CN116020498A - Preparation method of hydrogenation catalyst, catalyst prepared by method and application - Google Patents

Preparation method of hydrogenation catalyst, catalyst prepared by method and application Download PDF

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CN116020498A
CN116020498A CN202111255180.4A CN202111255180A CN116020498A CN 116020498 A CN116020498 A CN 116020498A CN 202111255180 A CN202111255180 A CN 202111255180A CN 116020498 A CN116020498 A CN 116020498A
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magnesium
pseudo
content
boehmite
catalyst
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贾燕子
户安鹏
曾双亲
胡大为
杨清河
赵新强
王轶凡
邓中活
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a preparation method of a hydrogenation catalyst, the catalyst prepared by the method and application, wherein the method comprises the following steps: (1) preparing pseudo-boehmite containing phosphorus and magnesium; (2) Mixing and shaping the pseudo-boehmite containing phosphorus and magnesium with a precursor of a hydrogenation active metal component, and then sequentially drying and activating to obtain the hydrogenation catalyst; the conditions of the activation include: the temperature rising speed is 50-600 ℃/h, the temperature is 400-1000 ℃ and the time is 1-10 h. According to the preparation method provided by the invention, the pseudo-boehmite is directly mixed with the precursor of the hydrogenation active metal component, and after being molded, the hydrogenation catalyst can be obtained after one-time drying and roasting, so that the process of preparing the carrier by drying and roasting the pseudo-boehmite is omitted, the preparation process is simplified, and the prepared catalyst has excellent hydrogenation activity and stability.

Description

Preparation method of hydrogenation catalyst, catalyst prepared by method and application
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a preparation method of a hydrogenation catalyst, a catalyst prepared by the method and application of the catalyst.
Background
The hydrogenation catalyst is the core of the perhydro refinery, and the hydrogenation catalyst mainly comprises a carrier and an active metal component. Alumina, particularly gamma-alumina, is often used as a support for catalyst preparation due to its relatively good pore structure, specific surface area and heat stability. Especially the pore structure of the alumina carrier is critical to the performance of the catalyst. The raw material of the alumina carrier is generally pseudo-boehmite, various different methods for preparing the phosphorus-containing pseudo-boehmite are disclosed in the prior art, the properties of the pseudo-boehmite and the alumina described in the prior art are excellent in some aspects in terms of controlling the pore distribution and pore volume of the alumina by different methods, but the phosphorus-containing alumina which has double-peak pores and has larger pore volume and total pore volume on two pore distributions is difficult to obtain.
In the prior art, a great number of hydrogenation catalysts and preparation methods are disclosed, and a great number of reports are also provided on the influence of carrier characteristics on the catalyst performance, including the influence of pore diameter, pore distribution, acidity, auxiliaries and the like on the final catalyst performance, but in the scheme in the prior art, the alumina carrier with large mesopore volume, large macropore volume and total pore volume is difficult to obtain, and the corresponding hydrogenation catalyst cannot be obtained.
Disclosure of Invention
The invention aims to overcome the defects that the preparation process of a catalyst is complicated and the activity and stability of the catalyst are required to be further improved in the prior art, and provides a preparation method of a hydrogenation catalyst, the hydrogenation catalyst and application thereof.
The inventor of the invention discovers in the research process that in the preparation process of the hydrogenation catalyst, after mixing and molding a pseudo-boehmite containing phosphorus and magnesium and a precursor of hydrogenation active metal components, the hydrogenation catalyst can be obtained after only once drying and roasting; compared with the prior art, the preparation method omits the process of preparing the carrier by drying and roasting pseudo-boehmite, simplifies the preparation process, and the prepared catalyst has excellent hydrogenation activity and stability.
In order to achieve the above object, the present invention provides a method for preparing a hydrogenation catalyst, comprising the steps of:
(1) Preparing pseudo-boehmite containing phosphorus and magnesium;
(2) Mixing and shaping the pseudo-boehmite containing phosphorus and magnesium with a precursor of a hydrogenation active metal component, and then sequentially drying and activating to obtain the hydrogenation catalyst;
the conditions of the activation include: the temperature rising speed is 50-600 ℃/h, the temperature is 400-1000 ℃ and the time is 1-10 h;
the hydrogenation active metal component comprises at least one VIB metal component and at least one VIII metal component
A group metal component; the components are used in amounts such that the content of the group VIB metal component in the final catalyst is 0.5 to 50% by weight and the content of the group VIII metal component is 0.5 to 20% by weight, calculated as oxides.
The invention also provides a hydrogenation catalyst prepared by the method and application of the hydrogenation catalyst in hydrocarbon oil hydrogenation reaction.
Compared with the prior art, the preparation method provided by the invention has the advantages that the pseudo-boehmite is directly mixed with the precursor of the hydrogenation active metal component, and after the mixture is molded, the hydrogenation catalyst can be obtained after only one-time drying and roasting, the process of preparing the carrier by drying and roasting the pseudo-boehmite is omitted, the preparation process is simplified, the prepared catalyst has excellent hydrogenation activity and stability, and has better demetallization, desulfurization and carbon residue removal activities under the same other conditions, so that the catalyst cost is reduced, the operation period of the catalyst is prolonged, and the improvement of the overall economic benefit of refineries is facilitated.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the pore distribution refers to a distribution of pore diameters unless otherwise specified. The pore diameter refers to the pore diameter.
