CN111822015B - Preparation method of hydrofining catalyst - Google Patents

Preparation method of hydrofining catalyst Download PDF

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CN111822015B
CN111822015B CN201910297418.6A CN201910297418A CN111822015B CN 111822015 B CN111822015 B CN 111822015B CN 201910297418 A CN201910297418 A CN 201910297418A CN 111822015 B CN111822015 B CN 111822015B
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mixed solution
catalyst
transition metal
aging
weight
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CN111822015A (en
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徐学军
王海涛
刘东香
王继锋
李娟�
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J35/393—
    • B01J35/394—
    • B01J35/615—
    • B01J35/633—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention discloses a preparation method of a hydrofining catalyst. The method comprises the following steps: (1) respectively preparing a mixed solution A and a mixed solution B containing transition metals; (2) adding the mixed solution A and the sodium metaaluminate alkaline solution into a reaction tank in a concurrent flow manner for gelling reaction to obtain slurry I, and aging; (3) adding the mixed solution B and the sodium metaaluminate alkaline solution into the aged slurry I in a concurrent flow manner to carry out gelling reaction to obtain slurry II, adding an organic phosphorus compound, and aging; (4) drying, molding and roasting the obtained material to obtain a phosphide catalyst precursor; (5) the obtained material is reduced by hydrogen programmed heating to obtain a hydrofining catalyst; wherein the organic assistant P1 is added in the step (2), and the organic assistant P2 is added in the step (3). The catalyst prepared by the method has small phosphide particles, more active centers, good dispersity and higher hydrodesulfurization and hydrodenitrogenation reaction performances, and is suitable for application in ultra-deep hydrodesulfurization and denitrogenation reactions of diesel fractions.

Description

Preparation method of hydrofining catalyst
Technical Field
The invention relates to a preparation method of a hydrofining catalyst, in particular to a preparation method of a phosphide hydrofining catalyst with high transition metal content.
Background
At present, crude oil is getting heavier and worse, and together with the continuous development of the world economy and the stricter environmental regulations, a large amount of light clean fuel needs to be produced. The development and use of ultra-low sulfur and even sulfur-free gasoline and diesel oil are the trend of the development of clean fuels worldwide nowadays. Sulfur-containing compounds with various structures and different molecular weights are contained in petroleum fractions, but in an ultra-deep desulfurization stage (the sulfur content is lower than 50 mu g/g), the sulfur-containing compounds with substituents such as 4, 6-dimethyldibenzothiophene and the like are mainly removed. Because the methyl group close to the sulfur atom generates steric hindrance between the sulfur atom and the active center of the catalyst, the sulfur atom is not easy to approach the active center of the reaction, thereby leading to the great reduction of the reaction rate.
The main method for solving the problems is to improve the existing catalyst; and the development of alternative novel catalysts is an effective way to solve the problem. Phosphide catalyst has been receiving great attention from researchers as a new hydrogenation catalyst due to its noble metal-like characteristics and excellent hydrogenation performance. Metal phosphides are a generic term for binary and multicomponent compounds of metals with phosphorus. Phosphorus can form various phosphides with most metals in the periodic table, and the formed chemical bonds are different. In the transition metal phosphide, metal atoms form the smallest structural units of a triangular prism structure, which form different lattice types in different combinations, and phosphorus atoms occupy the voids inside the triangular prism. Phosphide is a structure of triangular prism units, approximately spherical, and can expose more number of coordinately unsaturated surface atoms than sulfide, thereby having higher surface active site density.
The preparation methods of the transition metal phosphide are many, and the currently reported main synthesis methods are as follows: (1) directly combining metal and red phosphorus elementary substances at high temperature in a protective atmosphere; (2) solid displacement reaction of metal halide and phosphorus; (3) reaction of metal halides with phosphine; (4) decomposition of the organometallic compound; (5) electrolysis of molten salt; (6) reduction of metal phosphates, and the like. Of all these synthesis methods, the reduction method of metal phosphate is most applicable. Compared with other methods, the method has the characteristics of mild reaction conditions, cheap raw materials, less pollution to the environment and the like.
