A method for desoduration in the preparation of a bulk hydrogenation catalyst

Abstract

The application discloses a method for removing sodium in a preparation process of a bulk-phase hydrogenation catalyst, and comprises the following steps: (1) vacuum filtration is performed on slurry containing sodium obtained by preparing a bulk-phase hydrogenation catalyst by a coprecipitation method to obtain a slurry filter cake, and then first incubation treatment is performed; (2) deionized water is added to the top of the filter cake obtained in the step (1), first vacuum filtration desalination is performed, and then second incubation treatment is performed; (3) deionized water is added to the top of the filter cake obtained in the step (2), second vacuum filtration desalination is performed; (4) the deionized water is uniformly mixed with the filter cake obtained in the step (3), third vacuum filtration desalination is performed, and then temperature control drying treatment is performed, so as to obtain a catalyst precursor after sodium removal. The method solves the adverse effects of sodium-containing raw materials on catalyst molding, pore structure, other physical and chemical properties and hydrogenation activity, and is suitable for the process of preparing a bulk-phase hydrogenation catalyst by coprecipitation of sodium-containing raw materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of bulk phase hydrogenation catalyst preparation, and particularly relates to a method for removing impurity sodium in the process of preparing bulk phase catalyst by coprecipitation. BACKGROUND

[0002] The most effective means to meet the oil quality upgrading is to use high hydrogenation activity catalyst. As one of the highest activity hydrogenation catalysts, bulk phase catalyst is very suitable for oil quality upgrading in refinery due to its excellent hydrogenation performance.

[0003] Bulk phase hydrogenation catalyst is usually prepared by mixing or coprecipitation. Mixing method is difficult to obtain high metal content catalyst due to the difficulty in forming. Meanwhile, due to the limitation of preparation method, the components of active metal are difficult to be uniformly mixed, which cannot promote the synergistic effect between active metals, so that the catalyst cannot fully exert its activity.

[0004] Due to the ion reaction characteristics, each component can be uniformly mixed in the reaction process by coprecipitation method. Meanwhile, the coprecipitation method determines a wide range of raw material selection, which can use raw materials that cannot be used by impregnation and mixing method, thus expanding the selection range of raw materials, and enabling the production of bulk phase catalyst by using cheap and clean raw materials, so as to realize the purpose of reducing the cost of bulk phase catalyst raw materials and realizing green production. This is also the two main problems faced in the research and industrial application of bulk phase catalyst.

[0005] Most of the coprecipitation methods use ammonia as the precipitant and soluble salt containing nitrogen as the raw material. At present, the research on bulk phase catalyst shows that, compared with ammonium metatungstate, ammonium molybdate, thiomolybdate, nickel nitrate and other active metal raw materials, or using ammonia as an alkaline precipitant, using relatively low-cost sodium-containing raw materials such as sodium tungstate, sodium molybdate, nickel chloride, sodium hydroxide, sodium carbonate and sodium bicarbonate can not only reduce the cost of bulk phase catalyst, but also solve the problem of ammonia-nitrogen pollution in the production process of bulk phase catalyst from the source, because the raw materials do not contain ammonia-nitrogen.

[0006] However, with further research, it is found that the introduction of a large amount of sodium ions in the raw material will increase the sodium content in the bulk phase catalyst. It is difficult to completely remove sodium ions in the catalyst preparation process, and a large amount of sodium ions in the precipitated material will affect the catalyst extrusion forming difficulty due to poor adhesion of the material, which not only makes it difficult to form, but also affects the strength of the catalyst. The increase of sodium content in the finished catalyst is not conducive to the formation of catalyst pore structure, which will lead to more small pores in the catalyst, and will also change other physical and chemical properties of the catalyst, affecting the hydrogenation activity of the catalyst.