According to the method for preparing a catalyst provided by the present invention, there is no particular requirement for pseudo-boehmite containing phosphorus and magnesium therein. When the phosphorus and magnesium containing pseudo-boehmite in the step (1) meets the following requirements, the prepared hydrogenation catalyst has better performance, specifically, based on the total weight of the phosphorus and magnesium containing pseudo-boehmite, al 2 O 3 The content of (2) is 84 to 99.8 wt%, more preferably 84 to 99.7 wt%; p (P) 2 O 5 The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, the content of auxiliary element is 0-5 wt%, and more preferably 0.1-5 wt%; preferably, the phosphorus and magnesium containing pseudo-boehmite obtained after roasting at 600 ℃ for 3 hours has a bimodal pore structure, as measured by mercury intrusion, with a pore distribution of mesopore pore volume V in the range of 3-100nm Middle hole 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm Macropores are formed 1.7-4.7mL/g, total pore volume V Total (S) 2.4-6.4mL/g; further preferably, the pore distribution of the phosphorus and magnesium containing alumina is located at a mesopore volume V of 3-100nm Middle hole 0.9-1.5mL/g, pore distribution of 100-5000Macropore volume V at nm Macropores are formed 1.8-3.2mL/g, total pore volume V Total (S) 2.7-4.7mL/g.
In order to further improve the performance of the catalyst, the pseudo-boehmite containing phosphorus and magnesium can also contain optional auxiliary elements, wherein the auxiliary elements comprise metal auxiliary elements and/or non-metal auxiliary elements; the metal auxiliary element is at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium; the nonmetallic auxiliary agent element is selected from at least one of boron element, fluorine element and silicon element.
The catalyst obtained by the preparation method is subjected to hydrogen temperature programmed reduction (H) 2 TPR), peak height P of the low temperature reduction peak preferably located at 300-500 DEG C Low temperature peak Peak height P with high temperature reduction peak at 650-850 deg.c High temperature peak Ratio s=p of (2) Low temperature peak /P High temperature peak 0.5-2.0; further preferably, the peak height P of the low-temperature reduction peak Low temperature peak Peak height P from high temperature reduction peak High temperature peak Ratio s=p of (2) Low temperature peak /P High temperature peak From 0.7 to 1.9, preferably from 0.8 to 1.8.
According to the preparation method of the invention, the purpose of the activation in the step (2) is to convert pseudo-boehmite into alumina, convert hydrogenation active metals into oxidation state and enhance the acting force of hydrogenation active metal components and a carrier. Preferably, the activating conditions include: the temperature rising rate is 100-550 ℃/h, the temperature is 410-880 ℃, preferably 430-850 ℃, and most preferably 450-830 ℃.
The types and the contents of the hydrogenation metal active components are all conventional in the art, for example, the VIB metal component is Mo and/or W, and the VIII metal component is Co and/or Ni; the components are used in such amounts that the content of the group VIB metal component, calculated as oxides, is 5-45 wt.% and the content of the group VIII metal component is 1-15 wt.%, based on the total amount of the catalyst in the final catalyst.
The specific preparation method of the pseudo-boehmite containing phosphorus and magnesium is not particularly limited, and in order to obtain the alumina carrier with large mesopore volume, large macropore volume and total pore volume, the pseudo-boehmite containing phosphorus and magnesium can be prepared by the following steps:
(a) Contacting phosphorus-containing compound, magnesium-containing compound and inorganic aluminum-containing compound solution with acid or alkali to perform precipitation reaction, or contacting organic aluminum-containing compound with magnesium-containing compound and phosphorus-containing compound solution to perform hydrolysis reaction to obtain hydrated alumina containing phosphorus and magnesium;
(b) Aging the obtained hydrated alumina containing phosphorus and magnesium under the condition that the pH value is 7-10.5, and then drying the aged solid product to obtain pseudo-boehmite containing phosphorus and magnesium;
the precipitation reaction or the hydrolysis reaction of step (a) is carried out at a pH of 4 to 7.
Further preferably, the precipitation reaction or the hydrolysis reaction of step (a) is carried out at a pH of 4 to 6.5; the temperatures of the precipitation reaction and the hydrolysis reaction are each independently 30-90 ℃; the conditions of the precipitation reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 10-60 minutes, preferably 10-30 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 2-20 hours.
The inorganic aluminum-containing compound, phosphorus-containing compound, magnesium-containing compound, organic aluminum-containing compound, acid, alkali, etc. in the preparation step are all conventionally selected in the art, for example, the inorganic aluminum compound is an aluminum salt and/or aluminate; the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrated aluminum oxide precipitation through hydrolysis reaction with water; the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate; the magnesium-containing compound is an inorganic magnesium salt, and is selected from one or more of magnesium chloride, magnesium nitrate, magnesium sulfate and magnesium acetate; the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid; the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.