Under the condition of a distillate oil ultra-deep hydrodesulfurization reaction environment, organic nitrogen-containing compounds in the distillate oil generate an obvious inhibiting effect on the hydrodesulfurization reaction, and the hydrodesulfurization activity is reduced along with the increase of the nitrogen content in the raw material, because the nitrogen-containing compounds and sulfides in the distillate oil are subjected to competitive adsorption on the active sites of the catalyst, the nitride has strong adsorption capacity and occupies the active sites on the catalyst, the sulfides are difficult to approach, and the hydrodesulfurization reaction is inhibited, so when heavy diesel oil with high nitrogen content is treated to produce an ultra-low sulfur product, the catalyst needs to have excellent hydrodenitrogenation activity, the hydrodenitrogenation activity of the catalyst is improved, after the nitrogen content is reduced, the nitrides which are subjected to competitive adsorption with the sulfides are reduced, the sulfides are more easily and more adsorbed on the active sites of the catalyst, and the hydrodesulfurization reaction is promoted. Therefore, the improvement of the hydrodenitrogenation activity of the catalyst plays an extremely important role in improving the ultra-deep hydrodesulfurization activity of the phosphide catalyst.
The preparation method of the supported transition metal phosphide catalyst disclosed in CN1492025A comprises the steps of preparing a carrier from a composite of a mesoporous molecular sieve and a porous oxide; CN101168132A discloses a preparation method of a transition metal phosphide catalyst, which adds a proper amount of hydroxy acid as a chelating agent into an impregnation liquid. The method is to dip impregnation liquid containing various transition metal phosphide on a carrier, and the carrier-type transition metal phosphide is obtained through drying, roasting and programmed temperature reduction. Different methods are adopted in the preparation process to ensure that the active metal is more dispersedly distributed on the carrier. However, the transition metal phosphide obtained by the method has larger grain size and uneven distribution of active metal. CN101992109A discloses a transition metal phosphide hydrofining catalyst and a preparation method thereof, mesoporous carbon is taken as a carrier, one or more transition metal phosphate solutions of first transition metals (Fe, Co, Ni, W, Mo, Ru, Pd and Pt) are impregnated for loading, after drying and roasting, one or more metals or metal oxides of second transition metal elements (Ti, Ce, La, Y, Zn and Nb) are loaded by adopting an impregnation method, and then the final catalyst is obtained after drying, roasting and reduction. The method adopts secondary metal load to prepare the catalyst, so that the uneven distribution of active metal on the surface of the catalyst is easy to cause, and the preparation cost of the catalyst is increased by drying and roasting for many times in the preparation process. CN1660695 discloses a preparation method of transition metal phosphide, which is prepared by dissolving and mixing metal salt and diammonium hydrogen phosphate according to a certain proportion, drying, roasting, and carrying out temperature programming reduction and passivation under a certain oxygen concentration in a hydrogen atmosphere. The method adopts metal salt and diammonium hydrogen phosphate to prepare phosphide, easily generates aggregation of transition metal, and does not obviously improve the dispersion degree of the phosphide.
The phosphide prepared by adopting a load mode is influenced by a preparation mode, and the activity of the prepared catalyst is difficult to meet the requirement of ultra-deep hydrodesulfurization of diesel oil. The traditional supported catalyst is limited by the pore structure of the carrier, the loading of active metal is generally not more than 30wt%, and the supported phosphide catalyst can provide limited active centers, although the quantity and distribution of the active centers can be optimally adjusted, the limit bottleneck of the quantity of the active centers cannot be broken through. The bulk phase hydrofining catalyst prepared by adopting the coprecipitation method is not supported by a carrier, and the number of active centers can be greatly increased. The bulk phase hydrofining catalyst is mostly composed of active metal components, and although the method can get rid of the limitation of metal content, how to improve the comprehensive performance of the catalyst is still in the research and exploration stage.
CN106694004A discloses a transition metal phosphide catalyst and a preparation method thereof, the catalyst is prepared by a coprecipitation-temperature programming reduction method, and the precipitation mode is as follows: mixing Mg (NO) 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 A mixed solution of O and transition metal (Fe, Co and Ni) salts and a precipitant NaOH solution are slowly added dropwise to Na at the same time 2 HPO 4 In the solution, a precipitation reaction is carried out. The method directly carries out coprecipitation reaction on the metal solution, and is easy to cause local agglomeration of active metal, thereby influencing the performance of the catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrofining catalyst. The catalyst prepared by the method is a bulk phosphide catalyst with high content of transition metal, has larger specific surface area, small phosphide particles, more active centers, good dispersity and higher hydrodesulfurization and hydrodenitrogenation reaction performances, and is suitable for application in ultra-deep hydrodesulfurization and denitrogenation reactions of diesel fractions.
