Method for grading a residue hydroprocessing catalyst and use thereof

Abstract

The application discloses a method for grading a residual oil hydrogenation catalyst and application thereof. The method comprises three hydrogenation reactors in series, i.e., a first reactor, a second reactor and a third reactor. The first reactor is filled with at least a protective agent, the second reactor is filled with at least a hydrogenation demetallization catalyst, and the third reactor is filled with at least a hydrogenation desulfurization catalyst. The first reactor is filled with a hydrogenation catalyst A at the bottom and / or the second reactor is filled with a hydrogenation catalyst B at the bottom. The hydrogenation catalyst A and the hydrogenation catalyst B are filled in a specific way. The method can improve the problem that the catalyst activity cannot be fully exerted due to insufficient temperature compensation in the reactor. The method fully exerts the activity of each catalyst, makes each catalyst tend to be inactivated synchronously, improves the operation stability of the device, and helps prolong the operation period of the device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of hydrogenation, and particularly relates to a method for grading a residue oil hydrogenation catalyst and application thereof. BACKGROUND

[0002] Residue oil hydrogenation technology has the characteristics of strong raw material adaptability and simple production operation process, and can provide high-quality raw materials for the downstream catalytic cracking process, and has become one of the most important heavy oil processing processes in modern oil refining and petrochemical industry.

[0003] Generally, the catalyst grading loading technology is widely used in the fixed bed hydrogenation process. In the reactor sequence for processing heavy oil, protective catalyst, metal removal catalyst, desulfurization catalyst, and residual carbon removal catalyst (or denitrogenation catalyst) are sequentially loaded, and sometimes some transition catalysts are also loaded between two kinds of catalysts. However, due to the different characteristics of different crude oils, different catalyst grading loading methods need to be developed for different oil products to increase the utilization rate of catalyst activity, so as to achieve the purpose of fully exerting the catalytic performance of all catalysts, synchronous deactivation, and prolonging the overall service life of the series catalysts.

[0004] In recent years, the amount of residue oil hydrogenation treatment in China is increasing, while the types and sources of raw oil are becoming more and more complex. Therefore, many residue oil hydrogenation devices that have been in operation for a long time are facing the problem that the design load or design raw material does not match the existing treatment capacity requirements or actual raw materials. The design load of some equipment cannot meet the requirements of current treatment capacity or raw materials, for example, the heating furnace, which is the most important equipment in the fixed bed residue oil hydrogenation device. Because there is no heat supplement system in the reactor, if the heating furnace load is insufficient, and the heat exchange efficiency of the heat exchanger is insufficient (especially in the case of low heat exchange efficiency, which is easy to occur in the later stage of actual device operation), the backward condition of such equipment seriously limits the maximization of enterprise benefits. Among the series of reactions occurring in the residue oil hydrogenation treatment process, hydrogenation reactions are all exothermic reactions. Among them, the reaction heat release of metal removal is relatively moderate, while hydrogenation desulfurization and denitrogenation are strong exothermic reactions. Therefore, along the flow direction, the bed temperature in the front reactor and the reactor outlet temperature will probably remain in a relatively low temperature range. Because the reactions occurring in the front reactor are relatively moderate, the heat release is low, resulting in insufficient temperature compensation. The reaction temperature of the front reactor is always at a low level. Under the condition that other reaction parameters remain unchanged, the higher the bed temperature, the higher the conversion rate. If the conversion rate of the front reactor is continuously low, the hydrogenation treatment load will be shifted to the rear reactor along the flow direction, resulting in accelerated deactivation of the catalyst in the rear reactor, and incomplete activity of the catalyst in the front reactor. This goes against the original intention of catalyst grading, is not conducive to long-term operation of the device, and seriously damages the interests of the enterprise.

[0005] CN94117660.6 discloses a method for grading hydrogenation catalysts. The method mainly physically mixes high-voidage catalysts and low-voidage catalysts in different proportions, and improves the deposition effect of impurities such as iron and calcium in the catalyst bed through smooth transition from high void to low void.

[0006] In summary, the prior art cannot solve the problem that the design of heating furnaces and heat exchange load on some industrial devices cannot meet the current device processing capacity, and even some technical methods may exacerbate the insufficient temperature compensation of the bed. If equipment modification is performed, the cost is too high. Therefore, it is necessary to develop a low-cost solution that does not require device modification for the above problems. SUMMARY

[0007] In view of the deficiencies of the prior art, the present application provides a method for grading residual oil hydrogenation catalysts and its application. The grading method of the present application can improve the problem that the catalyst activity cannot be fully utilized due to insufficient temperature compensation in the reactor. The grading method fully utilizes the activity of each catalyst, so that each catalyst can be deactivated synchronously, thereby improving the operation stability of the device and helping to prolong the operation cycle of the device.