In the present invention, the manner of adding the phosphorus-containing compound and the magnesium-containing compound is not particularly limited, and the phosphorus-containing compound (or the aqueous solution of the phosphorus-containing compound) and the magnesium-containing compound (or the aqueous solution of the magnesium-containing compound) may be added separately, or the phosphorus-containing compound (or the aqueous solution thereof) and the magnesium-containing compound (or the aqueous solution thereof) may be mixed with one or more of the raw materials in advance, and then the raw materials containing the phosphorus-containing compound and the magnesium-containing compound are reacted, as long as the precipitation reaction or the hydrolysis reaction is ensured to be carried out in the presence of the phosphorus-containing compound and the magnesium-containing compound.
The pH of the aging step in the preparation of pseudo-boehmite is preferably from 8 to 10, the remainder of the procedure being conventional in the art, e.g., the aging conditions include: the temperature is 50-95deg.C, preferably 55-90deg.C; the time is 0.5 to 8 hours, preferably 2 to 6 hours. The drying conditions in step (b) may be: the temperature is 50-350deg.C, preferably 80-250deg.C, and the drying time is 1-12 hr, preferably 2-8 hr.
In order to introduce an auxiliary agent which is favorable for improving the performance of the catalyst, when preparing the pseudo-boehmite containing phosphorus and magnesium, an optional compound containing auxiliary agent elements is added in the precipitation reaction or the hydrolysis reaction of the step (a), wherein the auxiliary agent elements comprise metal auxiliary agent elements and/or nonmetal auxiliary agent elements; the metal auxiliary element is at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium, more preferably at least one of lithium, sodium, potassium, beryllium, calcium, zirconium and titanium; the nonmetallic auxiliary agent element is selected from at least one of boron element, fluorine element and silicon element. In order to further improve the catalyst performance, the components are used in such amounts that the total amount of the pseudo-boehmite dry basis containing phosphorus and magnesium is taken as the reference, al 2 O 3 The content of P is 85-99.8 wt%, more preferably 85-99.7 wt% 2 O 5 The content of (2) is 0.1-5 wt.%, the content of MgO is 0.1-5 wt.%, the content of auxiliary elements is 0-5 wt.%, more preferably 0.1-5 wt.%.
The step of preparing pseudo-boehmite containing phosphorus and magnesium according to the present invention further comprises separating, washing and drying the aged product after the aging reaction. The separation according to the method provided by the present invention may be a method known in the art, such as filtration or centrifugation. The washing and drying method may be a method commonly used in the preparation of pseudo-boehmite, for example, the washing agent may be water and the drying may be at least one of drying, forced air drying, spray drying and flash drying. The drying temperature may be 100-350 ℃, preferably 120-300 ℃.
According to the preparation method provided by the invention, in the preparation process of the catalyst, an organic additive can be introduced when the pseudo-boehmite is kneaded with the active metal component. The kind of the organic additive is not particularly limited in the present invention, and the organic additive is at least one selected from oxygen-containing and/or nitrogen-containing organic matters selected from organic alcohols and/or organic acids, and the nitrogen-containing organic matters are at least one selected from organic amines and organic amine salts; specifically, the oxygen-containing organic matter is selected from at least one of ethylene glycol, glycerol, polyethylene glycol (with a molecular weight of 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid, and preferably at least one of ethylene glycol, glycerol, polyethylene glycol and citric acid; the nitrogen-containing organic matter is selected from at least one of ethylenediamine, diethylenetriamine, cyclohexanediamine tetraacetic acid, glycine, nitrilotriacetic acid, EDTA and amine salts thereof, preferably EDTA and/or nitrilotriacetic acid.
According to the production method provided by the present invention, the conditions for drying after kneading the hydrogenation-active metal group with the pseudo-boehmite containing phosphorus and magnesium are not particularly limited, and preferably, the conditions for drying include: the drying temperature is 80-200deg.C, preferably 100-150deg.C; the drying time is 1 to 8 hours, preferably 2 to 6 hours. The drying mode is not particularly limited in the present invention, and the drying may be at least one of drying, forced air drying, spray drying and flash drying. According to the production method provided by the present invention, the atmosphere for the activation and the drying is not particularly limited, and may be at least one of air, oxygen and nitrogen, preferably air.
The invention also provides application of the hydrogenation catalyst prepared by the preparation method in hydrocarbon oil hydrogenation reaction. According to the present invention, the hydrogenation catalyst may be presulfided prior to use in accordance with conventional methods in the art to convert the active metal component supported thereon to a metal sulfide component; the pre-vulcanization method can be as follows: presulfiding the hydrogenation catalyst with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140-400 ℃. This pre-vulcanization may be performed ex-situ or in-situ.
The hydrogenation conditions in the application of the hydrogenation catalyst are not particularly limited, and reaction conditions common in the art can be adopted; preferably, the reaction temperature is 200-420 ℃, more preferably 220-400 ℃, the pressure is 2-18MPa, more preferably 2-16MPa, and the liquid hourly space velocity is 0.1-10 hours -1 And more preferably 0.15 to 6 hours -1 The hydrogen oil volume ratio is 50 to 5000, more preferably 50 to 4000. The hydrotreating reaction apparatus in the application of the hydrotreating catalyst in the present invention is not particularly limited, and may be any reactor sufficient to allow the feedstock oil to contact the hydrotreating catalyst under hydrotreating reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor or an ebullated bed reactor. The application object of the hydrogenation catalyst is not particularly limited, and the hydrogenation catalyst can be directly used for processing various hydrocarbon oil raw materials so as to carry out hydro-upgrading or hydro-cracking on the hydrocarbon oil raw materials. The hydrocarbon oil raw material may be various heavy mineral oils or synthetic oils or their mixed distillate oils, for example, may be at least one selected from crude oil, distillate oil, solvent refined oil, cerate, underfills oil, fischer-tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil; is particularly suitable for the hydrotreatment of at least one of gasoline, diesel oil, wax oil, lubricating oil, kerosene, naphtha, atmospheric residuum, vacuum residuum, petroleum wax and Fischer-Tropsch synthetic oil.
