CN119819378A - Preparation method of hydrogenation catalyst - Google Patents
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Abstract
本发明公开了一种加氢催化剂的制备方法。所述方法包括如下步骤：(1)将钼镍系废催化剂抽提除油后的固体进行粉碎；(2)将催化剂粉末与氯气反应后，冷却后转移至无水有机溶剂中超声处理，分离得到溶剂I和物料II；(3)将物料II与拟薄水铝石混捏成型，干燥，焙烧，得到催化剂载体；(4)将溶剂I滴加至含硼源和多元醇的溶液中得到第一浸渍液，浸渍到步骤(3)的载体上，经干燥和焙烧，得到催化剂中间体；(5)将含第VIII族金属、有机酸的第二浸渍液浸渍催化剂中间体，经干燥，制得加氢催化剂。该方法能够高效利用镍钼系废催化剂的金属组分和氧化铝载体，得到的新催化剂活性高、寿命长。The invention discloses a method for preparing a hydrogenation catalyst. The method comprises the following steps: (1) crushing the solid after extracting and removing oil from molybdenum-nickel waste catalyst; (2) reacting the catalyst powder with chlorine, cooling it, transferring it to an anhydrous organic solvent for ultrasonic treatment, and separating to obtain solvent I and material II; (3) kneading material II with pseudo-boehmite to form, drying, and roasting to obtain a catalyst carrier; (4) dripping solvent I into a solution containing a boron source and a polyol to obtain a first impregnation liquid, impregnating it on the carrier of step (3), drying and roasting to obtain a catalyst intermediate; (5) impregnating the catalyst intermediate with a second impregnation liquid containing a Group VIII metal and an organic acid, and drying to obtain a hydrogenation catalyst. The method can efficiently utilize the metal components and alumina carrier of the nickel-molybdenum waste catalyst, and the obtained new catalyst has high activity and long service life.
Description
Technical Field
The invention belongs to the field of hydrogenation catalysts, and particularly relates to a preparation method of a hydrogenation catalyst.
Background
At present, the hydrotreating catalyst mainly takes molybdenum and nickel as active components, and alumina as a carrier, and is widely applied to petroleum refining and chemical industry. However, after a certain period of use, the catalyst is gradually deactivated by carbon deposition and metal deposition, thereby generating a large amount of spent catalyst. The waste hydrogenation catalyst is rich in valuable metal elements, so that the waste hydrogenation catalyst has higher economic value. Therefore, the recovery and reutilization of the active metal and the alumina carrier in the waste hydrogenation catalyst are very necessary, the resource utilization of the waste hydrogenation catalyst is realized, the problem of environmental pollution can be solved, and good social and ecological benefits are obtained.
CN108067272a discloses a method for preparing a hydrotreating catalyst. The method comprises the steps of (1) extracting a molybdenum-nickel waste hydrogenation catalyst, carrying out microwave treatment and crushing, (2) uniformly mixing the crushed catalyst powder obtained in the step (1) with alkali, roasting at high temperature, (3) carrying out hot water impregnation on the roasted waste catalyst obtained in the step (2), (4) reacting filtrate obtained in the step (3) with an acid solution to prepare pseudo-boehmite, kneading, forming and roasting the pseudo-boehmite to prepare a carrier, (5) adding Na 2 S solution into the filtered solution obtained in the step (4) to prepare MoO 3, (6) adding acid into the filtered solid obtained in the step (3), then removing Fe and Al in the solution by adopting an alkaline solution, and finally preparing basic nickel carbonate, and (7) preparing molybdenum oxide obtained in the step (5) and basic nickel carbonate obtained in the step (6) into a molybdenum-nickel-phosphorus solution, impregnating the carrier obtained in the step (4), and drying and roasting to prepare the hydrogenation catalyst. The method is suitable for preparing a new catalyst by recycling the molybdenum-nickel dead catalyst, but the method has the problems of excessively complex technological process and low recycling rate of carriers and metals.
In summary, the existing hydrogenation catalyst recycling method has the problems of complicated process steps, low recycling rate of active metals and/or carriers, low activity of the prepared catalyst and short service life in different degrees. Therefore, the method has great significance in further intensive research on recycling of the waste hydrogenation catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrogenation catalyst. The method can efficiently utilize the metal components and the alumina carrier of the nickel-molybdenum series spent catalyst. The method has the advantages of simple recovery steps, high activity and long service life of the obtained new catalyst, and can efficiently utilize the metal components and the alumina carrier of the nickel-molybdenum series spent catalyst, and is particularly suitable for recovery and reuse of the nickel-molybdenum series catalyst.