The invention provides a preparation method of a hydrofining catalyst, which comprises the following steps:
(1) preparing a mixed solution A containing transition metal, and preparing a mixed solution B containing transition metal;
(2) adding the mixed solution A and the sodium metaaluminate alkaline solution into a reaction tank in a cocurrent flow manner for gelling reaction to obtain slurry I, and aging the slurry I;
(3) adding the mixed solution B and the sodium metaaluminate alkaline solution into the aged slurry I in a cocurrent flow manner to perform a gelling reaction to obtain slurry II, adding an organic phosphorus compound into the slurry II, and then aging;
(4) Drying, molding and roasting the material obtained in the step (3) to obtain a phosphide catalyst precursor;
(5) carrying out programmed temperature rise reduction on the material obtained in the step (4) by using hydrogen to obtain a hydrofining catalyst;
wherein the organic assistant P1 is added in the step (2), and the organic assistant P2 is added in the step (3).
In the preparation method of the hydrofining catalyst, the organic auxiliary agent P1 in the step (2) is added into the reaction tank before the gelling reaction, namely the organic auxiliary agent P1 is added into the reaction tank before the mixed solution A and the sodium metaaluminate alkaline solution are added into the reaction tank in parallel. The organic assistant P2 added in step (3) can be added during the gelling reaction, i.e. can be added separately and concurrently with the mixed solution B and the sodium metaaluminate alkaline solution and/or added when preparing the mixed solution B, preferably added separately and concurrently with the mixed solution B and the sodium metaaluminate alkaline solution.
In the preparation method of the hydrorefining catalyst, the organic auxiliary agent P1 is a quaternary ammonium salt compound, the quaternary ammonium salt compound can be one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide or dodecyltrimethylammonium chloride, and the molar ratio of the added amount of the organic auxiliary agent P1 to the transition metal in the mixed solution A added in the step (1) is 0.2: 1-3: 1, preferably 0.3: 1-2.5: 1.
In the preparation method of the hydrofining catalyst, the organic auxiliary agent P2 is organic amine, and the organic amine can be one or more selected from hexamethylenetetramine, pyridine, aniline, benzylamine, methyldiethanolamine, N-methyldiethanolamine, ethanolamine, dimethylethanolamine, N-butylamine, cyclohexylamine, phenylethylamine, phenylpropanolamine, methyldiethanolamine, isobutylamine or sec-butylamine. The molar ratio of the added amount of the organic auxiliary agent P2 to the transition metal in the mixed solution B is 0.1-2.5, preferably 0.2-2.0.
In the step (1), the transition metal in the mixed solution A is Ni and/or W, and the transition metal in the mixed solution B is Ni or W.
The mixed solution A in the step (1) is an acid solution, wherein the weight concentration of Ni calculated as NiO is 5-110 g/L, preferably 10-90 g/L, and W is WO 3 The weight concentration is 10-80 g/L, preferably 12-70 g/L. The mixed solution B is an acidic solution, wherein the weight concentration of Ni calculated as NiO is 5-90 g/L, preferably 10-80 g/L, and W is WO 3 The weight concentration is 5-70 g/L, preferably 8-60 g/L. When preparing the mixed solution a and the mixed solution B, the commonly used nickel source may be one or more of nickel sulfate, nickel nitrate and nickel chloride, and the commonly used tungsten source is ammonium metatungstate.
The weight of the transition metal introduced by the mixed solution A in the step (2) accounts for 20-80%, preferably 25-75% of the weight of the transition metal in the hydrofining catalyst obtained in the step (5). The weight of the transition metal introduced by the mixed solution B in the step (3) accounts for 20-80%, preferably 25-75% of the weight of the transition metal in the hydrofining catalyst obtained in the step (5). The weight of Al in the precipitate slurry I accounts for 25-80%, preferably 30-75% of the weight of Al in the hydrofining catalyst obtained in the step (5).
In the step (2), the concentration of the sodium metaaluminate alkaline solution is Al 2 O 3 The amount is 3-80 g/L, preferably 5-60 g/L.
In the step (2), the reaction conditions for gelling are as follows: the reaction temperature is 20-90 ℃, preferably 30-70 ℃, the pH value is controlled to be 6.0-9.0, preferably 6.5-8.0, and the gelling time is 0.2-2.0 hours, preferably 0.3-1.5 hours.
In the step (3), the concentration of the sodium metaaluminate alkaline solution is Al 2 O 3 The amount is 2 to 60g/L, preferably 3 to 50 g/L.
In the step (3), the reaction conditions of the gelling reaction are as follows: the reaction temperature is 20-90 ℃, preferably 30-80 ℃, the pH value is controlled to be 7.5-10.0, preferably 7.8-9.5, and the gelling time is 1.5-4.0 hours, preferably 1.7-3.5 hours. The gelling reaction conditions in step (3) are at least 0.5 higher, preferably at least 1.0 higher, than the gelling reaction conditions in step (2).
