogenation product is discharged from the top of the reactor, when the pressure drop of the catalyst bed of the reactor is larger than 0.3 times of the maximum pressure drop design value of the catalyst bed of the reactor, through the preset switch and/or valve of the external pipeline, the residual oil and hydrogen raw material are injected into the reactor from the cylinder wall or the position near to the reactor, sequentially pass through the 2 catalyst beds with equal cross-sectional area physically divided by the cylinder, so as to carry out hydrogenation reaction, and the hydrogenation product is discharged from the top of the reactor, wherein, the flow direction of the residual oil injected into the reactor from the wall of the reactor cylinder or the position close to the wall of the reactor cylinder is just opposite to the flow direction of the residual oil injected into the reactor from the central shaft of the reactor cylinder or the position close to the central shaft of the reactor cylinder.

3. A residual oil hydrogenation fixed bed reactor as claimed in claim 1, wherein, residual oil and hydrogen raw material are injected into the reactor from the wall of the reactor cylinder or its nearby position, and pass through the 2 catalyst beds with equal cross-sectional area physically divided by the cylinder in turn, so as to carry out hydrogenation reaction, and the hydrogenation product is discharged from the top of the reactor, when the pressure drop of the catalyst bed of the reactor is more than 0.3 times of the designed maximum pressure drop of the catalyst bed of the reactor, through the preset switch and/or valve of the external pipeline, the residual oil and hydrogen raw material become injected into the reactor from the central axis of the reactor cylinder or its nearby position, and pass through the 2 catalyst beds with equal cross-sectional area physically divided by the cylinder in turn, so as to carry out hydrogenation reaction, and the hydrogenation product is discharged from the top of the reactor, wherein, residual oil and hydrogen raw material are injected into the reactor from the central axis of the reactor cylinder or its nearby position The resid flow direction is exactly opposite to the resid flow direction in which resid and hydrogen feed are injected into the reactor from at or near the reactor vessel wall.

4. A residue hydrogenated fixed bed reactor according to claim 1 to 3, wherein the height of the reactor is 1/N of the original reactor, wherein N is 3 or more, and when N is 3 or more, the contact area of the fresh residue feedstock and the catalyst in the reactor is increased.

5. A residuum hydroprocessing fixed bed reactor as claimed in any one of claims 1-3, wherein the flow direction of residuum in said reactor is reversed and alternated, and when the pressure drop of the catalyst bed in said reactor is greater than 0.4-0.8 times of the designed maximum pressure drop of the catalyst bed in said reactor, the flow direction of residuum feedstock in said reactor is reversed and alternated by changing the flow direction of residuum feedstock in said reactor through a preset switch and/or valve of an external pipeline.

6. A residue hydrogenating fixed bed reactor according to one of claims 1 to 5, wherein the reactor is used as a protecting agent reactor and/or a demetallizing reactor, a first reactor of a residue hydrogenating reaction system.

7. A residue hydrogenation fixed bed reactor as claimed in any of claims 1 to 3, wherein the reactor can be combined with any type of residue hydrogenation fixed bed reactor, taking the first reactor with the original process, to form a complete residue hydrogenation reaction system.

8. A residuum hydrogenating fixed bed reactor according to any one of claims 1-3, wherein the reactor further comprises: the upper end enclosure, the lower end enclosure, the upper material inlet, the upper material outlet, the upper material inlet, the lower material outlet, the feeding pipe, the discharging pipe and the (slag) oil (hydrogen) gas distribution disc, wherein the feeding pipe and the discharging pipe are connected with the cylinder body, and the (slag) oil (hydrogen) gas distribution disc is arranged at the upper.

9. A residuum hydrogenating fixed bed reactor as set forth in any one of claims 1-3 wherein the mean pore size and/or spacing of the catalyst at the top oil inlet or product outlet of the intermediate layer at or near the wall of said reactor vessel and at the top oil inlet or product outlet of the intermediate layer at or near the central axis of said reactor vessel is greater than the mean pore size and/or spacing of the catalyst in other portions of the intermediate layer.