[0007] CN101172261A discloses a method for preparing a catalyst composition by using a sodium metaaluminate solution and a mixed solution of nickel and tungsten component salts in a parallel flow, and co-precipitation reaction; CN110038581B discloses a preparation method of a hydrofining catalyst. The preparation method adopts a co-precipitation method, and the two co-precipitation processes are respectively carried out by using a sodium tungstate alkaline solution and a sodium molybdate alkaline solution as a precipitant for precipitation. In the above two invention patents, the active metal salt containing sodium is introduced as a precipitant during the co-precipitation reaction, but the targeted desodium treatment is not carried out in the process, so that a certain amount of sodium ions are contained in the co-precipitation product, the material adhesion is poor, the crushing strength is relatively low, and the residual sodium ions also make the pore volume and specific surface area of the catalyst not large.

[0008] CN114471593A and CN114471594A both disclose a preparation method of a hydrofining catalyst. In the method, the co-precipitation method is adopted for preparation and desodium salt treatment. The sodium salt removal method is selected to be carried out after the catalyst is extruded into a strip, and the method has certain requirements for the total amount of sodium content of the catalyst preparation raw material. If the sodium content in the co-precipitation slurry cake exceeds 10wt%, the material will be relatively loose, the material cannot be extruded into a strip, or the strength of the material after extrusion is small. In addition to this, a large amount of sodium ions exist in the co-precipitation product, and part of the sodium chloride crystals will be precipitated and attached to the internal pores during the drying process before the catalyst is formed, which affects the pore expansion of the catalyst. In addition, the sodium salt removal is selected to be carried out after the catalyst is extruded into a strip, and the drying, extrusion and other treatments of the material before forming increase the adsorption degree of sodium ions on the catalyst, which makes it more difficult to remove the sodium salt, that is, the desalination treatment after forming is not thorough. SUMMARY

[0009] In view of the problems existing in the prior art, the present application provides a desodium method in the preparation process of a bulk phase hydrogenation catalyst. The method solves the adverse effects of sodium-containing raw materials on catalyst forming, pore structure, other physical and chemical properties and hydrogenation activity, and also has a good improvement on the strength and pore structure properties of the catalyst, and is especially suitable for the process of preparing a bulk phase hydrogenation catalyst by co-precipitation of high-sodium-content raw materials.

[0010] The desodium method in the preparation process of a bulk phase hydrogenation catalyst of the present application comprises the following contents:

[0011] (1) The sodium-containing slurry obtained by preparing a bulk phase hydrogenation catalyst by a co-precipitation method is vacuum filtered to obtain a slurry cake, and then a first aging treatment is carried out;

[0012] (2) Deionized water is added to the top of the cake obtained in step (1), and a first vacuum filtration desalination is carried out, and then a second aging treatment is carried out;

[0013] (3) Deionized water is added to the top of the cake obtained in step (2), and a second vacuum filtration desalination is carried out;

[0014] (4) mixing the deionized water with the filter cake obtained in step (3) uniformly, carrying out the third vacuum filtration desalination, and then carrying out temperature control drying treatment to obtain a sodium-removed catalyst precursor.

[0015] In the method, the raw material for preparing the bulk hydrogenation catalyst by the coprecipitation method in step (1) is at least one sodium-containing raw material, which generally comprises an acid working solution and an alkaline precipitant, wherein the acid working solution is a soluble salt solution of an active metal (one or any combination of tungsten, molybdenum, nickel and cobalt) and other components, such as sodium tungstate, sodium molybdate and sodium aluminate; the alkaline precipitant is a solution of alkali and / or alkaline salt, such as sodium hydroxide, sodium carbonate and sodium bicarbonate; the sodium-containing slurry in step (1) needs to take one or any combination of the above-mentioned sodium-containing or other sodium-containing raw materials as the coprecipitation reaction raw material.

[0016] In the method, the sodium content of the filter cake of the sodium-containing slurry in step (1) is 1.0wt%-18wt%, preferably 2wt%-16wt%, based on the sodium content in the solid after the filter cake is calcined at 500℃ in air for 4 hours.

[0017] In the method, the dry basis of the filter cake obtained by the vacuum filtration in step (1) is 15wt%-25wt%, preferably 18wt%-23wt%.