In the step (2), the aging conditions are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the pH value during aging is controlled to be 6.0-8.0, preferably 6.5-7.5, and the aging time is 0.2-1.0 hour, preferably 0.3-0.8 hour. The aging is carried out under stirring, the preferred stirring conditions being as follows: the stirring speed is 100-300 rpm, preferably 150-250 rpm.
In the step (3), the aging conditions are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the pH value during aging is controlled to be 7.5-11.5, preferably 8.5-11.0, and the aging time is 1.5-6.0 hours, preferably 2.0-5.0 hours. The aging is carried out under stirring, the preferred stirring conditions being as follows: the stirring speed is 300-500 rpm, preferably 300-450 rpm. The pH of the aging of step (3) is at least 0.5 higher, preferably at least 1.0 higher than the pH of the aging of step (2).
The organophosphine compound in step (3) may be selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 2-hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid, polyaminopolyether methylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, preferably one or more of ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, polyaminopolyether methylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid. The molar ratio of the added amount of the organic phosphine compound to the transition metal in the hydrofining catalyst obtained in the step (5) is 0.8: 1-6.0: 1, preferably 1.5: 1-5.0: 1.
The drying, shaping and firing of step (4) may be carried out by methods conventional in the art. The drying conditions were as follows: drying at 40-250 deg.C for 1-48 hr, preferably at 50-200 deg.C for 4-36 hr. In the forming process, conventional forming aids, such as one or more of peptizers, extrusion aids, and the like, can be added as required. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, the extrusion aid is a substance which is beneficial to extrusion forming, such as one or more of sesbania powder, carbon black, graphite powder, citric acid and the like, and the amount of the extrusion aid accounts for 1-10 wt% of the total dry basis of the materials. The roasting conditions were as follows: roasting at 350-700 ℃ for 1-24 hours, preferably 400-650 ℃ for 2-12 hours.
The temperature programming reduction process adopted in the step (5) is that the hydrogen purity of the precursor is more than 99 v% in a hydrogen atmosphere. The hydrogen flow rate is 150-700 mL/min, preferably 250-600 mL/min, the heating rate is 3-10 ℃/min, the temperature is increased from room temperature to 300-550 ℃, the temperature is kept constant for 1-5 hours, then the temperature is increased to 600-750 ℃ at the heating rate of 0.5-5 ℃/min, the temperature is kept constant for 2-8 hours, and the heating rate of the second stage is at least 1 ℃/min lower than that of the first stage, preferably at least 2 ℃/min lower than that of the first stage.
In order to prevent the phosphide from contacting with air to generate severe oxidation reaction, before the prepared catalyst sample contacts with air, O with the oxygen volume concentration of 0.5-3 percent is firstly used 2 /N 2 Passivating with passivating gas for 1-5 hours.
In the process for preparing the hydrorefining catalyst of the present invention, the catalyst may be in the form of a sheet, a sphere, a cylinder or a shaped bar (clover ), preferably a cylinder or a shaped bar (clover ) as required. The catalyst may be in the form of fine strands of 0.8-2.0 mm diameter and coarse strands > 2.5mm diameter.
The hydrofining catalyst prepared by the method is a catalyst containing transition metal phosphide, and comprises transition metal phosphide and alumina, wherein the total content of the transition metal phosphide is 40% -95%, preferably 60% -90%, the content of the alumina is 5% -45%, preferably 10% -40%, the dispersity of the transition metal phosphide is 17% -42%, preferably 20% -38%, and the average particle diameter of the transition metal phosphide is 3-8 nm, preferably 3-7 nm, based on the weight of the catalyst.
The hydrofining catalyst is a bulk hydrofining catalyst.
The properties of the catalyst are as follows: the specific surface area is 150-600 m 2 A pore volume of 0.25 to 0.90mL/g,
The pore size distribution of the hydrofining catalyst is as follows: the pore volume of pores with the diameter of less than 3nm accounts for 2-18% of the total pore volume, the pore volume of pores with the diameter of 3-10 nm accounts for 15-55% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 13-40% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 3-15% of the total pore volume.