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps:
(1) Crushing the solid obtained after the molybdenum-nickel series waste catalyst is extracted and deoiled;
(2) After the catalyst powder reacts with chlorine, cooling and transferring the catalyst powder into an anhydrous organic solvent for ultrasonic treatment, and separating to obtain a solvent I and a material II;
(3) Kneading the material II and pseudo-boehmite for molding, drying and roasting to obtain a catalyst carrier;
(4) Dropwise adding a solvent I into a solution containing a boron source and a polyalcohol to obtain a first impregnating solution, impregnating the first impregnating solution on the carrier in the step (3), and drying and roasting the first impregnating solution to obtain a catalyst intermediate;
(5) And (3) impregnating the catalyst intermediate with a second impregnating solution containing a group VIII metal and an organic acid, and drying to obtain the hydrogenation catalyst.
According to the invention, the waste hydrogenation catalyst in the step (1) is a nickel-molybdenum-based waste catalyst, namely an inactivated catalyst obtained by hydrotreating residual oil on a molybdenum-nickel-based catalyst. The waste hydrogenation catalyst comprises 70-90% of catalyst solids and 10-30% of petroleum fractions by weight. Further, the waste hydrogenation catalyst after oil removal is extracted, based on the mass of the catalyst, in terms of mass fraction, and comprises:
10% -25% of molybdenum by molybdenum trioxide;
3% -10% of nickel by nickel oxide;
3% -10% of vanadium calculated by vanadium pentoxide;
6% -14% of carbon;
41% -77% of carrier alumina.
According to the invention, the organic solvent extracted in the step (1) comprises one or more of toluene, petroleum ether and ethanol, the extraction temperature is 80-110 ℃, and the extraction time is 60-90 h. The mass ratio of the organic solvent to the catalyst is 25-50:1. The extraction is used for removing petroleum fractions in the nickel-molybdenum series spent catalyst.
According to the invention, the spent hydrogenation catalyst is extracted in step (1) and then dried and crushed. The drying temperature is 120-200 ℃, and the drying time is 3-8 hours. The crushing is to crush the waste hydrogenation catalyst to a granularity of 200-500 meshes, preferably 300-400 meshes.
According to the invention, the purity of the chlorine gas in the step (2) is more than 96% in terms of volume fraction. The flow rate of the chlorine gas in the step (2) is 2.7-6.8 mL/(min.g of catalyst), and the reaction conditions are as follows, the reaction temperature is 300-400 ℃, and the reaction time is 40-90 min.
According to the invention, in step (2), cooling is carried out to a temperature required for the ultrasonic treatment. The anhydrous organic solvent is one or more selected from acetone, tetrahydrofuran and acetic acid. The mass ratio of the dosage of the anhydrous organic solvent to the catalyst powder is 3-5:1.
According to the invention, the ultrasonic frequency in the step (2) is 10 KHz-150 KHz, the ultrasonic treatment temperature is 20 ℃ to 70 ℃, and the treatment time is 0.5-2 h.
According to the invention, in the step (3), the mass ratio of the pseudo-boehmite to the material II is 7-13:15-30 in terms of alumina. The kneading molding in the step (3) is carried out by a conventional method in the field, and an adhesive, an extrusion aid and water can be added according to the requirement in the molding process. The adhesive can be at least one of nitric acid, acetic acid and citric acid, and the extrusion assisting agent can be sesbania powder. The addition amount of the adhesive and the extrusion aid is added according to actual molding requirements, and the invention has no special requirement. For example, the addition amount of the adhesive is 0.5-4.0 wt% of the mass of the raw material. The addition amount of the extrusion aid is 0.5-5.0 wt% of the mass of the raw material. The addition amount of water is 85-100 wt% of the mass of the raw material.
According to the invention, in the step (3), the drying temperature is 120-160 ℃, the drying time is 2-6 hours, the roasting temperature is 550-750 ℃, and the roasting time is 2-6 hours.