[0008] The present application provides a method for grading residual oil hydrogenation catalysts, wherein the grading method comprises at least three hydrogenation reactors in series, i.e. a first reactor, a second reactor and a third reactor, wherein at least a guard catalyst is loaded in the first reactor, at least a hydrodemetalization catalyst is loaded in the second reactor, and at least a hydrodesulfurization catalyst is loaded in the third reactor; hydrogenation catalyst A is loaded at the bottom of the first reactor and / or hydrogenation catalyst B is loaded at the bottom of the second reactor, wherein the mass content of hydrogenation active metal in the hydrogenation catalyst A in terms of oxides is higher than that in the adjacent downstream catalyst (excluding the hydrogenation catalyst A), the void fraction of the hydrogenation catalyst A is higher than that of the adjacent upstream catalyst (excluding the hydrogenation catalyst A), the mass content of hydrogenation active metal in the hydrogenation catalyst B in terms of oxides is higher than that in the adjacent downstream catalyst (excluding the hydrogenation catalyst B), and the void fraction of the hydrogenation catalyst B is higher than that of the adjacent upstream catalyst (excluding the hydrogenation catalyst B).

[0009] According to the present application, the first reactor, the second reactor and the third reactor are connected in series, and the catalysts loaded therein are loaded according to the conventional grading principle except for the hydrogenation catalyst A and the hydrogenation catalyst B, i.e. along the flow direction, the content of hydrogenation active metal gradually increases, the particle size gradually decreases, and the void fraction gradually decreases.

[0010] According to the present application, the volume of hydrogenation catalyst A packed at the bottom of the first reactor accounts for 1% to 30%, preferably 5% to 30% of the total catalyst packing volume in the first reactor.

[0011] According to the present application, the volume of hydrogenation catalyst B packed at the bottom of the second reactor accounts for 1% to 30%, preferably 3% to 25% of the total catalyst packing volume in the second reactor.

[0012] According to the present application, the content of hydrogenation active metal in hydrogenation catalyst A in the first reactor is at least 0.5 percentage points higher than the mass content of hydrogenation active metal in the form of oxide in the adjacent downstream catalyst (excluding hydrogenation catalyst A), preferably 1 to 9.0 percentage points higher.

[0013] According to the present application, in hydrogenation catalyst A in the first reactor, preferably, the hydrogenation active metal is molybdenum, nickel and cobalt, and in the adjacent downstream catalyst (excluding hydrogenation catalyst A) of hydrogenation catalyst A, the hydrogenation active metal is molybdenum and nickel. Further preferably, the mass content of molybdenum in the form of oxide in hydrogenation catalyst A is at least 0.5 percentage points higher than the mass content of molybdenum in the form of oxide in the adjacent downstream catalyst (excluding hydrogenation catalyst A), preferably 1 to 5.0 percentage points higher, the mass content of nickel in the form of oxide in hydrogenation catalyst A is within 0.4 percentage points of the mass content of nickel in the form of oxide in the adjacent downstream catalyst (excluding hydrogenation catalyst A), and the mass content of cobalt in the form of oxide in hydrogenation catalyst A is at least 0.5 percentage points higher than the mass content of cobalt in the form of oxide in the adjacent downstream catalyst (excluding hydrogenation catalyst A), preferably 0.8 to 4.0 percentage points higher.

[0014] According to the present application, the porosity of hydrogenation catalyst A in the first reactor is at least 2 percentage points higher than the porosity of the adjacent upstream catalyst (excluding hydrogenation catalyst A), preferably 2 to 15 percentage points higher.

[0015] According to the present application, the mass content of hydrogenation active metal in hydrogenation catalyst B in the second reactor is at least 0.5 percentage points higher than the mass content of hydrogenation active metal in the form of oxide in the adjacent downstream catalyst (excluding hydrogenation catalyst B), preferably 1 to 9.0 percentage points higher.

[0016] According to the present application, in the first reactor, the hydrogenation catalyst B, preferably, the hydrogenation active metals are molybdenum, nickel and cobalt, and in the hydrogenation catalyst B adjacent to the downstream catalyst (not including the hydrogenation catalyst B), the hydrogenation active metals are molybdenum and nickel. Further preferably, the mass content of molybdenum in the hydrogenation catalyst B is at least 0.5 percentage points higher than the mass content of molybdenum in the adjacent downstream catalyst (not including the hydrogenation catalyst B) in terms of oxide, preferably 1-5.0 percentage points higher, and the mass content of nickel in the hydrogenation catalyst B is within 0.8 percentage points of the mass content of nickel in the adjacent downstream catalyst (not including the hydrogenation catalyst B) in terms of oxide. The mass content of cobalt in the hydrogenation catalyst B is at least 0.8 percentage points higher than the mass content of cobalt in the adjacent downstream catalyst (not including the hydrogenation catalyst B) in terms of oxide, preferably 1-4.0 percentage points higher.