Wherein the transition metal phosphide is WP and Ni 2 P, i.e. when the catalyst is a bimetallic phosphide catalyst, the Ni/W molar ratio is 0.1: 1-10: 1, preferably 0.3: 1-8: 1.
the hydrofining catalyst is a bulk phase catalyst, has high content of transition metal, small phosphide particles, good dispersion and higher activity, reasonably adjusts the pore distribution of the catalyst, is particularly suitable for ultra-deep hydrodesulfurization and denitrification reactions of light distillate oil, and has higher hydrodesulfurization and hydrodenitrogenation activities.
The method for preparing the hydrofining catalyst of the invention comprises the steps of carrying out concurrent flow precipitation on a mixed solution A containing transition metal and an alkaline solution of sodium metaaluminate in the prior precipitation, carrying out primary aging, then adding a mixed solution B containing transition metal and an alkaline solution of sodium metaaluminate into the aged slurry in a concurrent flow manner, then deep aging is carried out to prepare a mixed precipitate of transition metal and aluminum, an organic phosphine compound is added during deep aging to increase the stability and the dispersibility of the aged slurry, can prevent the aggregation of active metal, control the growth of particles, ensure that the generated phosphide particles are smaller, improve the utilization rate of the active metal in the catalyst, simultaneously, take the organic phosphine compound as a phosphorus source, after being added during deep aging, the catalyst is uniformly distributed on the surface of the catalyst, so that not only can metal on the surface of the catalyst be fully phosphated, but also the accumulation of phosphorus can be reduced, and the generation of nickel phosphide and the physicochemical property of the catalyst are prevented from being influenced; the prepared hydrofining catalyst has high transition metal content, good phosphide dispersibility and small phosphide particle crystal grains, is particularly suitable for ultra-deep hydrodesulfurization and denitrification reactions of light distillate oil, and has higher hydrodesulfurization and hydrodenitrogenation activities.
In the method for preparing the hydrofining catalyst, the quaternary ammonium salt compound is added in the first step of reaction, so that the pore channel of the primarily aged precipitate is regular and smooth, and the organic amine is added in the second step of reaction, so that the final precipitate is more uniform in crystal grain, phosphide is more easily generated in the hydrogen high-temperature reduction process, and the granularity of the phosphide is smaller.
Detailed Description
In the invention, the specific surface area, the pore volume and the pore distribution are measured by adopting a low-temperature liquid nitrogen adsorption method, the dispersion degree of phosphide is measured by adopting probe molecule CO, the mechanical strength is measured by adopting a side pressure method, and the diameter of transition metal phosphide particles is measured by adopting a TEM technology. In the present invention, wt% is a mass fraction and v% is a volume fraction.
Example 1
Respectively adding nickel nitrate into a dissolving tank 1 filled with deionized water to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A is 55g/L in terms of NiO. Adding nickel nitrate into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein the weight concentration of Ni in the solution B is 55g/L in terms of NiO. And adding cetyl trimethyl ammonium bromide and deionized water into the reaction tank, wherein the molar ratio of the cetyl trimethyl ammonium bromide to the nickel in the mixed solution A is 1.8: 1, the weight concentration is Al 2 O 3 30g/L of sodium metaaluminate solution and the mixed solution A were fed concurrently into the reaction tank. The gelling temperature is kept at 55 ℃, the pH value is controlled at 7.6 in the process of parallel-flow gelling reaction, the gelling time is controlled at 0.8 hour, and slurry I is generated. Aging the obtained precipitate slurry I under stirring at a stirring speed of 220 rpm at an aging temperatureAging at 75 deg.C and pH 7.3 for 0.7 hr. After the aging is finished, the solution B, benzylamine and Al with weight concentration 2 O 3 And adding 18g/L of sodium metaaluminate solution into the slurry I in a concurrent flow manner, wherein the molar ratio of benzylamine to nickel in the mixed solution B is 1.8: 1, keeping the gelling temperature at 55 ℃, controlling the pH value at 9.0 in the process of parallel-flow gelling reaction, controlling the gelling time at 2.5 hours to obtain nickel and aluminum precipitate slurry II, adding ethylenediamine tetramethylene phosphonic acid into the precipitate slurry II, wherein the molar ratio of the ethylenediamine tetramethylene phosphonic acid to the transition metal in the finally prepared hydrofining catalyst is 4.6: 1, stirring at 420 r/min, aging at 75 deg.C, controlling pH at 9.2, aging for 3.7 hr, drying the obtained material at 130 deg.C for 14 hr, rolling, extruding to form strips, and calcining at 530 deg.C for 4 hr to obtain phosphide catalyst precursor A. And (3) heating the precursor A from room temperature to 420 ℃ under a hydrogen atmosphere at a hydrogen flow rate of 280mL/min and a heating rate of 5 ℃/min, keeping the temperature for 3.5 hours, heating to 700 ℃ at a heating rate of 2.5 ℃/min, and keeping the temperature for 4 hours. To prevent severe oxidation reaction of phosphide in contact with air, oxygen concentration of 1% by volume of O is used before the catalyst sample is contacted with air 2 /N 2 Passivating the passivation gas for 2 hours to obtain a hydrofining catalyst A, wherein the weight of nickel introduced by the mixed solution A accounts for 62% of the weight of nickel in the hydrofining catalyst A, the weight of Al in the precipitate I accounts for 52% of the weight of Al in the hydrofining catalyst A, and the catalyst composition and the main physicochemical properties are shown in Table 1.