According to the invention, the boron source in the step (4) is boric acid, and the polyalcohol is one or more of 1, 4-butanediol, 1, 3-propanediol, tetrol, glycerol, polyethylene glycol (with molecular weight below 2000) and diethylene glycol. The mass ratio of the boric acid to the polyol is 2:1-4:1.
According to the invention, the solvent I in step (4) is added dropwise to the solution comprising the boron source and the polyol for a period of 30 to 180 minutes, preferably 60 to 120 minutes. And continuously stirring for 20-60 min after dripping.
According to the invention, the impregnation in step (4) may be by spray impregnation, and the impregnation may be by an isovolumetric impregnation or a supersaturation impregnation, preferably by isovolumetric impregnation. The drying conditions are that the drying temperature is 100-160 ℃, the drying time is 1-8 h, and the roasting conditions are that the roasting temperature is 450-650 ℃ and the roasting time is 2-7h.
According to the invention, in the step (5), the group VIII metal is nickel, and the concentration of the nickel source in the second impregnating solution is 40-120 g/L based on nickel oxide. The nickel source is selected from at least one of soluble salts such as nitrate, monohydrogen phosphate, dihydrogen phosphate, etc., and the organic acid is at least one of citric acid, malic acid, acetic acid, formic acid, malonic acid, and succinic acid. The molar ratio of the organic acid to the group VIII element is 0.5:1-2:1, preferably 0.8:1-1.5:1.
According to the invention, the impregnation in the step (5) can be an injection impregnation method, an equal volume impregnation method or a supersaturation impregnation method is adopted in the impregnation, preferably equal volume impregnation, and the drying condition is that the drying is carried out at 100-160 ℃ for 1-8 hours. Further, health maintenance can be performed before drying. The curing is to place the impregnated carrier in a closed container at 10-30 ℃ for 6-12 hours. The pressure of the curing is not particularly limited, and may be autogenous pressure.
According to the invention, the composition of the hydrogenation catalyst in step (5), based on the mass of the catalyst, comprises, in mass fraction:
based on molybdenum trioxide, the content of Mo in terms of oxide is 5.0% -22.0%,
Based on nickel oxide, the content of Ni is 3% -9%,
Based on vanadium pentoxide, the content of vanadium is 0.2% -3.0%,
Based on phosphorus pentoxide, the content of phosphorus is 0.5% -4.0%,
The boron content is 0.1% -0.5% based on the diboron trioxide,
The content of the organic acid is 0.5% -2.5%,
The content of the alumina is 59.0% -90.0%.
According to the invention, the catalyst in the step (5) has the characteristics of specific surface area of 170-280 m 2/g, pore volume of 0.6-1.3 mL/g, average pore diameter of 9-15 nm and mechanical strength of 150-200N/cm.
In another aspect the present invention provides a hydrogenation catalyst prepared by the above process, preferably the hydrogenation catalyst is a residuum hydrodemetallization catalyst or a residuum hydrodesulphurisation catalyst.
Compared with the prior art, the invention has the following advantages:
In the method of the invention, the catalyst powder can react with chlorine by controlling the reaction conditions, molybdenum can be simply extracted from the catalyst with high selectivity and transferred into a solvent phase, then the solvent phase is dripped into a solution containing a boron source and polyalcohol to obtain a first impregnating solution, meanwhile, carbon deposition in a dead catalyst can be effectively reserved in a carrier component while molybdenum is effectively extracted, the carrier component is mixed with pseudoboehmite and is roasted to obtain a carrier, carbon deposition is removed, finally, the first impregnating solution is loaded on the carrier and is roasted, and then is impregnated with a second impregnating solution of VIII group metal and organic acid to obtain the catalyst, thereby being beneficial to adjusting the pore structure of the catalyst on one hand and further increasing the surface of the carrier The quantity of acid sites can generate more coordination unsaturated sites, on the other hand, the load of active components is adjusted, particularly, the quantity of molybdenum entering into small holes is reduced, and the active components are more uniformly loaded on the surface of a carrier in a mode of +5-valent molybdenum and are more easily vulcanized into +4-valent MoS 2, so that the rate of Mo forming MoS 2 is accelerated, the introduction of complexing auxiliary agents delays the vulcanization of Ni, the efficient hydrogenation active phase structure taking MoS 2 as a framework and the outer surface of metallic nickel is more easily formed in the catalyst, and the activity and stability of the catalyst are improved.