[0017] According to the present application, the porosity of the hydrogenation catalyst B in the second reactor is at least 2 percentage points higher than the porosity of the adjacent upstream catalyst (not including the hydrogenation catalyst B), preferably 2-15 percentage points higher.

[0018] According to the present application, the first hydrogenation reactor is packed with a hydrogenation guard catalyst and a hydrogenation catalyst A, and a hydrogenation demetallization catalyst can also be packed between the hydrogenation guard catalyst and the hydrogenation catalyst A, and the second hydrogenation reactor is packed with a hydrogenation demetallization catalyst and a hydrogenation catalyst B.

[0019] According to the present application, the hydrogenation guard catalyst in the first hydrogenation reactor can be multiple, preferably 2-4. The demetallization catalyst in the first hydrogenation reactor can be multiple, preferably 2-4.

[0020] According to the present application, the second hydrogenation reactor is packed with at least one hydrogenation demetallization catalyst, preferably 1-4.

[0021] According to the present application, the number of hydrogenation reactors is preferably 3-6. The hydrogenation reactors are fixed bed reactors.

[0022] According to the present application, the particle size of the hydrogenation catalyst A in the first hydrogenation reactor is higher than the particle size of the adjacent upstream catalyst (not including the hydrogenation catalyst A), preferably at least 0.5 mm higher, preferably 0.8-10.0 mm higher, more preferably 0.8-5.0 mm higher.

[0023] According to the present application, the particle size of the hydrogenation catalyst B in the second hydrogenation reactor is higher than the particle size of the adjacent upstream catalyst (not including the hydrogenation catalyst B), preferably at least 0.5 mm higher, preferably 0.8-10.0 mm higher, more preferably 0.8-5.0 mm higher.

[0024] According to the present application, the third hydrogenation reactor is filled with a hydrodesulfurization catalyst, and a hydrodemetallization catalyst can be filled upstream of the hydrodesulfurization catalyst, and a hydrodecarbon residue catalyst can be filled downstream of the hydrodesulfurization catalyst.

[0025] According to the present application, preferably, the hydrogenation catalyst A is 1 to 4, preferably 2 to 4. The loading mode of the various hydrogenation catalyst A is that, along the flow direction, the porosity of the various hydrogenation catalyst A is from small to large, and the content of the hydrogenation active metal component is from large to small.

[0026] According to the present application, preferably, the hydrogenation catalyst B is 1 to 4, preferably 2 to 4. The loading mode of the various hydrogenation catalyst B is that, along the flow direction, the porosity of the various hydrogenation catalyst B is from small to large, and the content of the hydrogenation active metal component is from large to small.

[0027] According to the present application, the hydrogenation catalyst A comprises a carrier and a hydrogenation active metal component. The content of the hydrogenation active metal component is 1.7wt% to 23.5wt%, and the content of the carrier is 76.5wt% to 98.3wt%, based on the mass of the catalyst. The hydrogenation active metal comprises Group ⅥB and Group Ⅷ metal. The Group ⅥB metal is preferably Mo, and the Group Ⅷ metal is preferably Ni and Co. Preferably, the content of molybdenum oxide is 1.5wt% to 17.5wt%, the content of nickel oxide is 0.2wt% to 6.0wt%, and the content of cobalt oxide is 0.5wt% to 6.0wt%, based on the mass of the hydrogenation catalyst A. The hydrogenation catalyst A can selectively add an auxiliary agent in the art, such as one or more of fluorine, silicon, phosphorus, boron, titanium, zirconium, etc. Further, the carrier is generally inorganic oxide; the carrier comprises one or several of alumina, silica, calcium oxide, titanium oxide, activated carbon, etc., preferably alumina.

[0028] According to the present application, the hydrogenation catalyst B comprises a support and a hydrogenation active metal component. The content of the hydrogenation active metal component is 1.7wt% to 23.5wt% and the content of the support is 76.5wt% to 98.3wt% based on the mass of the catalyst. The hydrogenation active metal comprises Group VI B and Group VIII metals. The Group VI B metal is preferably Mo and the Group VIII metal is preferably Ni and Co. Preferably, the content of MoO3 is 1.5wt% to 17.5wt%, the content of NiO is 0.2wt% to 6.0wt% and the content of CoO is 0.5wt% to 6.0wt% based on the mass of the hydrogenation catalyst B. Optionally, one or more of the conventional additives in the art, such as fluorine, silicon, phosphorus, boron, titanium, zirconium, etc. can be added to the hydrogenation catalyst B. Further, the support is generally inorganic oxide; the support comprises one or more of alumina, silica, calcium oxide, titanium oxide, activated carbon, etc., preferably alumina.