Example 2
According to the method of example 1, the ammonium metatungstate is added into the dissolving tank 1 to prepare the mixed solution A according to the component content ratio of the catalyst B in the table 1, and the W in the mixed solution A is WO 3 The weight concentration was 30 g/L. Adding ammonium metatungstate into the dissolving tank 2 to prepare a mixed solution B, wherein W in the mixed solution B is WO 3 The weight concentration was 25 g/L. Adding tetraethylammonium hydroxide and deionized water into the reaction tank, wherein the molar ratio of the tetraethylammonium hydroxide to tungsten in the mixed solution A is 2.1: 1, the weight concentration is Al 2 O 3 28g/L sodium metaaluminate solution and the mixed solution A are added into the reaction in parallelIn a tank, the gelling temperature is kept at 52 ℃, the pH value is controlled at 7.4 in the parallel flow gelling reaction process, and the gelling time is controlled at 0.9 hour to generate slurry I. And ageing the obtained precipitate slurry I under stirring, wherein the stirring speed is 190 rpm, the ageing temperature is 74 ℃, the ageing pH value is controlled to be 7.1, and the ageing time is 0.6 hour. After the aging is finished, the solution B, ethanolamine and Al with the weight concentration 2 O 3 And (3) adding 15g/L of sodium metaaluminate solution into the slurry I in a concurrent flow mode, wherein the molar ratio of the ethanolamine to tungsten in the mixed solution B is 1.6: 1, keeping the gelling temperature at 58 ℃, controlling the pH value to be 9.4 in the process of cocurrent flow gelling reaction, controlling the gelling time to be 3.3 hours to obtain slurry II, adding diethylenetriamine pentamethylene phosphonic acid into the precipitate slurry II, wherein the molar ratio of the diethylenetriamine pentamethylene phosphonic acid to the transition metal in the finally prepared hydrofining catalyst is 4.5: 1, stirring at 405 rpm, ageing at 75 ℃, controlling the pH value at 9.7, ageing for 4.2 hours, drying the obtained material at 120 ℃ for 16 hours, rolling, extruding and forming. After molding, the mixture is roasted for 6 hours at 520 ℃ to obtain a phosphide catalyst precursor B. And (3) heating the precursor B from room temperature to 460 ℃ at the hydrogen flow rate of 380ml/min and the heating rate of 6.2 ℃/min under the hydrogen atmosphere, keeping the temperature for 4.0 hours, heating to 690 ℃ at the heating rate of 3.5 ℃/min, and keeping the temperature for 5 hours. To prevent severe oxidation reaction of phosphide in contact with air, oxygen concentration of 1.15% by volume of O was used before the catalyst sample was contacted with air 2 /N 2 Passivating the passivation gas for 2 hours to obtain a hydrofining catalyst B, wherein the weight of tungsten introduced by the mixed solution A accounts for 59% of the weight of tungsten in the hydrofining catalyst B, the weight of Al in the precipitate I accounts for 55% of the weight of Al in the hydrofining catalyst B, and the catalyst composition and the main physicochemical properties are shown in Table 1.