[0018] In the method, the first aging treatment condition in step (1) is as follows: the aging temperature is 28℃-45℃, preferably 35℃-40℃; the aging time is 0.4-2 hours, preferably 0.5-1 hour; and the humidity of the aging environment is greater than 80%, preferably greater than 85%. The above conditions prevent the filter cake from being excessively dehydrated or dehydrated too fast due to low environmental humidity and high temperature during the aging process, so that the precipitated sodium salt is quickly crystallized into large crystal grains, which affects the subsequent sodium salt removal efficiency.

[0019] In the method, after the aging process in step (1) is completed, the dry basis of the filter cake A is 20%-33%, preferably 23%-28%; and the aging process causes most of the hydrated sodium ions in the filter cake A to precipitate from the pores and retain vacancies, so that the pore volume of the filter cake is increased.

[0020] In the method, the first vacuum filtration desalination condition in step (2) is as follows: the liquid-solid mass ratio is greater than 2, preferably 3-4:1, wherein the solid phase mass is based on the final catalyst mass; and the deionized water temperature is 28℃-45℃, preferably the same as the aging temperature.

[0021] In the method, the second life treatment condition in step (2) is: life temperature 40-70 DEG C, preferably 50-60 DEG C; life time 0.5-2 hours, preferably 0.8-1.2 hours; life environment humidity is greater than 80%, preferably greater than 85%; in addition to preventing the sodium salt from crystallizing into larger grains due to the low environmental humidity during the life process, the pores left by the removal of most of the impurity sodium in step (2) rapidly diffuse water in the filter cake to the outside in the form of water vapor under the higher temperature and humidity environment of the second life, and the hole expansion effect is generated.

[0022] In the method, the dry basis of the filter cake obtained after the second life treatment is 28wt%-38wt%, preferably 30wt%-35wt%.

[0023] In the method, the second vacuum filtration desalination condition in step (3) is: liquid-solid mass ratio is greater than 0.5, preferably 2-3:1, wherein the solid phase mass is based on the final catalyst mass; and the deionized water temperature is 40-70 DEG C, preferably the same as the life temperature.

[0024] In the method, the third vacuum filtration desalination condition in step (4) is: liquid-solid mass ratio is greater than 0.3, preferably 0.5-0.8:1, wherein the solid phase mass is based on the final catalyst mass; and the deionized water temperature is 30-60 DEG C.

[0025] In the method, the vacuum filtration in steps (1)-(4) is generally carried out in a vacuum filtration device.

[0026] In the method, the life treatment process in steps (1) and (2) can be carried out in any environment that meets the life treatment conditions, and is preferably directly carried out in a vacuum filtration device without moving the filter cake, thereby simplifying the operation process.

[0027] In the method, the temperature control drying condition in step (4) is: temperature 45-95 DEG C, preferably 50-70 DEG C; and the control filter cake dry basis is 40wt%-68wt%, preferably 43wt%-55wt%.

[0028] The catalyst precursor in step (4) of the method is further extruded, molded, dried and calcined, and finally prepared into a bulk phase hydrogenation catalyst, which is well known to those skilled in the art.

[0029] The method directly removes the impurity sodium from the co-precipitation product obtained during the preparation of the bulk phase catalyst by the co-precipitation method, and has the advantages of simple process, saving of water resources and high impurity removal efficiency, is not limited by the sodium content in the raw material, and can better reflect the advantages of the method for raw materials with high sodium content.

[0030] The method removes the impurity sodium in a short time after the end of the coprecipitation reaction by vacuum filtration desalination combined with health treatment, reduces the adsorption degree of sodium ions to the catalyst due to the increase in the late drying and extrusion treatment, and is easier to remove. Compared with the traditional coprecipitation product beating and washing to remove impurities, or water washing after shaping to remove sodium, the method can remove a large amount of impurity sodium in the filter cake with a small amount of water, meet the requirement that the sodium content in the filter cake (catalyst shaping material) is ≯0.1%, reduce the washing frequency, and greatly reduce the water consumption in the catalyst preparation process, thereby achieving the purpose of water saving.