[0029] According to the present application, the composition of the hydrogenation guard comprises a support and a hydrogenation active metal component. The selection can be made according to the conventional catalysts in the art. The content of the hydrogenation active metal component is 0 to 13.0wt% and the content of the support is 87.0wt% to 100wt% based on the mass of the catalyst; preferably, the content of MoO3 is 0% to 10wt%, preferably 0.01wt% to 10wt%, the content of NiO is 0 to 3wt%, preferably 0.01wt% to 3wt%, and the content of the support is 87wt% to 100wt%, preferably 87wt% to 99.98wt% based on the mass of the hydrogenation guard.

[0030] According to the present application, the composition of the hydrogenation demetallization catalyst comprises a support and a hydrogenation active metal component. The selection can be made according to the conventional catalysts in the art. The content of the hydrogenation active metal component is 1.2wt% to 17.7wt% and the content of the support is 82.3wt% to 98.8wt% based on the mass of the hydrogenation demetallization catalyst. Preferably, the content of MoO3 is 1.0wt% to 13.5wt%, the content of NiO is 0.2wt% to 4.2wt%, and the content of the support is 82.3wt% to 98.8wt% based on the mass of the hydrogenation demetallization catalyst.

[0031] According to the present application, preferably, when there are multiple hydrogenation catalysts A, the mass content of the active metal in terms of oxide between any two adjacent hydrogenation catalysts A differs by at least 0.5 percentage points, preferably 1.0 to 5.0 percentage points, more preferably 1.3 to 3.0 percentage points.

[0032] According to the present application, preferably, when there are multiple hydrogenation catalysts A, the mass content of molybdenum oxide between two adjacent hydrogenation catalysts A differs by at least 0.4 percentage points, preferably 1.0-4.9 percentage points, the mass content of cobalt oxide differs by at least 0.1 percentage points, preferably 0.1-1.0 percentage points, and the mass content of nickel oxide can be equal or differ by less than 0.4 percentage points.

[0033] According to the present application, preferably, when there are multiple hydrogenation catalysts B, the mass content of hydrogenation active metals in oxide form between two adjacent hydrogenation catalysts B differs by at least 0.5 percentage points, preferably 1.0-5.0 percentage points, more preferably 1.5-3.0 percentage points.

[0034] According to the present application, preferably, when there are multiple hydrogenation catalysts B, the mass content of molybdenum oxide between two adjacent hydrogenation catalysts B differs by at least 0.5 percentage points, preferably 0.8-4.9 percentage points, the mass content of cobalt oxide differs by at least 0.2 percentage points, preferably 0.2-1.5 percentage points, and the mass content of nickel oxide can be equal or differ by less than 0.4 percentage points.

[0035] According to the present application, preferably, the particle size of two adjacent hydrogenation catalysts A differs by at least 0.5 mm, preferably 0.8-10.0 mm, more preferably 0.8-4.0 mm.

[0036] According to the present application, preferably, the particle size of two adjacent hydrogenation catalysts B differs by at least 0.5 mm, preferably 0.8-10.0 mm, more preferably 0.8-4.0 mm.

[0037] According to the present application, the shape of the hydrogenation catalyst A or hydrogenation catalyst B can be spherical, spheroidal, cylindrical, multi-vane, strip-shaped, trilobal, or quadrilobal, preferably spheroidal or trilobal. The spheroidal shape is preferably denticular.

[0038] According to the present application, when the first hydrogenation reactor is not loaded with hydrogenation catalyst A, the hydrogenation catalyst loading volume ratio in the first hydrogenation reactor is loaded according to the conventional method. When the second hydrogenation reactor is not loaded with hydrogenation catalyst B, the hydrogenation catalyst loading volume ratio in the second hydrogenation reactor is loaded according to the conventional method.

[0039] According to the present application, when the first hydrogenation reactor is loaded with hydrogenation guard catalyst, hydrogenation demetallization catalyst, and hydrogenation catalyst A, the loading volume of hydrogenation catalyst A is 5%-30% of the total volume of all catalysts in the first reactor, the loading volume of hydrogenation guard catalyst is 10%-80%, and the loading volume of hydrogenation demetallization catalyst is 15%-60%.

[0040] According to the present application, when the hydrogen demetallization catalyst and the hydrogenation catalyst B are loaded in the second reactor, the loading volume of the hydrogenation catalyst B is 3% to 25% and the loading volume of the hydrogen demetallization catalyst is 75% to 97% based on the total volume of all catalysts in the second reactor.

[0041] According to the present application, the catalyst loading volume ratio of the first hydrogenation reactor, the second hydrogenation reactor, the third hydrogenation reactor, the fourth hydrogenation reactor and the like is according to the conventional loading.

[0042] The second aspect of the present application provides an application of the above hydrogenation catalyst grading method in a residue oil hydrogenation reaction.

[0043] According to the present application, the method of the application is specifically that: under the hydrogenation treatment reaction conditions, the residue oil is contacted with the catalyst loaded by the above grading method to perform hydrogenation reaction, and a hydrogenation treatment product is obtained.