Example 3
According to the component content proportion of the catalyst C in the table 1, nickel nitrate and ammonium metatungstate are added into a dissolving tank 1 to prepare a mixed solution A, the weight concentration of Ni in the mixed solution A is 23.4g/L in terms of NiO, and W in the mixed solution A is WO 3 The weight concentration is 20 g/L. Nickel nitrate is added into the dissolving tank 2 to prepare a mixed solution B, and the weight concentration of Ni in the mixed solution B calculated by NiO is28 g/L. Adding tetrapropylammonium bromide and deionized water into a reaction tank, wherein the total molar ratio of the tetrapropylammonium bromide to tungsten and nickel in the mixed solution A is 1.5: 1, weight concentration is Al 2 O 3 And (3) adding 30g/L of sodium metaaluminate solution and the mixed solution A into a reaction tank in a concurrent flow manner, keeping the gelling temperature at 53 ℃, controlling the pH value at 7.5 in the concurrent flow gelling reaction process, and controlling the gelling time at 1.3 hours to generate precipitate slurry I. Aging the obtained precipitate slurry I under stirring at 215 rpm, at 72 deg.C and pH 7.1 for 0.4 hr. After the aging is finished, the solution B, phenethylamine and Al with weight concentration 2 O 3 And adding 24g/L sodium metaaluminate solution into the slurry I in a concurrent flow mode, wherein the molar ratio of phenylethylamine to nickel in the mixed solution B is 1.3: 1, keeping the gelling temperature at 52 ℃, controlling the pH value at 8.7 in the process of parallel-flow gelling reaction, controlling the gelling time at 2.7 hours to obtain precipitate slurry II, adding hexamethylenediamine tetramethylene phosphonic acid into the precipitate slurry II, wherein the molar ratio of the hexamethylenediamine tetramethylene phosphonic acid to the transition metal in the finally prepared hydrofining catalyst is 4.0: 1, stirring at 380 r/min, ageing at 75 deg.C, controlling pH at 9.1, ageing for 4.6 hr, drying at 160 deg.C for 10 hr, rolling, extruding to form. After molding, the mixture was calcined at 490 ℃ for 6 hours to obtain a phosphide catalyst precursor C. And (3) heating the precursor C from room temperature to 510 ℃ under a hydrogen atmosphere at a hydrogen flow rate of 450mL/min and a heating rate of 5.8 ℃/min, keeping the temperature for 5 hours, heating to 710 ℃ at a heating rate of 3.2 ℃/min, and keeping the temperature for 6 hours. To prevent severe oxidation reaction of phosphide in contact with air, oxygen concentration of 1.1% by volume of O was used before the catalyst sample was contacted with air 2 /N 2 Passivating the passivation gas for 4 hours to obtain a hydrofining catalyst C, wherein the weight of nickel and tungsten introduced by the mixed solution A accounts for 55% of the weight of the nickel and tungsten in the hydrofining catalyst C, the weight of Al in the precipitate I accounts for 62% of the weight of Al in the hydrofining catalyst C, and the catalyst composition and the main physicochemical properties are shown in Table 1.
Example 4
According to the component content proportion of the catalyst D in the table 1, adding the mixture into a dissolving tank1 adding ammonium metatungstate into the mixed solution A to prepare a mixed solution A, wherein W in the mixed solution A is WO 3 The weight concentration is 20 g/L. Nickel nitrate is added into the dissolving tank 2 to prepare a mixed solution B, and the weight concentration of Ni in the mixed solution B is 33g/L in terms of NiO. Adding tetrabutylammonium hydroxide and deionized water into a reaction tank, wherein the molar ratio of the tetrabutylammonium hydroxide to tungsten in the mixed solution A is 1.9:1, and the weight concentration of Al 2 O 3 Adding 28g/L sodium metaaluminate solution and the mixed solution A into a reaction tank in parallel, keeping the gelling temperature at 58 ℃, controlling the pH value at 7.3 in the process of parallel-flow gelling reaction, and controlling the gelling time at 0.9 h to generate precipitate slurry I. And ageing the obtained precipitate slurry I under stirring, wherein the stirring speed is 235 rpm, the ageing temperature is 75 ℃, the ageing pH value is controlled at 7.0, and the ageing time is 0.6 hour. After aging is finished, the weight concentration of the solution B and the phenylpropanolamine is Al 2 O 3 Adding 16g/L sodium metaaluminate solution into the slurry I in a parallel flow mode, wherein the molar ratio of phenylpropanolamine to nickel in the mixed solution B is 1.2:1, the gelling temperature is kept at 48 ℃, the pH value in the process of the parallel flow gelling reaction is controlled at 9.3, the gelling time is controlled at 2.5 hours, so as to obtain precipitate slurry II, adding polyamino polyether methylene phosphonic acid into the precipitate slurry II, and the molar ratio of the polyamino polyether methylene phosphonic acid to transition metals in the finally prepared hydrofining catalyst is 4.3: 1, stirring at 430 rpm, aging at 75 deg.C, controlling pH at 9.9, aging for 3.9 hr, drying at 130 deg.C for 15 hr, rolling, extruding to form. After molding, the mixture is roasted for 4 hours at 560 ℃ to obtain a phosphide catalyst precursor D. And (3) heating the precursor D from room temperature to 480 ℃ under a hydrogen atmosphere at a hydrogen flow rate of 360ml/min and a heating rate of 5.3 ℃/min, keeping the temperature for 3.9 hours, then heating to 705 ℃ at a heating rate of 2.9 ℃/min, and keeping the temperature for 5.2 hours. To prevent severe oxidation reaction of phosphide in contact with air, oxygen concentration of 1.2% by volume of O is used before the catalyst sample is contacted with air 2 /N 2 Passivating the passivation gas for 3 hours to obtain a hydrofining catalyst D, wherein the weight of tungsten introduced by the mixed solution A accounts for 42.6 percent of the weight of nickel and tungsten in the hydrofining catalyst D, and the weight of Al in the precipitate I accounts for the hydrofining catalyst D 57% by weight of Al in the catalyst D, the catalyst composition and the main physicochemical properties are shown in Table 1.