10. A residual oil hydrogenation reaction system is characterized in that: the system comprises a residual oil hydrogenation fixed bed reactor with the material flow direction changing alternately according to any one of claims 1 to 9, wherein the residual oil hydrogenation fixed bed reactor with the material flow direction changing alternately is used as a protective agent reactor and/or a demetallization reactor and a first reactor of a residual oil hydrogenation reaction system.

11. A residuum hydroprocessing reaction system according to claim 10, wherein the system further comprises a hydrodesulfurization reactor, a hydrodenitrogenation reactor, a carbon residue removal reactor, and/or a partial hydroconversion reactor.

12. A process for hydrogenating residual oil is characterized in that: a residuum hydroprocessing reaction system as recited in any of claims 10-11, 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: 200-2000 parts; the reaction conditions further comprise: reaction temperature: 350-400 ℃ and reaction pressure: 14-18 MPa, airspeed: 0.2 to 0.5h^-1Hydrogen-oil volume ratio: 400-1000.

Technical Field

The invention relates to the technical field of residual oil hydrogenation, in particular to a residual oil hydrogenation reactor with alternately changed material flow directions, a residual oil hydrogenation system comprising the reactor and a residual oil hydrogenation process.

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, becomes the most mature main technology of residual oil hydrogenation, more and more oil refining enterprises select the fixed bed residual oil hydrogenation and residual oil catalytic cracking combined process to realize the purpose of producing high-quality gasoline, kerosene and diesel oil to the maximum extent, and has remarkable economic benefit and social benefit.

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, CN99225198.2, CN99225197.4, CN03213520.3 and 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, CN 00807042.3.

It is also proposed to overcome the above disadvantages of the above fixed bed reactor for residual oil hydrogenation by adding a material inlet/outlet switch and/or a valve to change the flow direction of the reaction oil gas. For example, CN204490818U and CN103773451A, which are obtained by adding adjustable valves and/or switches to each fixed bed reactor, the oil gas reaction raw materials such as residual oil and hydrogen gas flow in the fixed bed reactor from one direction first, when the pressure difference of the reactor reaches 30-70% of the theoretical maximum pressure difference, the flow direction of the residual oil is changed to the opposite direction of the original flow direction, thereby alleviating the effect of the pressure difference on the operation of the reactor, and so on, until the theoretical maximum pressure difference of the reactor is reached or the apparatus is shut down. Although the residual oil hydrogenation fixed bed reactor can obviously prolong the operation period of a hydrotreatment device, the reaction flow and the reaction time of oil-gas reaction materials are not changed, the activity and the impurity removal rate of each functional catalyst are reduced along with the prolonging of the operation time of the reactor, and finally, the reasonable catalytic activity of each functional catalyst still has to be maintained by increasing the operation temperature of the reactor.

In the related patent technology, no matter the special-shaped catalyst is adopted to increase the bed voidage, or an up-flow reactor is adopted, or the flow direction of reaction oil gas is changed by additionally arranging a material inlet and outlet pipe switch and/or a valve, the reaction material flow always flows along the axial direction of the reactor, the flow cross section area is smaller, solid sediments are firstly coalesced on a front catalyst bed layer and gradually extend towards a rear catalyst bed layer, the problems of synchronous inactivation of the catalyst, larger pressure drop of the catalyst bed layer and the like cannot be fundamentally solved, and the problem of larger waste of active resources of the rear catalyst always exists.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a residual oil hydrogenation reactor with alternately changed material flow directions, a residual oil hydrogenation system containing the reactor and a residual oil hydrogenation process thereof. The invention can increase the contact area of the fresh residual oil material and the catalyst by changing the material flow direction alternately and increasing the sectional area of the catalyst bed layer, thereby relieving the pressure drop of the whole catalyst bed layer of the reactor and prolonging the service cycle of the reactor.