[0031] The filter cake is obtained through vacuum filtration desalination, and then the temperature control drying treatment of step (4) is performed. Due to the removal of the impurity sodium, the sodium chloride crystals precipitated due to drying are eliminated, the influence of the crystals on the pore expansion is eliminated, the water in the filter cake rapidly diffuses outward in the form of water vapor during the drying process, the pore structure is further optimized, the pore volume is improved, and the pore structure of the catalyst is further optimized. Embodiment

[0032] The technical solutions of the present application will be clearly and completely described below in combination with specific embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments.

[0033] The specific surface area and pore volume of the catalyst are measured on an ASAP-2405 type BET nitrogen adsorption instrument in the United States; the crush strength of the catalyst is measured on a particle strength tester; and the sodium content of the catalyst, catalyst precursor and slurry filter cake is measured on an inductively coupled plasma spectrometer, wherein the sodium content of the catalyst precursor and slurry filter cake is measured as the sodium content in the solid after the sample is calcined at 500°C in air for 4 hours.

[0034] The coprecipitation reaction slurry used in the examples and comparative examples is the reaction slurry commonly used in the preparation of a body-phase hydrogenation catalyst from sodium-containing raw materials. For example, the slurry can be prepared by the following process:

[0035] A mixed solution A of aluminum chloride and nickel chloride is prepared (the mass concentration of aluminum chloride calculated as Al2O3 is 15 g / L, and the mass concentration of nickel chloride calculated as NiO is 30 g / L); a mixed solution B of sodium tungstate and sodium molybdate is prepared (the mass concentration of sodium tungstate calculated as WO3 is 45 g / L, and the mass concentration of sodium molybdate calculated as MoO3 is 15 g / L); solution A is used as the bottom water for the coprecipitation reaction, and under the condition of high-speed stirring, the mixed solution B and an alkaline precipitant sodium hydroxide solution (the mass concentration of NaOH is 10 g / L) are added into the mixed solution A in a parallel flow manner to obtain a coprecipitation product slurry ①.

[0036] A mixed solution of sodium metaaluminate and nickel chloride was prepared (the mass concentration of sodium metaaluminate was 15 g / L as Al2O3, and the mass concentration of nickel chloride was 30 g / L as NiO); a mixed solution of sodium tungstate and sodium molybdate was prepared (the mass concentration of sodium tungstate was 45 g / L as WO3, and the mass concentration of sodium molybdate was 15 g / L as MoO3); solution A was used as the bottom water for the coprecipitation reaction, and mixed solution B, a basic precipitator sodium hydroxide solution (the mass concentration of NaOH was 10 g / L) were added into mixed solution A under high-speed stirring to obtain a coprecipitation product slurry ②.

[0037] According to the sodium content in the raw material, the coprecipitation product slurries ① and ② were selected for the examples and comparative examples of the present application. The element sodium content in the filter cake of slurry ① was 8.32 wt%, and the element sodium content in the filter cake of slurry ② was 11.32 wt%. Example 1

[0038] The slurry ① was vacuum filtered to obtain a coprecipitation product filter cake with a dry basis of 20.3 wt%; the filter cake was aged, the aging process was directly carried out in the vacuum filter, the humidity of the aging environment was maintained at 86%, the aging temperature was 35℃, the time was 0.75 hours, and the dry basis of the filter cake after aging was 26 wt%; deionized water with a mass ratio of 4:1 to the catalyst preparation was added to the upper layer of the filter cake, the temperature of the deionized water was 35℃, and the vacuum filtration was continued until there was no suspended liquid on the surface of the filter cake.

[0039] The filter cake was further aged in the vacuum filter, the humidity of the aging environment was maintained at 88%, the aging temperature was 52℃, the time was 1.0 hour, and the dry basis of the filter cake after aging was 32 wt%; deionized water with a mass ratio of 2:1 to the catalyst preparation was added to the upper layer of the filter cake, the temperature of the deionized water was 52℃, and the vacuum filtration was continued until there was no suspended liquid on the surface of the filter cake.