The present invention will be described in detail by examples. In the following examples, the materials involved are commercially available unless otherwise indicated.
Pore volumes in the different pore size ranges of the phosphorus and magnesium containing alumina were measured using mercury porosimetry.
H of oxidation state catalyst 2 TPR (temperature programmed reduction) experiments were carried out on an Autochem II 2920 multifunctional adsorption apparatus from Micromeritics, USA. The experimental procedure was as follows: filling 0.20g of 40-60 mesh catalyst into a U-shaped quartz tube, heating to 50 ℃ at a speed of 2 ℃/min in 50mL/min argon, preprocessing a sample for 10min, and switching into Ar carrier gas with a volume fraction of 10% of H2, wherein the gas flow is 50mL/min. After the base line is stabilized, the temperature is raised to 1000 ℃ at the speed of 10 ℃/min, carrier gas enters a cold trap after passing through a reactor, water generated in the reduction process is condensed, and meanwhile, a thermal conductivity cell detector is used for detecting signals, so that a TPR spectrogram of a sample is obtained.
Example 1
This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.
(1) Preparation of pseudo-boehmite PA1:
in a 2L reaction tank, 5000 mL of aluminum sulfate solution with the concentration of 60 g/L, containing 40 g of magnesium nitrate, 8.0mL of 85 wt% concentrated phosphoric acid and ammonia water solution with the concentration of 6 wt% are added in parallel to carry out precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia water solution is controlled to enable the pH value of a reaction system to be 5.0, after the precipitation reaction is finished, a proper amount of ammonia water is added into slurry to enable the pH value of the slurry to be 8.7, the slurry is aged for 120 minutes at 70 ℃ and then filtered, a filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried for 24 hours at 120 ℃ to obtain PA1, the structure and the composition of the PA1 are characterized by adopting XRD, and the PA1 has a pseudo-boehmite structure. The contents of phosphorus element, magnesium element and auxiliary element in PA1 are shown in table 1. The pore structure of the resulting alumina was measured by firing PA1 at 600℃for 3 hours, and the results are shown in Table 1.
(2) Preparation of hydrogenation catalyst C1:
1000 g of PA1, 30 g of sesbania powder (manufactured by Shun trade limited company of Jiangsu Feng county), 317g of ammonium molybdate, 218g of nickel nitrate and 25g of nitric acid, 1200 g of water are uniformly mixed, then a butterfly wet strip with the outer diameter of 1.7mm is extruded on a plunger type strip extruder, the butterfly wet strip is dried for 4 hours at 130 ℃, the temperature rising speed of 180 ℃/h is increased to 620 ℃, and the hydrogenation catalyst C1 is obtained after activation for 3 hours. The metal oxide content of the hydrogenation catalyst is shown in table 2.
Comparative example 1
Pseudo-boehmite and catalyst were prepared as in example 1, except that only 8.0mL of 85 wt.% phosphoric acid was added to the aluminum sulfate solution, without magnesium nitrate, to give CPA1. XRD characterization was performed according to the method of example 1, CPA1 had pseudo-boehmite structure, the composition of CPA1 calculated by XRD characterization is shown in Table 1, DC1 was prepared according to the method of preparing catalyst C1 in example 1, pore structure of alumina obtained after roasting CPA1 at 600℃for 3 hours was measured, the results are shown in Table 1, and the content of metal oxide in DC1 is shown in Table 2.
Comparative example 2
Pseudo-boehmite and a catalyst were prepared as in example 1, except that the aluminum sulfate solution contained no magnesium nitrate, and the flow rate of the aqueous ammonia solution was directly controlled to bring the pH of the reaction system to 8.7, and after the precipitation reaction was completed, it was not necessary to add aqueous ammonia to the slurry to adjust the pH to obtain CPA2. The composition of CPA2, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA2 having a pseudo-boehmite structure. DC2 was prepared by the method of preparing catalyst C1 in example 1, and the pore structure of the alumina obtained after CPA2 was calcined at 600℃for 3 hours was measured, and the results are shown in Table 1, and the content of the metal oxide in DC2 is shown in Table 2.
Comparative example 3
The hydrogenation catalyst was prepared by the method of example 1, except that the activation conditions were different, specifically: roasting for 3 hours at 350 ℃ to obtain the hydrogenation catalyst DC3. The metal oxide content of the hydrogenation catalyst is shown in table 2.
Example 2
This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.