The internal space of the residual oil hydrogenation fixed bed reactor with the material flow direction alternating change is provided with 2 cylindrical interlayers with the same central shaft and the same cross section area as the cylinder body of the reactor, wherein under the condition of not changing the volume and the filling amount of the original reactor, the height of the reactor is 1/N of the height of the original reactor, wherein N is more than or equal to 2, the flow directions of residual oil materials in two adjacent catalyst bed layers which are physically separated by the cylinder and have the same cross section area are opposite, and when the pressure drop of the catalyst bed layers of the reactor is more than 0.3 times of the maximum pressure drop design value of the catalyst bed layers of the reactor, the flow direction of the residual oil materials in the reactor is changed through a preset switch and/or valve of an external pipeline, so that the reverse alternating change of the flow direction of the residual oil materials in the.

The residual oil hydrogenation reaction system comprises a residual oil hydrogenation fixed bed reactor with the material flow direction being alternately changed.

The residual oil hydrogenation process of the invention uses the residual oil hydrogenation reaction system of the residual oil hydrogenation fixed bed reactor with the material flow direction being alternately changed.

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 or vacuum residue oil obtained by primary processing or secondary processing of crude oil, or the atmospheric residue oil or the vacuum residue oilMixing residual oil and vacuum residual oil in any proportion, and mixing atmospheric residual oil or vacuum residual 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/cm³The 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 petrochemical research institute are pacified.

According to the invention, through the improvement of the reactor structure, the flow directions of oil gas materials in the catalyst bed layer of the reactor are regularly and reversely exchanged, deposits in the catalyst bed layer of the reactor are alternately dispersed and deposited at two ends of the residual oil material inlet of the interlayer, and meanwhile, when the N value is more than or equal to 3, the contact area between the fresh oil gas materials and the catalyst of the reactor is increased, so that the space for accommodating impurities in the raw oil is increased under the condition that the volume of the catalyst is not increased, namely, the space for accommodating metal deposits in the whole catalyst bed layer of the reactor is increased, and the service cycle of the catalyst bed layer is correspondingly prolonged. After the protective agent and the hydrodemetallization catalyst in the first reactor are partially deactivated, the hydrodesulfurization catalyst and the hydrodenitrogenation/carbon residue removal catalyst in the subsequent reactor can also continue to normally exert the main functional activity, so that the utilization rate of the active resources of the catalysts is maximized.

The reactor of the invention slows down the pressure drop of the catalyst bed by periodically and alternately changing the flow direction of the oil gas material in the reverse direction and/or increasing the contact area of the fresh oil and the catalyst under the condition of not changing the volume and the filling amount of the catalyst, therefore, the invention does not need to excessively increase the bed voidage of the protective agent and the hydrodemetallization catalyst and also does not need to adopt a grading method of excessive catalyst varieties to balance the reaction performance, thereby effectively reducing the variety and the specification of the catalyst, leading the raw oil to be capable of stably running for a long time at the optimal reaction temperature without carrying out temperature raising operation for compensating the activity of the catalyst, and also 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 residual oil hydrogenation process flow chart corresponding to a reactor with alternately changed material flow directions.

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 material flow direction alternating, wherein the inner space of the reactor is provided with 2 cylindrical interlayers with the same central shaft as the cylinder body of the reactor, a catalyst bed layer positioned in the reactor is physically divided into 2 parts with the same cross section area by the cylinder, the flow directions of residual oil materials in two adjacent catalyst bed layers physically divided by the cylinder are just opposite, and when the pressure drop of the catalyst bed layers of the reactor is more than 0.3 times of the maximum pressure drop design value of the catalyst bed layers of the reactor, the flow direction of the residual oil materials in the reactor is changed through a preset switch and/or a valve of an external pipeline, so that the flow direction of the residual oil materials in the reactor is reversely and alternately changed.