Detailed Description
The operation and effect of the present invention will be further illustrated by the following examples, which are not to be construed as limiting the process of the present invention.
In the invention, the percentages are mass fractions unless otherwise specified.
The specific surface area, pore volume and pore distribution are measured by adopting an ASAP2420 type full-automatic physical adsorption instrument of America microphone instrument company, wherein the measuring method comprises the steps of treating a sample for 4 hours at 300 ℃ and 0.1MPa, taking liquid N 2 as an adsorbate, accurately weighing the sample at-196 ℃, and then analyzing and testing the sample. Wherein the specific surface area is calculated by BET method, and the pore volume and pore distribution are calculated by BJH method.
In the invention, the catalyst composition is tested by spectrophotometry. The test instrument was a Lambda 365 ultraviolet spectrophotometer.
In the present invention, the composition and properties of the catalysts prepared in each example are shown in Table 1.
In the invention, the composition of the waste hydrogenation catalyst adopted in each example is 85% of catalyst solids and 15% of petroleum fraction by mass fraction.
In the invention, the extraction and deoiling conditions of each example are that the organic solvent is toluene, the extraction temperature is 100 ℃, the extraction time is 72 hours, and the mass ratio of the organic solvent to the catalyst is 30:1. The composition of the waste hydrogenation catalyst after oil removal by extraction is as follows by mass percent:
19.2% molybdenum, calculated as molybdenum trioxide;
8.6% nickel calculated as nickel oxide;
4.2% vanadium calculated as vanadium pentoxide;
9.1% of carbon, based on the total weight of the alloy,
The balance being alumina as carrier.
Example 1
(1) And (3) extracting and degreasing the waste hydrogenation catalyst after industrial operation, drying at 120 ℃ for 6 hours, and crushing to 300 meshes.
(2) 334G of catalyst powder is taken and placed in a container, 3.9 mL/(min.g of catalyst) of chlorine with the purity of 98v% is introduced for reaction, the reaction temperature is 350 ℃, and the reaction time is 80min. And cooling the reacted catalyst to 30 ℃, then moving the catalyst to 1169g of acetone, uniformly mixing the catalyst, then placing the catalyst into an ultrasonic generator, treating the catalyst for 1 hour at the ultrasonic frequency of 50KHz under the temperature of 30 ℃ by taking the acetone as a medium, and separating the catalyst to obtain a solvent I and a material II respectively. Wherein the material II is 269g.
(3) Taking 179g of pseudo-boehmite (the mass content of alumina is 69.1%), mixing and kneading 9g of sesbania powder, 4.5g of nitric acid and 428g of water for molding, drying at 120 ℃ for 3 hours, and roasting at 700 ℃ for 4 hours to obtain the catalyst carrier A-0.
(4) Solvent I was added dropwise to a solution containing 5.6g of boric acid and 2.5g of 1, 4-butanediol for 90min. And stirring was continued for 30min to the impregnation liquor L-0. The impregnating solution L-0 is impregnated on the carrier A-0 by adopting a spraying mode, and is dried for 4 hours at 130 ℃ and roasted for 3 hours at 500 ℃ to obtain A-1.
(5) 21G of nickel nitrate hexahydrate and 6.3g of acetic acid were weighed and dissolved in 100.0mL of water, the obtained solution was designated as L-1, and the impregnating solution L-1 was impregnated on the carrier A-1 by spraying to obtain DA-1. DA-1 was left in a closed container at room temperature of 20℃for 6 hours and dried at 120℃for 4 hours to give CA-1. The composition of catalyst CA-1 is shown in Table 1.
Example 2
(1) And (3) extracting and degreasing the waste hydrogenation catalyst after industrial operation, drying at 140 ℃ for 4 hours, and crushing to 500 meshes.
(2) 298G of catalyst powder is placed in a container, 6.3 mL/(min.g of catalyst) of chlorine with the purity of 99v% is introduced for reaction, the reaction temperature is 350 ℃, the reaction time is 50min, the catalyst after the reaction is cooled to 30 ℃, then the catalyst is moved to 1192g of tetrahydrofuran for uniform mixing and then is placed in an ultrasonic generator, tetrahydrofuran is used as a medium, the treatment is carried out for 2 hours at the ultrasonic frequency of 100KHz at 50 ℃, and the solvent I and the material II are respectively obtained after separation. Wherein the amount of the material II is 240g.