Preparation of pseudo-boehmite PA2:
in a 2L reaction tank, 4000 mL of an alumina solution containing 85 wt% concentrated phosphoric acid and having a concentration of 45 g/L, 22.1mL of magnesium nitrate and 20g of a sodium metaaluminate solution containing 210 g/L of alumina and having a caustic coefficient of 1.58 are added in parallel to carry out precipitation reaction, the reaction temperature is 80 ℃, the flow rate of reactants is adjusted to enable the neutralization pH value to be 4.0, and the reaction residence time is 15 minutes; dilute ammonia water with the concentration of 5 weight percent is added into the obtained slurry to adjust the pH of the slurry to 9.0, the temperature is raised to 85 ℃, the aging is carried out for 3 hours, then a vacuum filter is used for filtering, and after the filtering is finished, 20 liters of deionized water (the temperature is 85 ℃) is added on a filter cake to wash the filter cake for about 30 minutes. And adding the qualified filter cake into 3 liters of deionized water, stirring to form slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer to be in the range of 100-110 ℃, and drying the material for about 2 minutes to obtain PA2. The composition of PA2, as calculated by XRD characterization, is listed in table 1, as characterized by XRD for PA2 having a pseudo-boehmite structure.
The pore structure of the alumina obtained after firing PA2 at 600℃for 3 hours was measured in the same manner as in example 1, and the results are shown in Table 1. .
Catalyst C2 was prepared as in example 1, except that the activation temperature rise rate was 150℃per hour, the activation temperature was 650℃and the metal oxide content of C2 was as shown in Table 2.
Example 3
This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.
(1) Preparation of pseudo-boehmite PA3:
into a2 liter three-neck flask with stirring and reflux condenser, 1000 g of isopropyl alcohol-water azeotrope (water content 15 wt%) was added, 4.6mL of 85% concentrated phosphoric acid and 8g of magnesium nitrate were added, the pH was adjusted to 5.1 by adding ammonia water, then heated to 60 ℃, 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel, reacted for 2 hours, then adjusted to 8.5 by adding ammonia water, after reflux reaction for 20 hours, dehydrated isopropyl alcohol was distilled off, aged for 6 hours at 80 ℃, aqueous isopropyl alcohol was distilled off while aging, and after aging, hydrated alumina was filtered, dried for 24 hours at 120 ℃ to obtain PA3. The composition of PA3, as calculated by XRD characterization, is listed in table 1, as characterized by XRD for PA3 having a pseudo-boehmite structure.
(2) PA3 was prepared as in example 1 to prepare C3; the pore structure of the alumina obtained after firing PA3 at 600 ℃ for 3 hours was measured, and the results are shown in table 1, and the content of the metal oxide in C3 is shown in table 2.
Comparative example 4
The phosphorus-containing pseudo-boehmite is prepared according to the typical method in heavy oil hydrogenation catalyst carrier material research, and the concentration of 8.8mL of 85% concentrated phosphoric acid is 57 g.L -1 3000mL of aluminum sulfate solution with a concentration of 64 g.L -1 2500mL of sodium metaaluminate solution is subjected to precipitation reaction, the neutralization pH value is 8.0, the reaction time is 70min, then the aging is carried out, the aging temperature is 90 ℃, the aging pH value is 8.5, the filtering is carried out after the aging, the filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried at 120 ℃ for 24 hours to prepare the phosphorus-containing pseudo-boehmite CPA4. The composition of CPA4, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA4 having a pseudo-boehmite structure.
DC4 was prepared by the method of example 1 using CPA4. The pore structure of the alumina obtained after CPA4 was calcined at 600 ℃ for 3 hours was measured, and the results are shown in table 1, and the content of the metal oxide in DC4 is shown in table 2.
Example 4
Pseudo-boehmite and alumina carrier were prepared as in example 1 except that 2 g of sodium acetate was further added to the aluminum sulfate solution to obtain PA4. The composition of PA4, as calculated by XRD characterization, is listed in table 1, as characterized by XRD for PA4 having a pseudo-boehmite structure. PA4 was prepared as in example 1. The pore structure of the alumina obtained after firing PA4 at 600 ℃ for 3 hours was measured, and the results are shown in table 1, and the content of the metal oxide in C4 is shown in table 2.
Example 5
Pseudo-boehmite and alumina carrier were prepared as in example 1 except that 4g of ammonium fluoride was also added to the aluminum sulfate solution to give PA5.
The composition of PA5, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA5 having a pseudo-boehmite structure. PA5 was prepared as in example 1 to prepare C5; the pore structure of the alumina obtained after firing PA5 at 600 ℃ for 3 hours was measured, and the results are shown in table 1, and the content of the metal oxide in C5 is shown in table 2.
Comparative example 5
The procedure of example 1 was followed except that the PA1 was calcined at 350℃for 3 hours before kneading with the hydrogenation-active metal to give a catalyst of DC5, and the content of the catalyst metal component was shown in Table 2.
Comparative example 6
Catalyst DC6 was prepared according to the method of example 1, except that the hydrogenation-active metal component was introduced by impregnation, in particular:
1000 g of PA1 and 30 g of sesbania powder (manufactured by Shun trade Co., ltd. In Jiangsu Feng county) are taken and mixed uniformly, 1320 ml of aqueous solution containing 25g of nitric acid is added for mixing, then butterfly-shaped wet strips with the outer diameter of 1.7mm are extruded on a plunger type strip extruder, and the butterfly-shaped wet strips are dried for 4 hours at 130 ℃ to obtain a molded carrier. 130 g of the carrier was taken and 140 ml of a mixed aqueous solution composed of ammonium molybdate, nickel nitrate and citric acid (the mixed aqueous solution contains MoO 3 250 g/l, niO 60 g/l) impregnated the support for 3 hours, oven dried at 110 ℃ for 4 hours, heated to 620 ℃ at a rate of 180 ℃/h, and activated for 3 hours to give hydrogenation catalyst DC6. The metal oxide content of the hydrogenation catalyst is shown in table 2.