In a preferred technical scheme of the invention, the height of the residual oil hydrogenation fixed bed reactor is 1/2 of the height of the original (conventional) reactor, residual oil and hydrogen raw materials are firstly injected into the reactor from the central axis of the cylinder body of the reactor or the position near the central axis, and sequentially pass through 2 catalyst beds with equal cross section areas physically divided by the cylinder, so as to carry out hydrogenation reaction, hydrogenation products are finally discharged from the top of the reactor, when the pressure drop of the catalyst bed of the reactor is more than 0.3 times of the maximum pressure drop design value of the catalyst bed of the reactor, the residual oil and hydrogen raw materials are changed to be injected into the reactor from the cylinder wall of the reactor or the position near the cylinder wall through a preset switch and/or a valve of an external pipeline, and sequentially pass through 2 catalyst beds with equal cross section areas physically divided by the cylinder, so as to carry out hydrogenation reaction, the hydrogenated product is finally discharged from the top of the reactor, wherein the residual oil and hydrogen raw material are injected into the reactor from the wall of the reactor cylinder or the position close to the wall of the reactor cylinder in the opposite flow direction of the residual oil and hydrogen raw material injected into the reactor from the central shaft of the reactor cylinder or the position close to the central shaft of the reactor cylinder.

In another preferred technical scheme of the invention, for 1/3 that the height of the above-mentioned residuum hydrogenation fixed bed reactor is the height of the original (conventional) reactor, the sectional area of the reactor is increased to 1.5 times of the sectional area of the original (conventional) reactor, residuum and hydrogen raw materials are firstly injected into the reactor from the cylinder wall of the reactor or the position near the reactor, and sequentially pass through 2 catalyst beds with equal sectional areas physically divided by the cylinder, so as to carry out hydrogenation reaction, the hydrogenation product is finally discharged from the top of the reactor, when the pressure drop of the catalyst bed of the reactor is greater than 0.3 times of the maximum pressure drop design value of the catalyst bed of the reactor, through the preset switch and/or valve of the external pipeline, the residuum and hydrogen raw materials are changed to be injected into the reactor from the central axis of the cylinder of the reactor or the position near the cylinder, and sequentially pass through 2 catalyst beds with equal sectional areas physically divided by the cylinder, thereby carrying out hydrogenation reaction, and finally discharging hydrogenation products from the top of the reactor, wherein the flow direction of residual oil and hydrogen raw materials injected into the reactor from the central shaft of the cylinder of the reactor or the position nearby the central shaft of the cylinder of the reactor is just opposite to the flow direction of residual oil and hydrogen raw materials injected into the reactor from the cylinder wall of the reactor or the position nearby the cylindrical wall of the reactor.

Figure 2 of the accompanying drawings represents a residuum hydrogenation process scheme corresponding to a reactor with alternating feed flow for N of 2, i.e., its height is the original (conventional) reactor height 1/2.

In the above-described residue hydrogenation fixed bed reactor of the present invention, preferably, the flow directions of the residue materials are alternately exchanged in opposite directions until the maximum pressure drop design value of the catalyst bed of the reactor is reached.

In another preferred technical scheme of the invention, when the pressure drop of the catalyst bed of the residual oil hydrogenation fixed bed reactor is 0.4-0.8 times of the maximum pressure drop design value of the catalyst bed of the reactor, the flow direction of the residual oil raw material in the reactor is changed through a preset switch and/or valve of an external pipeline, so that the flow direction of the residual oil raw material in the reactor is reversely and alternately changed.

The residual oil hydrogenation fixed bed reactor can be used as a first reactor of a residual oil hydrogenation reaction system, and particularly can be used as a protective agent reactor and/or a demetallization reactor.

In general, the residue hydrogenation fixed bed reactor with alternating material flow directions can be combined with any type of residue hydrogenation fixed bed reactor to form a complete residue hydrogenation reaction system.