[0040] The filter cake was again added with deionized water at 50℃ with a mass ratio of 0.5:1 to the catalyst preparation, and after being mixed uniformly with the filter cake, the vacuum filtration was continued until there was no filter liquid dripping from the filter cake, and the washing was completed.

[0041] The filter cake was dried at 70℃ to obtain a catalyst precursor with a dry basis of 50 wt%.

[0042] The material was subjected to conventional extrusion molding treatment of the bulk catalyst, and then dried and calcined to obtain a bulk catalyst A1-1, and the main properties are shown in Table 1. Example 2

[0043] The slurry 1 is vacuum filtered to obtain the co-precipitation product filter cake with a dry basis of 22.5wt%; the filter cake is aged, the aging process is directly carried out in the vacuum filter, the aging environment humidity is kept at 89%, the aging temperature is 40℃, the time is 0.5 hours, and the dry basis of the filter cake after aging is 29wt%; deionized water with a mass ratio of 3.5:1 to the catalyst preparation is added to the upper layer of the filter cake, the temperature of the deionized water is 43℃, and the vacuum filtration is carried out until there is no suspended liquid on the surface of the filter cake.

[0044] The filter cake is continuously aged in the vacuum filter for the second time, the aging environment humidity is kept at 85%, the aging temperature is 58℃, the time is 1.2 hours, and the dry basis of the filter cake after aging is 36wt%; deionized water with a mass ratio of 2.5:1 to the catalyst preparation is added to the upper layer of the filter cake, the temperature of the deionized water is 58℃, and the vacuum filtration is carried out until there is no suspended liquid on the surface of the filter cake.

[0045] The filter cake is again added with deionized water at 30℃ with a mass ratio of 1.0:1 to the catalyst preparation, and after being uniformly mixed with the filter cake, the vacuum filtration is carried out until there is no filter liquid dripping down from the filter cake, and the washing is completed.

[0046] The filter cake is dried at 60℃ to obtain a catalyst precursor with a dry basis of 46wt%.

[0047] The material is subjected to conventional extrusion molding treatment of the bulk catalyst, and then dried and calcined to obtain the bulk catalyst A2-1, and the main properties are shown in Table 1. Example 3

[0048] The slurry 1 is vacuum filtered to obtain the co-precipitation product filter cake with a dry basis of 25.0wt%; the filter cake is aged, the aging process is directly carried out in the vacuum filter, the aging environment humidity is kept at 82%, the aging temperature is 45℃, the time is 1.0 hour, and the dry basis of the filter cake after aging is 32wt%; deionized water with a mass ratio of 3:1 to the catalyst preparation is added to the upper layer of the filter cake, the temperature of the deionized water is 28℃, and the vacuum filtration is carried out until there is no suspended liquid on the surface of the filter cake.

[0049] The filter cake is continuously aged in the vacuum filter for the second time, the aging environment humidity is kept at 82%, the aging temperature is 65℃, the time is 1.5 hours, and the dry basis of the filter cake after aging is 34wt%; deionized water with a mass ratio of 3:1 to the catalyst preparation is added to the upper layer of the filter cake, the temperature of the deionized water is 65℃, and the vacuum filtration is carried out until there is no suspended liquid on the surface of the filter cake.

[0050] The filter cake is again added with deionized water at 60℃ with a mass ratio of 0.7:1 to the catalyst preparation, and after being uniformly mixed with the filter cake, the vacuum filtration is carried out until there is no filter liquid dripping down from the filter cake, and the washing is completed.

[0051] The filter cake is dried at 50℃ to obtain a catalyst precursor with a dry basis of 42wt%.