TABLE 1
Figure BDA0003323900590000131
Note that: v (V) Middle hole Refers to the mesoporous pore volume with the pore distribution of 3-100nm, and the unit is mL/g; v (V) Macropores are formed Refers to the macropore pore volume with the pore distribution of 100-5000nm, and the unit is mL/g; v (V) Total (S) Refers to total pore volume in units ofIs mL/g.
As can be seen from the results of Table 1, the pseudo-boehmite containing phosphorus and magnesium prepared by the method of the present invention has a bimodal pore structure, which is measured by mercury intrusion, with a pore distribution of a mesopore volume V ranging from 3 to 100nm Middle hole 0.9-1.4mL/g, a macropore pore volume V with a pore distribution of 100-5000nm Macropores are formed 1.8-2.5mL/g, total pore volume V Total (S) 2.7-3.9mL/g, and various pseudo-boehmite V prepared by the prior art method and the method in the comparative example Middle hole Are all below 0.7, V Macropores are formed Are all below 1, total pore volume V Total (S) Are all below 2.
TABLE 2
Figure BDA0003323900590000141
Example 6
The hydrogenation catalysts prepared in examples 1 to 5 and comparative examples 1 to 5, respectively, were crushed into particles having a diameter of 2 to 3 mm and then subjected to presulfiding under the conditions including: the vulcanized oil adopts Shanghai normal two-line diesel oil containing 5w percent of dimethyl disulfide, and the liquid hourly space velocity of the vulcanized oil is 1.2h -1 The hydrogen partial pressure is 14.0MPa, the hydrogen oil volume ratio is 600, and the constant temperature is carried out for 3 hours at 360 ℃.
Then, a poor heavy oil (Ni element content 11ppm, V element content 31ppm, density 0.973, carbon residue value 11.9%, S content 3.5%, N content 0.21%) was used as a raw material, the hydrogenation activity and stability of the catalyst were evaluated in a 100ml small fixed bed reactor, the reaction temperature was 380 ℃, the hydrogen partial pressure was 15 MPa, and the liquid hourly space velocity was 0.6 hours -1 Sample analysis was performed after 200 hours of reaction at a hydrogen/oil volume ratio of 600, and the results are shown in table 3.
Wherein, the calculation methods of the de (Ni+V) rate, the desulfurization rate and the carbon residue removal rate are the same; the present invention exemplifies a calculation method by taking the removal (ni+v) rate as an example, and the removal (ni+v) rate= (the (ni+v) content in the raw material-the (ni+v) content in the hydrogenated product)/the (ni+v) content in the raw material.
The content of nickel and vanadium in the oil sample is measured by adopting an inductively coupled plasma emission spectrometer (ICP-AES) (the used instrument is a PE-5300 type plasma light meter of PE company in the United states, and the specific method is shown in RIPP124-90 of petrochemical analysis method); the sulfur content in the oil sample is measured by an electric quantity method (the specific method is shown in the petrochemical analysis method RIPP 62-90); the carbon residue content in the oil sample is determined by a micro method (the specific method is shown in the petrochemical analysis method RIPP 149-90).
TABLE 3 Table 3
Examples numbering Sample name Rate of des (Ni+V)/% Desulfurization rate/% Carbon removal rate/%
Example 1 C1 80 85 60
Comparative example 1 DC1 59 51 49
Comparative example 2 DC2 57 61 41
Comparative example 3 DC3 63 58 39
Example 2 C2 82 86 58
Example 3 C3 79 83 59
Comparative example 4 DC4 61 53 40
Example 4 C4 82 84 56
Example 5 C5 83 82 59
Comparative example 5 DC5 71 69 52
Comparative example 6 DC6 79 84 61
As can be seen from Table 3, the catalyst provided by the invention has better demetallization, desulfurization and carbon residue removal activities under the same other conditions, and has excellent activity and stability.
The preferred embodiments of the present invention have been described in detail above, 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, the method comprising the steps of:
(1) Preparing pseudo-boehmite containing phosphorus and magnesium;
(2) Mixing and shaping the pseudo-boehmite containing phosphorus and magnesium with a precursor of a hydrogenation active metal component, and then sequentially drying and activating to obtain the hydrogenation catalyst;
the conditions of the activation include: the temperature rising speed is 50-600 ℃/h, the temperature is 400-1000 ℃ and the time is 1-10 h;
the hydrogenation active metal component comprises at least one VIB metal component and at least one VIII metal component; the components are used in amounts such that the content of the group VIB metal component in the final catalyst is 0.5 to 50% by weight and the content of the group VIII metal component is 0.5 to 20% by weight, calculated as oxides.