The residual oil hydrogenation fixed bed reactor with the material flow direction changing alternately can also comprise: the upper end enclosure, the lower end enclosure, the upper part feed inlet and the upper part discharge outlet, the feed pipe and the discharge pipe which are connected with the cylinder body, and the (slag) oil (hydrogen) gas distribution disc at the upper end and the lower end of the catalyst bed layer.

The invention also provides a residual oil hydrogenation reaction system, which comprises a residual oil hydrogenation fixed bed reactor with the material flow direction being alternately changed. The residual oil hydrogenation reaction system comprises a residual oil hydrogenation fixed bed reactor with the material flow direction being changed alternately as a first 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 hydroconversion reactor.

Preferably, in the above-mentioned residue hydrogenation fixed bed reactor with alternating material flow direction, the average pore diameter and/or gap of the catalyst at the residue material inlet or product oil outlet of the interlayer at the position of the wall of the reactor cylinder or the position near the wall of the reactor cylinder and at the residue material inlet or product oil outlet of the interlayer at the position of the central axis of the reactor cylinder or the position near the central axis of the reactor cylinder are larger than the average pore diameter and/or gap of the catalyst at other positions of the interlayer.

The invention also provides a residual oil hydrogenation process, which uses the residual oil hydrogenation reaction system and a residual oil hydrogenation fixed bed reactor with the material flow direction being alternately changed.

The residual oil hydrogenation process flow of the invention is as follows: raw oil mixed with dissolved hydrogen enters the reactor from a central shaft at the upper part of the reactor or a position near the central shaft and a cylinder wall of the reactor or a position near the cylinder wall of the reactor through a feeding pipe, firstly flows into a catalyst bed layer positioned in an interlayer near the central shaft or a catalyst bed layer positioned in an interlayer near the cylinder wall of the reactor through small holes on an oil-gas distributor, and supplementary hydrogen uniformly distributed through a hydrogen distribution disc upwards passes through the catalyst bed layer, is mixed with the raw oil and then is subjected to hydrogenation reaction on the catalyst bed layer. Raw material (slag) oil and hydrogen gas pass through the protective agent layer and/or the hydrodemetallization catalyst layer in the 2 catalyst bed layers with equal cross-sectional areas, which are physically divided by the cylinder in the reactor, from top to bottom or from bottom to top in sequence along the axial direction of the reactor, when the pressure drop of the catalyst bed layers is more than 0.3 times, for example, 0.4 to 0.8 times of the maximum pressure drop design value of the catalyst bed layers, the flow direction of the residual oil raw material in the reactor is changed through a preset switch and/or valve of an external pipeline, so that the flow direction of the residual oil raw material in the reactor is reversely and alternately changed, and the operation is repeated until the maximum pressure drop design value of the catalyst bed layers is reached. The final oil (hydrogenation product) produced in the reaction is discharged from the collecting area at the upper part of the reactor through an outlet and further flows through a fixed bed reactor with a hydrodesulfurization catalyst bed, a reactor with a hydrodenitrogenation and/or carbon residue removal catalyst bed and a reactor with a partial hydroconversion catalyst bed. In the first reactor of the invention, the removed mechanical impurities and easily removed iron and calcium impurities are deposited on the protective agent bed, the metal impurities such as nickel, vanadium and the like are mainly deposited on the hydrogenation demetallization catalyst bed, and the obtained 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 materials, catalyst varieties and filling methods thereof as in comparative example 1 below were used to compare the operation of the residue hydrogenation fixed bed reactor, system and process with the material flow direction alternating according to the present invention as shown in fig. 2 with the operation of the conventional residue hydrogenation fixed bed reactor, system and process as shown in fig. 1.