[0052] The material was treated by conventional bulk catalyst extrusion forming, and then dried and calcined to obtain bulk catalyst A3, the main properties of which are shown in Table 1. Example 4

[0053] The slurry ① was vacuum filtered to obtain a co-precipitation product filter cake with a dry basis of 17.2 wt%; the filter cake was aged, and the aging process was directly performed in a vacuum filter, the humidity of the aging environment was maintained at 93%, the aging temperature was 30°C, and the time was 1.8 hours, and the dry basis of the filter cake after aging was 22 wt%; deionized water with a catalyst preparation mass ratio of 2.5:1 was added to the upper layer of the filter cake, the temperature of the deionized water was 30°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0054] The filter cake was further aged in the vacuum filter, the humidity of the aging environment was maintained at 94%, the aging temperature was 45°C, and the time was 2.0 hours, and the dry basis of the filter cake after aging was 29 wt%; deionized water with a catalyst preparation mass ratio of 1:1 was added to the upper layer of the filter cake, the temperature of the deionized water was 45°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0055] The filter cake was further aged in the vacuum filter, the humidity of the aging environment was maintained at 94%, the aging temperature was 45°C, and the time was 2.0 hours, and the dry basis of the filter cake after aging was 29 wt%; deionized water with a catalyst preparation mass ratio of 1:1 was added to the upper layer of the filter cake, the temperature of the deionized water was 45°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0056] The filter cake was further aged in the vacuum filter, the humidity of the aging environment was maintained at 94%, the aging temperature was 45°C, and the time was 2.0 hours, and the dry basis of the filter cake after aging was 29 wt%; deionized water with a catalyst preparation mass ratio of 1:1 was added to the upper layer of the filter cake, the temperature of the deionized water was 45°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0057] The material was treated by conventional bulk catalyst extrusion forming, and then dried and calcined to obtain bulk catalyst A3, the main properties of which are shown in Table 1. Example 5

[0058] The slurry ① was vacuum filtered to obtain a co-precipitation product filter cake with a dry basis of 17.2 wt%; the filter cake was aged, and the aging process was directly performed in a vacuum filter, the humidity of the aging environment was maintained at 93%, the aging temperature was 30°C, and the time was 1.8 hours, and the dry basis of the filter cake after aging was 22 wt%; deionized water with a catalyst preparation mass ratio of 2.5:1 was added to the upper layer of the filter cake, the temperature of the deionized water was 30°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0059] The filter cake was further aged in the vacuum filter, the humidity of the aging environment was maintained at 94%, the aging temperature was 45°C, and the time was 2.0 hours, and the dry basis of the filter cake after aging was 29 wt%; deionized water with a catalyst preparation mass ratio of 1:1 was added to the upper layer of the filter cake, the temperature of the deionized water was 45°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0060] The filter cake was added with 50℃ deionized water at a mass ratio of 0.8:1 to the catalyst preparation, and after being uniformly mixed with the filter cake, vacuum filtration was performed until no filter liquid dropped from the filter cake, and the washing was completed.

[0061] The filter cake was dried at 65℃, and a catalyst precursor with a dry basis of 48wt% was obtained.

[0062] The material was subjected to conventional extrusion molding treatment of the bulk catalyst, and then dried and calcined to obtain the bulk catalyst A5, and the main properties are shown in Table 1. Example 6

[0063] The other steps of this example were consistent with Example 1, except that slurry ② was used in this example to obtain catalyst B1, and the main properties are shown in Table 1.

[0064] Comparative Example 1

[0065] The slurry ② was vacuum filtered to obtain a co-precipitation product filter cake with a dry basis of 20.6wt%; the filter cake was dried at 70℃, and a material with a dry basis of 50wt% was obtained.

[0066] The material was subjected to conventional extrusion molding treatment of the bulk catalyst, but due to the high sodium content, the material was loose, the molded material was pulverized, and the catalyst could not be molded.

[0067] Comparative Example 2

[0068] The slurry ① was vacuum filtered to obtain a co-precipitation product filter cake with a dry basis of 20.5wt%; the filter cake was dried at 70℃, and a catalyst precursor with a dry basis of 50wt% was obtained.

[0069] After the material was subjected to conventional extrusion molding treatment of the bulk catalyst, impurity sodium was removed according to the method disclosed in CN114471593A: after the molded material was incubated at 85℃ for 48 hours, it was cooled to 28℃ and incubated for another 30 hours, and then washed with deionized water twice, with a deionized water to catalyst preparation mass ratio of 5:1.

[0070] Then dried and calcined to obtain the bulk catalyst C1, and the main properties are shown in Table 1.