[0044] According to the present application, in the application, the operating conditions of each reactor are independently 8.0 to 20.0 MPa of hydrogen partial pressure, 320 to 420℃ of reaction temperature, 0.15 to 2.0 h-1 of liquid hourly space velocity, and 400:1 to 1000:1 of hydrogen to oil volume ratio. -1

[0045] Compared with the prior art, the present application has the following advantages:

[0046] 1. By using the grading method of the present application, the problem of insufficient compensation of the reactor inlet temperature and / or the bed temperature of the existing residue oil hydrogenation industrial device can be solved at the lowest cost without device modification.

[0047] 2. In the present application, the grading method improves the reaction load of the first reactor and / or the second reactor, so that the catalyst bed layer at the rear part of the flow direction is not moved backward, and the problems of accelerated deactivation of the catalyst, radial temperature difference, hot spots and the like caused by excessively high reaction load of the rear bed layer are avoided, the operation efficiency of the device is improved, and the operation cycle is prolonged.

[0048] 3. The grading method of the present application applied to the residue oil hydrogenation treatment method can improve the flow distribution in the reactor, reduce the radial temperature difference at the bottom of the reactor, and prolong the operation cycle of the device. DETAILED DESCRIPTION

[0049] The technical solutions of the present application will be further described below in combination with examples, but are not limited to the following examples.

[0050] ​The device used in the present application, the embodiment, is a fixed bed hydrogenation treatment experimental device for testing residual oil feedstock. Four fixed bed reactors with a volume of 400 mL are arranged in series on the device. The four reactors are, in sequence along the flow direction, a first reactor (one reactor), a second reactor (two reactor), a third reactor (three reactor), and a fourth reactor (four reactor). The total loading volume of the catalyst in each reactor is 275 mL.

[0051] The hydrogenation catalyst A or the hydrogenation catalyst B in the present application, the embodiment, is prepared by using the conventional preparation method of catalysts in the field, i.e. impregnation method. The other catalysts in each example are commercial hydrogenation catalysts.

[0052] The feedstock oil used in the present application, the embodiment, and the comparative example is completely the same. The properties of the feedstock oil are shown in Table 1.

[0053] The overall process conditions in the present application, the embodiment, and the comparative example are the same. The hydrogenation reaction process conditions are shown in Table 2. In each reactor, the flow direction is from top to bottom.

[0054] In the present application, the hydrogenation catalyst A or the hydrogenation catalyst B in the embodiment is represented by A or B followed by a number, respectively. For example, A1, A2, B1, B2.

[0055] In the present application, the protective agent in each example is represented by HG followed by a number. For example, HG1, HG2, HG3.

[0056] In the present application, the hydrogen demetallization catalyst in each example is represented by HDM followed by a number. For example, HDM1, HDM2, HDM3.

[0057] In the present application, the particle size is the minimum value of the distance between any two parallel tangent lines on the cross section of the catalyst (the minimum Feret diameter). F .

[0058] In the present application, the method for measuring the porosity is as follows:

[0059] A certain amount of catalyst particles (the mass of the catalyst is m 催化剂自重 ) is soaked in an appropriate amount of water for one hour. The amount of water should be enough to completely soak the catalyst in water. Then, the mass of the catalyst particles m 吸水后催化剂重 is weighed after spinning to remove the water adsorbed on the surface. The water absorption rate is calculated according to the formula as follows:

[0060] Water absorption rate = [(m 吸水后催化剂重 -m 催化剂自重 ) / ρ 水 ] / m 催化剂自重 .

[0061] Fill the catalyst particles in a 1000 mL measuring cylinder, shake the measuring cylinder constantly during the filling process to make the catalyst reach the tap density state. When the catalyst particles are filled to 1000 mL (the mass of the catalyst is m 量筒中催化剂自重 ), plug the porous rubber plug at the interface of the catalyst particles. Inject an appropriate amount of water into the measuring cylinder to reach the interface of the catalyst particles. The volume of the water added is V 水 . Calculate the porosity according to the formula as follows:

[0062] Porosity = (V 水 - water absorption rate x m 量筒中催化剂自重 ) / 1000 mL.

[0063] The catalyst loading methods in the three-stage and four-stage in the present application, examples and comparative examples are the same. In the four-stage, the hydrogenation desulfurization catalyst FZC-33B and the hydrogenation desulfurization catalyst FZC-41A are loaded in turn along the flow direction, and the loading volume ratio of the above-mentioned catalysts in the four-stage is 20:80. The FZC series catalysts in the four-stage are all residual oil hydroprocessing catalysts developed by Dalian Institute of Petrochemical Technology. The loading volume ratio of the catalysts in the first stage, the second stage, the third stage and the fourth stage is 1:1:1:1. The loading scheme of the catalysts in the third stage is shown in Table 3, wherein HDS is a hydrogenation desulfurization catalyst.