(3) Taking 184g of pseudo-boehmite (the mass content of alumina is 69.1%), mixing and kneading 6g of sesbania powder, 7.2g of nitric acid and 408g of water for molding, drying at 120 ℃ for 4 hours, and roasting at 750 ℃ for 3 hours to obtain the catalyst carrier B-0.
(4) Solvent I was added dropwise to a solution containing 4.5g of boric acid and 2.0g of 1, 4-butanediol for 60 minutes. And continuously stirring for 30min until reaching the impregnating solution L-0, impregnating the impregnating solution L-0 on the carrier B-0 by adopting a spraying mode, drying at 120 ℃ for 4 hours, and roasting at 480 ℃ for 3 hours to obtain B-1.
(5) 20G of nickel nitrate hexahydrate and 4.2g of acetic acid were weighed and dissolved in 100.0mL of water, the obtained solution was designated as L-1, and the above-mentioned impregnating solution L-1 was impregnated on the carrier B-2 by spraying to obtain DB-2. DB-2 in room temperature 20 ℃ closed container after 6 hours, at 120 ℃ drying 4 hours, CB-2. The composition of catalyst CB-2 is shown in Table 1.
Example 3
(1) And (3) extracting and degreasing the waste hydrogenation catalyst after industrial operation, drying at 120 ℃ for 6 hours, and crushing to 300 meshes.
(2) 334G of catalyst powder is placed in a container, 3.9 mL/(min.g of catalyst) of chlorine with the purity of 98v% is introduced for reaction, the reaction temperature is 400 ℃, the reaction time is 80min, the catalyst after the reaction is cooled to 30 ℃, then the catalyst is moved to 1336g of acetic acid for uniform mixing and then placed in an ultrasonic generator, acetic acid is used as a medium, the ultrasonic generator is treated for 1 hour at the ultrasonic frequency of 120KHz at 30 ℃, and the solvent I and the material II are respectively obtained after separation. Wherein the material II is 269g.
(3) Taking 179g of pseudo-boehmite (the mass content of alumina is 69.1%), mixing and kneading 9g of sesbania powder, 4.5g of nitric acid and 428g of water for molding, drying at 130 ℃ for 3 hours, and roasting at 730 ℃ for 4 hours to obtain the catalyst carrier C-0.
(4) Solvent I was added dropwise to a solution containing 6g of boric acid and 1.5g of 1, 3-propanediol for 120min. And continuously stirring for 30min until reaching the impregnating solution L-0, impregnating the impregnating solution L-0 on the carrier C-0 by adopting a spraying mode, drying at 130 ℃ for 4 hours, and roasting at 480 ℃ for 3 hours to obtain C-1.
(5) 10.3G of nickel nitrate hexahydrate and 2.9g of acetic acid were weighed and dissolved in 60.0mL of water, the obtained solution was designated as L-1, and the impregnating solution L-1 was impregnated on the carrier C-1 by spraying to obtain DC-1. After placing DC-1 in a closed container at room temperature of 20 ℃ for 6 hours, drying is carried out at 120 ℃ for 4 hours, thus obtaining CC-1. The composition of catalyst CC-1 is shown in Table 1.
Example 4
(1) And (3) extracting and degreasing the waste hydrogenation catalyst after industrial operation, drying at 120 ℃ for 6 hours, and crushing to 300 meshes.
(2) 400G of catalyst powder is placed in a container, 5.3 mL/(min g of catalyst) of chlorine with the purity of 98v% is introduced for reaction, the reaction temperature is 300 ℃, the reaction time is 60min, the catalyst after the reaction is cooled to 30 ℃, then the catalyst is moved to 1760g of acetone for uniform mixing and then placed in an ultrasonic generator, the acetone is used as a medium, the solvent I and the material II are obtained by separation after the treatment of the acetone as a medium at the ultrasonic frequency of 50KHz for 1 hour. Wherein the material II is 323g.
(3) Taking 184g of pseudo-boehmite (the mass content of alumina is 69.1%), mixing and kneading 9g of sesbania powder, 4.5g of nitric acid and 450g of water for molding, drying at 120 ℃ for 3 hours, and roasting at 700 ℃ for 4 hours to obtain the catalyst carrier D-0.