[0071] Comparative Example 3

[0072] The slurry ① was vacuum filtered to obtain a co-precipitation product filter cake with a dry basis of 20.3wt%.

[0073] Deionized water was added to the filter cake at a mass ratio of 10:1 to the catalyst preparation, and the slurry was washed for 1.5 hours, and the slurry was vacuum filtered to obtain a filter cake with a dry basis of 20.7wt%.

[0074] The filter cake was dried at 70°C to obtain a catalyst precursor with a dry basis of 50wt%. The material was subjected to a conventional bulk catalyst extrusion process, and the extruded material was washed three times with deionized water at a deionized water to catalyst preparation mass ratio of 5:1, and then dried and calcined to obtain bulk catalyst C2, the main properties of which are shown in Table 1.

[0075] Comparative Example 4

[0076] The other steps of this example were the same as in Example 1, except that in this comparative example, the first aging treatment in step (1) was performed at an aging environment humidity of 70%, an aging temperature of 60°C, and for a time of 2.5 hours, and the filter cake had a dry basis of 36wt% at the end of the aging.

[0077] Bulk catalyst A1-2 was finally obtained, and the main properties thereof are shown in Table 1.

[0078] Comparative Example 5

[0079] The other steps of this example were the same as in Example 1, except that in this comparative example, the first vacuum filtration and desalination in step (2) was performed by adding deionized water to the upper layer of the filter cake at a deionized water to catalyst preparation mass ratio of 1:1, and the deionized water was at a temperature of 35°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0080] Bulk catalyst A1-3 was finally obtained, and the main properties thereof are shown in Table 1.

[0081] Comparative Example 6

[0082] The other steps of this example were the same as in Example 2, except that in this comparative example, the second aging treatment in step (2) was performed at an aging environment humidity of 65%, an aging temperature of 25°C, and for a time of 0.4 hours, and the filter cake had a dry basis of 30wt% at the end of the aging.

[0083] Bulk catalyst A2-2 was finally obtained, and the main properties thereof are shown in Table 1.

[0084] Comparative Example 7

[0085] The other steps of this example were the same as in Example 2, except that in this comparative example, the second vacuum filtration and desalination in step (3) was performed by adding deionized water to the upper layer of the filter cake at a deionized water to catalyst preparation mass ratio of 0.3:1, and the deionized water was at a temperature of 50°C, and the vacuum filtration was performed until there was no suspended liquid on the surface of the filter cake.

[0086] Bulk catalyst A2-3 was finally obtained, and the main properties thereof are shown in Table 1.

[0087] Comparative Example 8

[0088] The other steps of this example are identical to example 2, except that in this comparative example the second vacuum filtration to remove the salt in step (3) is stopped as soon as no more filtrate is coming out, and step (4) is not performed.

[0089] The final bulk catalyst A2-4 is obtained, the main properties are given in table 1.

[0090] Table 1 Properties of catalysts prepared in examples and comparative examples

[0091] A1-1 A2-1 A3 A4 A5 B1 Sodium content of catalyst precursor, ppm 148 106 522 431 337 350 Catalyst product Pore volume, mL / g 0.479 0.463 0.447 0.443 0.466 0.441 Specific surface, m 2 / g]] 356 353 341 338 347 350 Mechanical strength, N / mm 19.4 20.9 18.5 18.7 19.3 20.2 Sodium content, ppm, 101 83 501 408 286 321

[0092] Table 1 (continued) Properties of catalysts prepared in examples and comparative examples

[0093] C1 C2 A1-2 A1-3 A2-2 A2-3 A2-4 Sodium content of catalyst precursor, ppm 83219 21837 1242 1093 769 884 312 Catalyst product Pore volume, mL / g 0.423 0.394 0.434 0.441 0.446 0.453 0.459 Specific surface, m 2 / g]] 322 310 331 335 342 342 347 Mechanical strength, N / mm 12.6 14.8 18.6 18.5 19.1 20.1 19.7 Sodium content, ppm, 1436 2904 1279 1017 706 821 285