[0064] Table 1 Properties of raw oil

[0065]

[0066]

[0067] Table 2 Hydrogenation reaction process conditions

[0068] Hydrogen partial pressure / MPa 15.7 Liquid hourly space velocity / h -1 ]] 0.21 Hydrogen-oil volume ratio 650：1 Reaction inlet temperature / ℃ 355

[0069] Table 3 Loading scheme of catalysts in the third stage

[0070]

[0071] Example 1

[0072] The loading scheme of the catalysts in the first stage and the second stage in this example is shown in Tables 4 and 5.

[0073] Table 4 Loading scheme of catalysts in the first stage

[0074]

[0075] Table 5 Loading scheme of catalysts in the second stage

[0076]

[0077]

[0078] Example 2

[0079] The one- and two-reverse catalyst loading schemes for this example are shown in Tables 6, 7.

[0080] Table 6 One-reverse catalyst loading scheme

[0081]

[0082] Table 7 Two-reverse catalyst loading scheme

[0083]

[0084] Example 3

[0085] The one- and two-reverse catalyst loading schemes for this example are shown in Tables 8, 9.

[0086] Table 8 One-reverse catalyst loading scheme

[0087]

[0088] Table 9 Two-reverse catalyst loading scheme

[0089]

[0090] Example 4

[0091] The one- and two-reverse catalyst loading schemes for this example are shown in Tables 10, 11.

[0092] Table 10 One-reverse catalyst loading scheme

[0093]

[0094] Table 11 Two-reverse catalyst loading scheme

[0095]

[0096] Comparative Example 1

[0097] The one- and two-reverse catalyst loading schemes for this example are shown in Tables 12, 13.

[0098] Table 12 One-reverse catalyst loading scheme

[0099]

[0100]

[0101] Table 13 Two-reverse catalyst loading scheme

[0102]

[0103] Test Example

[0104] When the device starts to run, the raw oil and hydrogen enter a reactor, and then enter the second reactor, the third reactor and the fourth reactor in turn. After 500 hours of reaction, the bed temperature at different positions in the reactor is shown in Table 14, and the impurity removal effect of the reaction is shown in Tables 15-19. The impurity removal rate of the final product when the raw oil is stably operated for 500h, 2500h and 4500h is shown in Table 20.

[0105] Table 14 Comparison of bed temperature at different positions in the reactor

[0106]

[0107] Table 15 Reaction impurity removal activity of Example 1

[0108]

[0109] Table 16 Reaction impurity removal activity of Example 2

[0110]

[0111] Table 17 Reaction impurity removal activity of Example 3

[0112]

[0113] Table 18 Reaction impurity removal activity of Example 4

[0114]

[0115] Table 19 Reaction impurity removal activity of Comparative Example 1

[0116]

[0117] Table 20 Impurity removal rate of the final product when stably operated for 500h, 2500h and 4500h

[0118]

[0119] As can be seen from the examples and comparative examples, the grading method of the catalysts of the present application can effectively improve the bed temperature and the bed void fraction at the positions of the hydrogenation catalyst A in the lower part of the first reactor and the hydrogenation catalyst B in the lower part of the second reactor. Not only the activity of each catalyst can be fully utilized, but also the activity of the catalysts loaded in the first two reactors can be fully utilized. By improving the bed void fraction, the metal capacity of the catalyst bed is improved, and at the same time, the risk of uneven flow distribution or the formation of "hot spots" due to the increase in the bed temperature and the possible violent reaction is prevented. Therefore, the operating efficiency of the residue hydrogenation device can be improved, and the operating cycle of the device can be greatly prolonged, thereby realizing greater economy of the fixed-bed residue hydrogenation device.

Claims

1. A method for grading a residue hydroprocessing catalyst, the method comprising at least three hydroprocessing reactors in series, a first reactor, a second reactor, and a third reactor, wherein, The first reactor is filled with at least a preservative, the second reactor is filled with at least a hydrodemetallization catalyst, and the third reactor is filled with at least a hydrodesulfurization catalyst; The first reactor is filled with at least a preservative, the second reactor is filled with at least a hydrodemetallization catalyst, and the third reactor is filled with at least a hydrodesulfurization catalyst; The hydrogenation catalyst B comprises a carrier and a hydrogenation active metal component; the content of the hydrogenation active metal component in the hydrogenation catalyst B is 1.7 wt% to 23.5 wt% and the content of the carrier is 76.5 wt% to 98.3 wt% based on the mass of the catalyst; the hydrogenation active metal comprises Group VI B and Group VIII metals; the Group VI B metal is Mo and the Group VIII metal is Ni and Co; The mass content of Mo in the hydrogenation catalyst B in terms of oxides is at least 0.5 percentage points higher than the mass content of Mo in terms of oxides in the adjacent downstream catalyst; the mass content of Ni in the hydrogenation catalyst B in terms of oxides is within 0.8 percentage points of the mass content of Ni in terms of oxides in the adjacent downstream catalyst; and the mass content of Co in the hydrogenation catalyst B in terms of oxides is at least 0.8 percentage points higher than the mass content of Co in terms of oxides in the adjacent downstream catalyst. The void fraction of the hydrogenation catalyst B in the second reactor is at least 2 percentage points higher than the void fraction of the adjacent upstream catalyst.