(4) Solvent I was added dropwise to a solution containing 4g of boric acid and 2g of glycerol for 90min. And continuously stirring for 30min until reaching the impregnating solution L-0, impregnating the impregnating solution L-0 on the carrier D-0 by adopting a spraying mode, drying at 130 ℃ for 4 hours, and roasting at 485 ℃ for 3 hours to obtain D-1.
(5) 18G of nickel nitrate hexahydrate and 4g of acetic acid are weighed and dissolved in 100.0mL of water, the obtained solution is marked as L-1, and the dipping liquid L-1 is dipped on the carrier D-1 in a spraying mode to obtain DD-1. DD-1 was left in a closed container at room temperature of 20℃for 6 hours and dried at 120℃for 4 hours to give CD-1. The composition of catalyst CD-1 is shown in Table 1.
Comparative example 1
In comparison with example 1, only the chlorine gas in step (2) was replaced with air. The other steps are the same as in example 1.
The comparative hydrogenation catalyst DCA-1 was prepared.
Comparative example 2
In comparison with example 1, a fresh catalyst before deactivation was used for comparison.
The comparative hydrogenation catalyst DCA-2 was prepared.
Comparative example 3
Compared with the embodiment 1, the difference is that the pseudo-boehmite is not added in the step (3), but the material II is directly kneaded with the adhesive, the extrusion aid and the water for molding.
The comparative hydrogenation catalyst DCA-3 was prepared.
Comparative example 4
The difference compared with example 1 is that no organic acid is added during the preparation of the impregnating solution in step (5).
The comparative hydrogenation catalyst DCA-4 was prepared.
Comparative example 5
Compared with example 1, the comparative hydrogenation catalyst DCA-5 was prepared by using only solvent I as the first impregnation solution without adding the boron source and the polyol in step (4).
Comparative example 6
Steps (1) - (3) of this example are the same as in example 1. Step (4) and step (5) in example 1 were replaced with the following step A. The step A of this example is that the impregnating solution of this example is a mixed solution of the first impregnating solution L-0 and the second impregnating solution L-1 in example 1. The catalyst support of step (3) was then impregnated with the above impregnation solution, dried at 130℃for 4 hours and calcined at 500℃for 3 hours to give catalyst DCA-6.
Table 1 composition of the catalysts obtained in each example
TABLE 2 Properties of the catalysts obtained in each example
Catalyst evaluation
The catalysts obtained in examples and comparative examples were evaluated by using the raw oil as shown in Table 3, and the reaction conditions are shown in Table 3, and the evaluation results are shown in Table 4.
TABLE 3 raw oil Properties and reaction conditions
Table 4 evaluation results of catalysts of examples
| Removal rate | Run time, h | Example 1 | Example 2 | Example 3 | Example 4 |
| HDM,% | 200 | 98.1 | 98.3 | 98.5 | 98.3 |
| HDM,% | 2000 | 88.4 | 88.3 | 88.3 | 88.6 |
| HDS,% | 200 | 94.6 | 95.3 | 94.8 | 95.2 |
| HDS,% | 2000 | 83.6 | 83.5 | 84.4 | 83.5 |
| HDN,% | 200 | 84.7 | 81.4 | 82.6 | 83.5 |
| HDN,% | 2000 | 71.5 | 72.6 | 73.3 | 72.6 |
Table 3 shows the sequence
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A method for preparing a hydrogenation catalyst, comprising the steps of:
(1) Crushing the solid obtained after the molybdenum-nickel series waste catalyst is extracted and deoiled;
(2) After the catalyst powder reacts with chlorine, cooling and transferring the catalyst powder into an anhydrous organic solvent for ultrasonic treatment, and separating to obtain a solvent I and a material II;
(3) Kneading the material II and pseudo-boehmite for molding, drying and roasting to obtain a catalyst carrier;
(4) Dropwise adding a solvent I into a solution containing a boron source and a polyalcohol to obtain a first impregnating solution, impregnating the first impregnating solution on the carrier in the step (3), and drying and roasting the first impregnating solution to obtain a catalyst intermediate;
(5) And (3) impregnating the catalyst intermediate with a second impregnating solution containing a group VIII metal and an organic acid, and drying to obtain the hydrogenation catalyst.