Claims

1. A method for sodium removal during the preparation of a bulk hydrogenation catalyst, characterized in that... The method comprises the following steps: (1) vacuum filtration of a slurry containing sodium obtained by co-precipitation method for preparing a bulk hydrogenation catalyst to obtain a slurry filter cake, and then first aging treatment; (2) adding deionized water to the top of the filter cake obtained in step (1), and then performing first vacuum filtration desalination, and then second aging treatment; (3) adding deionized water to the top of the filter cake obtained in step (2), and then performing second vacuum filtration desalination; (4) mixing deionized water with the filter cake obtained in step (3), and then performing third vacuum filtration desalination, and then temperature-controlled drying treatment to obtain a catalyst precursor with sodium removed; the first aging treatment in step (1) is performed at a temperature of 28-45 DEG C for 0.4-2 hours in an environment with a humidity of greater than 80%; the first vacuum filtration desalination in step (2) is performed at a liquid-solid mass ratio of greater than 2, wherein the solid phase mass is based on the mass of the final catalyst, and the deionized water is at a temperature of 28-45 DEG C; the second aging treatment in step (2) is performed at a temperature of 40-70 DEG C for 0.5-2 hours in an environment with a humidity of greater than 80%; the second vacuum filtration desalination in step (3) is performed at a liquid-solid mass ratio of greater than 0.5, wherein the solid phase mass is based on the mass of the final catalyst, and the deionized water is at a temperature of 40-70 DEG C; the third vacuum filtration desalination in step (4) is performed at a liquid-solid mass ratio of greater than 0.3, wherein the solid phase mass is based on the mass of the final catalyst, and the deionized water is at a temperature of 30-60 DEG C.

2. The desodtion process of claim 1 wherein: In step (1), at least one of the raw materials for preparing the bulk hydrogenation catalyst by the co-precipitation method is a sodium-containing raw material.

3. The desodtion process of claim 1 wherein: In step (1), the sodium content of the sodium-containing slurry filter cake is 1.0-18 wt% based on the sodium content in the solid after the slurry filter cake is calcined at 500 DEG C in air for 4 hours.

4. The desodtion process of claim 1 wherein: In step (1), the dry basis content of the filter cake obtained by the vacuum filtration is 15-25 wt%.

5. The desodtion process of claim 1 wherein: In step (1), the first aging treatment is performed at a temperature of 35-40 DEG C for 0.5-1 hour in an environment with a humidity of greater than 85%.

6. The desodtion process of claim 1 wherein: After the aging process in step (1) is completed, the dry basis content of the filter cake is 20-33%.

7. The desodtion process of claim 1 wherein: In step (2), the first vacuum filtration desalination is performed at a liquid-solid mass ratio of 3-4:1, wherein the solid phase mass is based on the mass of the final catalyst.

8. The desodtion process of claim 1 wherein: In step (2), the second aging treatment is performed at a temperature of 50-60 DEG C for 0.8-1.2 hours in an environment with a humidity of greater than 85%.

9. The desodtion process of claim 1 wherein: After the second aging treatment, the dry basis content of the filter cake is 28-38 wt%.

10. The desodtion process of claim 1 wherein: In step (3), the second vacuum filtration desalination is performed at a liquid-solid mass ratio of 2-3:1, wherein the solid phase mass is based on the mass of the final catalyst.

11. The desodtion process of claim 1 wherein: In step (4), the third vacuum filtration desalination is performed at a liquid-solid mass ratio of 0.5-0.8:1, wherein the solid phase mass is based on the mass of the final catalyst.

12. The desodtion process of claim 1 wherein: The aging treatment processes in steps (1) and (2) are directly performed in the vacuum filtration equipment.

13. The desodtion process of claim 1 wherein: In step (4), the temperature-controlled drying treatment is performed at a temperature of 45-95 DEG C to control the dry basis content of the filter cake to be 40-68 wt%.

14. The desodtion process of claim 1 wherein: The catalyst precursor of step (4) is finally prepared into bulk-phase hydrogenation catalyst through extrusion, molding, drying and calcination processes.