2. The method of claim 1, wherein, The first reactor is filled with at least a preservative, the second reactor is filled with at least a hydrodemetallization catalyst, and the third reactor is filled with at least a hydrodesulfurization catalyst; 3. The method of claim 2, wherein, The volume of the hydrogenation catalyst A filled at the bottom of the first reactor accounts for 1% to 30% of the total catalyst filling volume in the first reactor; and the volume of the hydrogenation catalyst B filled at the bottom of the second reactor accounts for 1% to 30% of the total catalyst filling volume in the second reactor.

4. The method of claim 2, wherein, The volume of the hydrogenation catalyst A filled at the bottom of the first reactor accounts for 5% to 30% of the total catalyst filling volume in the first reactor; and the volume of the hydrogenation catalyst B filled at the bottom of the second reactor accounts for 3% to 25% of the total catalyst filling volume in the second reactor.

5. The method of claim 2, wherein, The mass content of the hydrogenation active metal in the hydrogenation catalyst A in the first reactor in terms of oxides is at least 0.5 percentage points higher than the mass content of the hydrogenation active metal in terms of oxides in the adjacent downstream catalyst.

6. The method of claim 1, wherein, The mass content of the hydrogenation active metal in the hydrogenation catalyst B in the second reactor is at least 0.5 percentage points higher than the mass content of the hydrogenation active metal in terms of oxides in the adjacent downstream catalyst.

7. The method of claim 2, wherein, The mass content of the hydrogenation active metal in the hydrogenation catalyst A in the first reactor in terms of oxides is 1 to 9.0 percentage points higher than the mass content of the hydrogenation active metal in terms of oxides in the adjacent downstream catalyst.

8. The method of claim 1, wherein, The mass content of the hydrogenation active metal in the hydrogenation catalyst B in the second reactor is 1 to 9.0 percentage points higher than the mass content of the hydrogenation active metal in terms of oxides in the adjacent downstream catalyst.

9. The method of claim 2, wherein, The hydrogenation catalyst A in the first reactor has molybdenum, nickel and cobalt as hydrogenation active metals, and the hydrogenation catalyst A adjacent to the downstream catalyst has molybdenum and nickel as hydrogenation active metals.

10. The method of claim 1, wherein, The hydrogenation catalyst B in the second reactor has molybdenum, nickel and cobalt as hydrogenation active metals, and the hydrogenation catalyst B adjacent to the downstream catalyst has molybdenum and nickel as hydrogenation active metals.

11. The method of claim 2 or 9, wherein, The mass content of molybdenum in the hydrogenation catalyst A in terms of oxide is at least 0.5 percentage points higher than that in the adjacent downstream catalyst; the mass content of nickel in the hydrogenation catalyst A in terms of oxide is within 0.4 percentage points of that in the adjacent downstream catalyst; and the mass content of cobalt in the hydrogenation catalyst A in terms of oxide is at least 0.5 percentage points higher than that in the adjacent downstream catalyst.

12. The method of claim 11, wherein, The mass content of molybdenum in the hydrogenation catalyst A in terms of oxide is 1-5.0 percentage points higher than that in the adjacent downstream catalyst; and the mass content of cobalt in the hydrogenation catalyst A in terms of oxide is 0.8-4.0 percentage points higher than that in the adjacent downstream catalyst.

13. The method of claim 1 wherein, The mass content of molybdenum in the hydrogenation catalyst B in terms of oxide is 1-5.0 percentage points higher than that in the adjacent downstream catalyst; and the mass content of cobalt in the hydrogenation catalyst B in terms of oxide is 1-4.0 percentage points higher than that in the adjacent downstream catalyst.

14. The method of claim 2, wherein, The porosity of the hydrogenation catalyst A in the first reactor is at least 2 percentage points higher than that of the adjacent upstream catalyst.

15. The method of claim 14, wherein, The porosity of the hydrogenation catalyst A in the first reactor is 2-15 percentage points higher than that of the adjacent upstream catalyst.

16. The method of claim 1, wherein, The porosity of the hydrogenation catalyst B in the second reactor is 2-15 percentage points higher than that of the adjacent upstream catalyst.

17. The method of claim 2, 3, 4, or 5, wherein, The hydrogenation catalyst A is 1-4 kinds; and the loading mode of each kind of hydrogenation catalyst A is that, along the flow direction, the porosity of each kind of hydrogenation catalyst A increases from small to large, and the content of hydrogenation active metal components decreases from large to small.