2. The process according to claim 1, wherein Al is based on the total amount of the phosphorus and magnesium-containing pseudo-boehmite dry basis 2 O 3 The content of (2) is 84 to 99.8 wt%, more preferably 84 to 99.7 wt%; p (P) 2 O 5 The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, the content of auxiliary element is 0-5 wt%, and more preferably 0.1-5 wt%;
the phosphorus and magnesium containing pseudo-boehmite obtained by roasting at 600 ℃ for 3 hours has a bimodal pore structure, the bimodal pore structure is measured by mercury intrusion method, and the pore distribution is positioned at the mesoporous pore volume V of 3-100nm Middle hole 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm Macropores are formed 1.7-4.7mL/g, total pore volume V Total (S) 2.4-6.4mL/g; preferably, the pore distribution of the alumina containing phosphorus and magnesium is located at a mesopore volume V of 3-100nm Middle hole 0.9-1.5mL/g, a macropore pore volume V with a pore distribution of 100-5000nm Macropores are formed 1.8-3.2mL/g, total pore volume V Total (S) 2.7-4.7mL/g.
3. The preparation method according to claim 1, wherein the pseudo-boehmite containing phosphorus and magnesium further contains optional auxiliary elements, wherein the auxiliary elements comprise metal auxiliary elements and/or non-metal auxiliary elements; the metal auxiliary element is at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium; the nonmetallic auxiliary agent element is selected from at least one of boron element, fluorine element and silicon element.
4. The production method according to claim 1, wherein the catalyst is produced by a hydrogen temperature-programmed reduction method (H 2 -TPR) at 300-500 DEG CPeak height P of low temperature reduction peak at Low temperature peak Peak height P with high temperature reduction peak at 650-850 deg.c High temperature peak Ratio s=p of (2) Low temperature peak /P High temperature peak 0.5-2.0; preferably, the peak height P of the low temperature reduction peak Low temperature peak Peak height P from high temperature reduction peak High temperature peak Ratio s=p of (2) Low temperature peak /P High temperature peak From 0.7 to 1.9, preferably from 0.8 to 1.8.
5. The production method according to claim 1, wherein the activation condition comprises: the temperature rising speed is 100-550 ℃/h, the temperature is 410-880 ℃, preferably 430-850 ℃, and most preferably 450-830 ℃;
the VIB metal component is Mo and/or W, and the VIII metal component is Co and/or Ni; the components are used in such amounts that the content of the group VIB metal component, calculated as oxides, is 5-45 wt.% and the content of the group VIII metal component is 1-15 wt.%, based on the total amount of the catalyst in the final catalyst.
6. The preparation method as claimed in claim 1, wherein the step of preparing pseudo-boehmite containing phosphorus and magnesium comprises the steps of:
(a) Contacting phosphorus-containing compound, magnesium-containing compound and inorganic aluminum-containing compound solution with acid or alkali to perform precipitation reaction, or contacting organic aluminum-containing compound with magnesium-containing compound and phosphorus-containing compound solution to perform hydrolysis reaction to obtain hydrated alumina containing phosphorus and magnesium;
(b) Aging the obtained hydrated alumina containing phosphorus and magnesium under the condition that the pH value is 7-10.5, and then drying the aged solid product to obtain pseudo-boehmite containing phosphorus and magnesium;
the precipitation reaction or the hydrolysis reaction of step (a) is carried out at a pH of 4 to 7.
7. The preparation method according to claim 6, wherein the precipitation reaction or the hydrolysis reaction of step (a) is performed at a pH of 4 to 6.5; the temperatures of the precipitation reaction and the hydrolysis reaction are each independently 30-90 ℃; the conditions of the precipitation reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 10-60 minutes, preferably 10-30 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 2-20 hours;
the inorganic aluminum-containing compound is aluminum salt and/or aluminate;
the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrated aluminum oxide precipitation through hydrolysis reaction with water;
the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate;
the magnesium-containing compound is one or more selected from magnesium chloride, magnesium nitrate, magnesium sulfate and magnesium acetate;
the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid;
the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.
8. The process of claim 6, wherein the aging of step (b) is performed at a pH of 8-10; the aging conditions include: the temperature is 50-95deg.C, preferably 55-90deg.C; the time is 0.5-8 hours, preferably 2-6 hours;
the drying conditions in step (b) include: the temperature is 50-350deg.C, preferably 80-250deg.C, and the drying time is 1-12 hr, preferably 2-8 hr.
9. The production method according to claim 6, wherein the precipitation reaction or the hydrolysis reaction in step (a) further comprises adding an optional auxiliary element-containing compound, the auxiliary element comprising a metal auxiliary element and/or a non-metal auxiliary element;
the metal auxiliary element is at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium, more preferably at least one of lithium, sodium, potassium, beryllium, calcium, zirconium and titanium;
the nonmetallic auxiliary agent element is at least one selected from boron element, fluorine element and silicon element;
the content of each component is such that the total dry weight of the pseudo-boehmite containing phosphorus and magnesium is taken as the reference, al 2 O 3 The content of P is 85-99.8 wt%, more preferably 85-99.7 wt% 2 O 5 The content of (2) is 0.1-5 wt.%, the content of MgO is 0.1-5 wt.%, the content of auxiliary elements is 0-5 wt.%, more preferably 0.1-5 wt.%.