Wherein the reactor with the material flow direction alternating according to the present invention is used as a protecting agent and/or demetallization reactor, i.e. a first reactor, as shown in fig. 2, the catalyst bed in the reactor is physically divided into 2 sandwich structures with the same central axis as the reactor cylinder body, the height of the sandwich structure is 1/2 of the height of the original conventional reactor (the first reactor in fig. 1), the flow directions of the residual oil raw material in the two catalyst beds with the same cross section (sandwich structures) physically divided by the cylinder are exactly opposite, when the pressure drop of the catalyst beds is more than 0.5-0.7 times of the designed maximum pressure drop value of the catalyst beds, the flow direction of the residual oil raw material in the reactor is changed through a preset switch and/or valve of an external pipeline, so that the flow direction of the residual oil raw material in the reactor is reversely and alternately changed, until reaching the maximum pressure drop design value of 0.7MPa of the catalyst bed.

In this example 1, a self-developed and produced ZRH-102SP catalyst is used, the hydrodemetallization catalyst is ZRH-112AS, the hydrodemetallization/hydrodesulfurization transition catalyst is ZRH-213AS, the hydrodesulfurization catalyst is ZRH-311AS, the hydrodenitrogenation catalyst is ZRH-412AS, and the grading loading ratio of each functional catalyst in each reactor is ZRH-102 SP: ZRH-112 AS: ZRH-213 AS: ZRH-311 AS: ZRH-412AS ═ 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^-1On a basis, the removal rate of various impurities is taken from the hydrogenation reaction 20Data at 00 h. The reaction results are shown in table 1.

TABLE 1

After the hydrogenation system operates for 1500 hours, the pressure drop of the catalyst bed layer of the first reactor (protective reactor) reaches 0.35MPa (which is 50 percent of the theoretical maximum pressure difference), at the moment, the flow direction of the residual oil raw material in the first reactor is reversely changed, and other test conditions are unchanged. After a total operating time of 6000 hours, the differential pressure in the guard reactor reached 0.68MPa and the entire system was shut down.

Comparative example 1

The same raw materials, functional catalysts, catalyst loading ratios and reaction conditions as those in example 1 were used, and a conventional residue hydrogenation fixed bed reactor, system and process thereof as shown in fig. 1 were used, and the volume of the first reactor was equal to that in example 1. The reaction results are shown in table 2.

TABLE 2

After the hydrogenation system operates for 1600 hours, the pressure difference of the first reactor reaches 0.35 MPa; after 4000 hours of operation of the system, the pressure difference of the first reactor reaches 0.69MPa, the device is shut down, and the operation period of the comparative example 1 is shortened by 2000 hours compared with that of the example 1, namely the operation period of the example 1 is prolonged by 50 percent compared with that of the comparative example 1.

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 airspeed, the removal rate of nickel, vanadium, sulfur and nitrogen is reduced by about 5 percent along with the increase of 10 percent of the benchmark, and the removal rate of residual carbon is reduced by 7 to 8 percent.

The residue oil hydrogenation fixed bed reactor process of the invention is adopted, and impurities are removed under the same standardThe quality rate is higher than that of the conventional residual oil hydrogenation fixed bed reactor process; with the increase of the oil inlet amount benchmark, the reaction space velocity can also be increased by 0.20h^-1Increased to 0.26h^-1However, the material flow direction is changed alternately, so that the pressure drop of the whole catalyst bed layer of the reactor is relieved, the service cycle of the reactor is prolonged, the deactivation rate of the catalyst is reduced, and finally, although the removal rate of various impurities is reduced, the reduction rate is reduced, the removal rate of nickel, vanadium, sulfur and nitrogen is reduced by about 3 percent along with the increase of 10 percent of the benchmark, and the removal rate of residual carbon is reduced by about 4 percent.

Example 2

The same raw materials, functional catalysts, catalyst grading loading ratios and reaction conditions as in comparative example 2 below were used to perform a comparison of the process operations of the residue hydrogenation fixed bed reactor, system and process according to the present invention as shown in fig. 2 and the process of the conventional residue hydrogenation fixed bed reactor, system and process as shown in fig. 1.