18. The method of claim 17, wherein, The hydrogenation catalyst A is 2-4 kinds.

19. The method of claim 17, wherein, When there are multiple kinds of hydrogenation catalyst A, the mass content of active metal in terms of oxide between two adjacent kinds of hydrogenation catalyst A is at least 0.5 percentage points different.

20. The method of claim 17, wherein, When there are multiple kinds of hydrogenation catalyst A, the mass content of molybdenum oxide between two adjacent kinds of hydrogenation catalyst A is at least 0.4 percentage points different, the mass content of cobalt oxide is at least 0.1 percentage points different, and the mass content of nickel oxide is within 0.4 percentage points different.

21. The method of claim 17, wherein, When there are multiple kinds of hydrogenation catalyst A, the mass content of molybdenum oxide between two adjacent kinds of hydrogenation catalyst A is 1.0-4.9 percentage points different, and the mass content of cobalt oxide is 0.1-1.0 percentage points different.

22. The method of claim 1-5, wherein, The hydrogenation catalyst B is 1-4 kinds; and the loading mode of each kind of hydrogenation catalyst B is that, along the flow direction, the porosity of each kind of hydrogenation catalyst B increases from small to large, and the content of hydrogenation active metal components decreases from large to small.

23. The method of claim 22, wherein, The hydrogenation catalyst B is 2-4 kinds.

24. The method of claim 22, wherein, When there are multiple kinds of hydrogenation catalyst B, the mass content of hydrogenation active metal in terms of oxide between two adjacent kinds of hydrogenation catalyst B is at least 0.5 percentage points different.

25. The method of claim 22, wherein, When the hydrogenation catalyst B is multiple, the mass content of hydrogenation active metal in terms of oxide between two adjacent hydrogenation catalyst B differs by 1.0-5.0 percentage points.

26. The method of claim 22, wherein, When the hydrogenation catalyst B is multiple, the mass content of hydrogenation active metal in terms of oxide between two adjacent hydrogenation catalyst B differs by 1.5-3.0 percentage points.

27. The method of claim 22, wherein, When the hydrogenation catalyst B is multiple, the mass content of molybdenum oxide between two adjacent hydrogenation catalyst B differs by at least 0.5 percentage points, the mass content of cobalt oxide differs by at least 0.2 percentage points, and the mass content of nickel oxide differs by within 0.4 percentage points.

28. The method of claim 22, wherein, When the hydrogenation catalyst B is multiple, the mass content of molybdenum oxide between two adjacent hydrogenation catalyst B differs by 0.8-4.9 percentage points, and the mass content of cobalt oxide differs by 0.2-1.5 percentage points.

29. The method of claim 2, wherein, The particle size between two adjacent hydrogenation catalyst A differs by at least 0.5 mm.

30. The method of claim 2, wherein, The particle size between two adjacent hydrogenation catalyst A differs by 0.8-10.0 mm.

31. The method of claim 2, wherein, The particle size between two adjacent hydrogenation catalyst A differs by 0.8-4.0 mm.

32. The method of claim 1, wherein, The particle size between two adjacent hydrogenation catalyst B differs by at least 0.5 mm.

33. The method of claim 1, wherein, The particle size between two adjacent hydrogenation catalyst B differs by 0.8-10.0 mm.

34. The method of claim 1, wherein, The particle size between two adjacent hydrogenation catalyst B differs by 0.8-4.0 mm.

35. The method of claim 2, wherein, The hydrogenation catalyst A comprises a carrier and a hydrogenation active metal component; the content of the hydrogenation active metal component is 1.7wt%-23.5wt% and the content of the carrier is 76.5wt%-98.3wt% based on the mass of the catalyst; the hydrogenation active metal comprises Group ⅥB and Group Ⅷ metal.

36. The method of claim 35, wherein, The hydrogenation catalyst A, the Group ⅥB metal is Mo, and the Group Ⅷ metal is Ni and Co.

37. The method of claim 35, wherein the grading is performed by a method comprising: In the hydrogenation catalyst A, the content of molybdenum oxide is 1.5wt%-17.5wt%, the content of nickel oxide is 0.2wt%-6.0wt%, and the content of cobalt oxide is 0.5wt%-6.0wt% based on the mass of the hydrogenation catalyst A.

38. The method of claim 1, wherein, The content of molybdenum oxide is 1.5wt%-17.5wt%, the content of nickel oxide is 0.2wt%-6.0wt%, and the content of cobalt oxide is 0.5wt%-6.0wt% based on the mass of the hydrogenation catalyst B.

39. The method of claim 2, wherein, The first hydrogenation reactor is filled with a hydrogenation protective agent and a hydrogenation catalyst A, and a hydrogenation demetallization catalyst is filled between the hydrogenation protective agent and the hydrogenation catalyst A; the second hydrogenation reactor is filled with a hydrogenation demetallization catalyst and a hydrogenation catalyst B.

40. Application of the grading method of any one of claims 1-39 in a residue hydroprocessing reaction.

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