10. A hydrogenation catalyst prepared by the process of any one of claims 1-9.
11. Use of the hydrogenation catalyst of claim 10 in a hydrocarbon oil hydrogenation reaction.
CN202111255180.4A 2021-10-27 2021-10-27 Preparation method of hydrogenation catalyst, catalyst prepared by method and application Pending CN116020498A (en)

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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002032570A2 (en) * 2000-10-19 2002-04-25 Shell Internationale Research Maatschappij B.V. Hydrodemetallation catalyst and method for making same
CN1803283A (en) * 2005-01-14 2006-07-19 中国石油化工股份有限公司 Hydrotreatment catalyst and its preparing method
CN101070488A (en) * 2006-05-13 2007-11-14 林方 Hydrogenation refining catalyst, preparing method and use
US20080081920A1 (en) * 2006-09-29 2008-04-03 Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg Catalyst with bimodal pore size distribution and the use thereof
CN102247882A (en) * 2010-05-20 2011-11-23 中国石油化工股份有限公司 Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst
CN103357417A (en) * 2012-03-31 2013-10-23 中国石油化工股份有限公司 Guard catalyst with hydrogenation activity as well as preparation and application thereof
CN103861607A (en) * 2012-12-12 2014-06-18 中国石油化工股份有限公司 Hydrogenation and asphaltene-removing catalyst, preparation and application thereof
CN103861602A (en) * 2012-12-12 2014-06-18 中国石油化工股份有限公司 Hydrogenation activity protection catalyst, preparation and application thereof
CN104226322A (en) * 2013-06-13 2014-12-24 中国石油化工股份有限公司 Heavy-oil hydrotreatment catalyst and preparation and application thereof
US20150266006A1 (en) * 2014-03-20 2015-09-24 IFP Energies Nouvelles Fischer-tropsch catalyst based on a metal of group viiib and an oxides support comprising alumina, silica, a spinel and phosphorus
US20170120229A1 (en) * 2014-06-13 2017-05-04 IFP Energies Nouvelles Active phase bimodal commixed catalyst, process for its preparation and use in hydrotreating residue
CN108187709A (en) * 2017-12-22 2018-06-22 洛阳金达石化有限责任公司 A kind of preparation method of deep hydrodesulfurizationof catalyst and the application of the catalyst
WO2018161952A1 (en) * 2017-03-09 2018-09-13 武汉凯迪工程技术研究总院有限公司 Method for preparing hydrotreating catalyst by impregnation method
CN110404552A (en) * 2018-04-27 2019-11-05 中国石油化工股份有限公司 A kind of hydrodenitrogenation catalyst and its application

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002032570A2 (en) * 2000-10-19 2002-04-25 Shell Internationale Research Maatschappij B.V. Hydrodemetallation catalyst and method for making same
CN1803283A (en) * 2005-01-14 2006-07-19 中国石油化工股份有限公司 Hydrotreatment catalyst and its preparing method
CN101070488A (en) * 2006-05-13 2007-11-14 林方 Hydrogenation refining catalyst, preparing method and use
US20080081920A1 (en) * 2006-09-29 2008-04-03 Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg Catalyst with bimodal pore size distribution and the use thereof
CN102247882A (en) * 2010-05-20 2011-11-23 中国石油化工股份有限公司 Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst
CN103357417A (en) * 2012-03-31 2013-10-23 中国石油化工股份有限公司 Guard catalyst with hydrogenation activity as well as preparation and application thereof
CN103861607A (en) * 2012-12-12 2014-06-18 中国石油化工股份有限公司 Hydrogenation and asphaltene-removing catalyst, preparation and application thereof
CN103861602A (en) * 2012-12-12 2014-06-18 中国石油化工股份有限公司 Hydrogenation activity protection catalyst, preparation and application thereof
CN104226322A (en) * 2013-06-13 2014-12-24 中国石油化工股份有限公司 Heavy-oil hydrotreatment catalyst and preparation and application thereof
US20150266006A1 (en) * 2014-03-20 2015-09-24 IFP Energies Nouvelles Fischer-tropsch catalyst based on a metal of group viiib and an oxides support comprising alumina, silica, a spinel and phosphorus
US20170120229A1 (en) * 2014-06-13 2017-05-04 IFP Energies Nouvelles Active phase bimodal commixed catalyst, process for its preparation and use in hydrotreating residue
WO2018161952A1 (en) * 2017-03-09 2018-09-13 武汉凯迪工程技术研究总院有限公司 Method for preparing hydrotreating catalyst by impregnation method
CN108187709A (en) * 2017-12-22 2018-06-22 洛阳金达石化有限责任公司 A kind of preparation method of deep hydrodesulfurizationof catalyst and the application of the catalyst
CN110404552A (en) * 2018-04-27 2019-11-05 中国石油化工股份有限公司 A kind of hydrodenitrogenation catalyst and its application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
唐国旗;张春富;孙长山;严斌;杨国祥;戴伟;田保亮;: "活性氧化铝载体的研究进展", 化工进展, no. 08, 5 August 2011 (2011-08-05) *
程昌瑞, 朱华青, 高志贤, 杜明仙, 翟效珍: "重油加氢脱氮催化剂的研制 Ⅱ.钼镍磷催化剂的制备与评价", 石油炼制与化工, no. 05, 18 May 1999 (1999-05-18) *

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