Wherein the reactor with the material flow direction alternating according to the invention is used as a protective agent and/or demetallization reactor, namely a first reactor, the catalyst bed in the reactor is physically divided into 2 sandwich structures with the same central axis as the reactor cylinder by 1 cylinder with the same central axis as the reactor cylinder, the height of the sandwich structure is 1/3 of the height of the original conventional reactor (the first reactor in figure 1), the flow directions of the residual oil in the 2 catalyst beds with the same cross section (the sandwich structures) physically divided by the cylinder are just opposite, when the pressure drop of the catalyst beds is more than 0.3-0.7 times of the maximum pressure drop design value of the catalyst beds, the flow direction of the residual oil raw material in the reactor is changed through a preset switch and/or valve of an external pipeline, so that the flow direction of the residual oil raw material in the reactor is reversely and alternately changed, and the process is repeated, until reaching the maximum pressure drop design value of 0.7MPa of the catalyst bed.

In this example 2, the self-developed ZRH-series catalyst was used, the protecting agent was ZRH-103SP, the hydrodemetallization catalyst was ZRH-116AS, the hydrodemetallization/hydrodesulfurization transition catalyst was ZRH-214AS, the hydrodesulfurization catalyst was ZRH-313AS, the hydrodenitrogenation catalyst was ZRH-412AS, and each reaction was performedIn the reactor, the grading filling proportion of each functional catalyst is ZRH-103 SP: ZRH-116 AS: ZRH-214 AS: ZRH-313 AS: ZRH-412AS ═ 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, 13.57w% 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

After the hydrogenation system operates for 1000 hours, the pressure drop of the catalyst bed layer of the first reactor reaches 0.25MPa (35.7 percent of the theoretical maximum pressure difference), at the moment, the flow direction of the residual oil raw material in the first reactor is reversely changed, and other test conditions are unchanged. The reverse operation was thereafter switched every 500 hours until the plant was shut down. The pressure drop of the first reactor catalyst bed layer after 1500 hours of operation reaches 0.31MPa, the pressure drop of the first reactor catalyst bed layer after 2000 hours of operation reaches 0.36MPa, the pressure drop of the first reactor catalyst bed layer after 2500 hours of operation reaches 0.4MPa, the pressure drop of the first reactor catalyst bed layer after 7500 hours of operation reaches 0.68MPa, and the device is shut down.

Comparative example 2

The same raw materials, functional catalysts, catalyst loading ratios and reaction conditions as those in example 2 were used, and a conventional residue hydrogenation fixed bed reactor, system and process thereof as shown in fig. 1 were used, and the volume of the first reactor was equal to that in example 2. The reaction results are shown in Table 4.

TABLE 4

After the hydrogenation system device is operated for 4500 hours, the pressure drop of the catalyst bed layer of the first reactor is 0.69MPa, and the device is shut down. It can be seen that the operating cycle of comparative example 2 is shortened by 3000 hours compared to example 2, i.e. the operating cycle of example 2 is extended by 67% for comparative example 2.

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, the residual oil hydrogenation fixed bed system and the residual oil hydrogenation fixed bed process have higher impurity removal rate than that of a conventional fixed bed reactor. With the prolonging of the operation time, from 1000h to 2000h, the removal rate of various impurities of the conventional fixed bed reactor is reduced by 4 percent, and from 2000h to 3000h, the removal rate of various impurities is reduced by 6 percent; in the residual oil hydrogenation fixed bed reactor, the system and the process thereof, the catalyst positioned in the fixed bed layer of the first reactor starts to switch the feed inlet after 1000 hours, so that the pressure drop of the system is increased and the inactivation rate of the catalyst is slowed, and the removal rate of various impurities is reduced by less than that of the conventional fixed bed reactor from 1000 hours to 2000 hours, the removal rate of various impurities of the conventional fixed bed reactor is reduced by 2 percent, and the removal rate of various impurities is reduced by about 3 percent from 2000 hours to 3000 hours.