2. The method according to claim 1, wherein the spent hydrogenation catalyst after oil removal in step (1) is extracted by mass fraction based on the catalyst mass, comprising:
10% -25% of molybdenum by molybdenum trioxide;
3% -10% of nickel by nickel oxide;
3% -10% of vanadium calculated by vanadium pentoxide;
6% -14% of carbon;
41% -77% of carrier alumina.
3. The method of claim 1, wherein the purity of the chlorine gas in step (2) is 96% or more by volume fraction;
And/or the flow rate of the chlorine gas in the step (2) is 2.7-6.8 mL/(min g of catalyst).
4. The method according to claim 1, wherein the reaction conditions in the step (2) are that the reaction temperature is 300-400 ℃ and the reaction time is 40-90 min.
5. The method according to claim 1, wherein the ultrasonic frequency in the step (2) is 10-150 KHz, and/or the ultrasonic treatment temperature is 20-70 ℃ and the treatment time is 0.5-2 h.
6. The method according to claim 1, wherein the mass ratio of the pseudo-boehmite in the step (3) to the material II is 7-13:15-30 in terms of alumina.
7. The method of claim 1, wherein the boron source in step (4) is boric acid;
and/or the polyalcohol is one or more of 1, 4-butanediol, 1, 3-propanediol, tetrol, glycerol, polyethylene glycol and diethylene glycol;
And/or the mass ratio of the boric acid to the polyol is 2:1-4:1.
8. The method of claim 1, wherein in step (5), the group VIII metal is nickel;
and/or the concentration of the nickel source in the second impregnating solution is 40-120 g/L;
And/or the nickel source is derived from at least one of soluble salts, such as nitrate, monohydrogen phosphate, dihydrogen phosphate;
and/or the organic acid is at least one of citric acid, malic acid, acetic acid, formic acid, malonic acid and succinic acid;
And/or the molar ratio of the organic acid to the group VIII element is 0.5:1-2:1, preferably 0.8:1-1.5:1.
9. The process of claim 1, wherein the composition of the hydrogenation catalyst in step (5), in mass fraction based on the mass of the catalyst, comprises:
based on molybdenum trioxide, the content of Mo in terms of oxide is 5.0% -22.0%,
Based on nickel oxide, the content of Ni is 3% -9%,
Based on vanadium pentoxide, the content of vanadium is 0.2% -3.0%,
Based on phosphorus pentoxide, the content of phosphorus is 0.5% -4.0%,
The boron content is 0.1% -0.5% based on the diboron trioxide,
The content of the organic acid is 0.5% -2.5%,
The content of the alumina is 59.0% -90.0%.
10. The method according to claim 1, wherein the catalyst in the step (5) has a specific surface area of 170-280 m 2/g, a pore volume of 0.6-1.3 mL/g, an average pore diameter of 9-15 nm, and a mechanical strength of 150-200N/cm.
11. The hydrogenation catalyst prepared by the method of any one of claims 1 to 10, preferably a residuum hydrodemetallization catalyst or a residuum hydrodesulfurization catalyst.
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| CN202311317028.3A CN119819378A (en) | 2023-10-12 | 2023-10-12 | Preparation method of hydrogenation catalyst |
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| CN202311317028.3A CN119819378A (en) | 2023-10-12 | 2023-10-12 | Preparation method of hydrogenation catalyst |
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| US4350609A (en) * | 1981-02-26 | 1982-09-21 | Gulf Research & Development Company | Process for producing a catalyst by depositing molybdenum removed from a waste catalyst |
| CN105709853A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Method for recycling waste hydrogenation catalyst |
| CN108067272A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst preparation method |
| CN113976137A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| JP2022142809A (en) * | 2021-03-17 | 2022-10-03 | Ｊｆｅスチール株式会社 | Method for recovering valuable elements |
| CN116060059A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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| US4350609A (en) * | 1981-02-26 | 1982-09-21 | Gulf Research & Development Company | Process for producing a catalyst by depositing molybdenum removed from a waste catalyst |
| CN105709853A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Method for recycling waste hydrogenation catalyst |
| CN108067272A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst preparation method |
| CN113976137A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| JP2022142809A (en) * | 2021-03-17 | 2022-10-03 | Ｊｆｅスチール株式会社 | Method for recovering valuable elements |
| CN116060059A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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