Comparative example 1
According to the catalyst composition of example 1, nickel nitrate and diammonium hydrogen phosphate are dissolved in deionized water to prepare a mixed solution, wherein the weight concentration of Ni in NiO is 55g/L, and the element molar ratio of nickel to phosphorus in the mixed solution is 1: 4. adding 500mL of deionized water into a reaction tank, and adding Al according to the weight concentration 2 O 3 And (3) adding the 30g/L sodium metaaluminate solution and the mixed solution into a reaction tank in a concurrent flow manner for gelatinizing, wherein the gelatinizing temperature is kept at 55 ℃, the pH value is controlled at 7.6 in the gelatinizing process, and the gelatinizing time is controlled at 1.0 hour to generate slurry. And then aging for 2.0 hours at 75 ℃ and controlling the pH value at 7.8 during aging to obtain a material, drying for 14 hours at 130 ℃, rolling, extruding and molding, and roasting for 4 hours at 530 ℃ to obtain a phosphide catalyst precursor E. And (3) heating the precursor E from room temperature to 420 ℃ under a hydrogen atmosphere at a hydrogen flow rate of 280ml/min and a heating rate of 5 ℃/min, keeping the temperature for 3.5 hours, heating to 700 ℃ at a heating rate of 2.5 ℃/min, and keeping the temperature for 4 hours. To prevent severe oxidation reaction of phosphide in contact with air, oxygen concentration of 1% by volume of O is used before the catalyst sample is contacted with air 2 /N 2 Passivating the reaction product with passivating gas for 2 hours to obtain phosphide catalyst E. The catalyst composition and the main physicochemical properties are shown in table 1.
Comparative example 2
According to the catalyst composition of example 1, nickel nitrate and diammonium phosphate are dissolved in deionized water to prepare a mixed solution, wherein the weight concentration of Ni in NiO is 55 g/L. The molar ratio of the elements of nickel and phosphorus in the mixed solution is 1: 4. adding the mixed solution into a reaction tank, and adding Al in a weight concentration 2 O 3 And dripping 30g/L sodium metaaluminate solution into a reaction tank for gelling, keeping the gelling temperature at 55 ℃, controlling the pH value at 7.6 when gelling is finished, and controlling the gelling time at 1.0 hour to generate slurry. Aging at 75 deg.C for 2.0 hr to obtain a material, drying at 130 deg.C for 14 hr, rolling, extruding, and calcining at 530 deg.C for 4 hr to obtain the final productTo phosphide procatalyst F. And (3) heating the precursor F from room temperature to 420 ℃ at the hydrogen flow rate of 280mL/min and the heating rate of 5 ℃/min under the hydrogen atmosphere, keeping the temperature for 3.5 hours, heating to 700 ℃ at the heating rate of 2.5 ℃/min, and keeping the temperature for 4 hours. To prevent severe oxidation reaction of phosphide in contact with air, oxygen concentration of 1% by volume of O is used before the catalyst sample is contacted with air 2 /N 2 Passivating the reaction product with passivating gas for 2 hours to obtain phosphide catalyst F. The catalyst composition and the main physicochemical properties are shown in table 1.
Example 5
This example is an evaluation experiment of the activity of the catalyst of the present invention and is compared with the catalyst of the comparative example. A comparative evaluation test was conducted on a 200mL compact hydrogenation apparatus using the A, B, C, D catalyst of the present invention and the E, F catalyst of comparative example, respectively. The experimental procedure was as follows: 60mL of hydrofining catalyst and 340mL of quartz sand are uniformly mixed and then are filled in a small fixed bed reactor. Introducing hydrogen into the catalyst before reaction, heating to 660 ℃ at the speed of 10 ℃/min, and keeping for 40 minutes to remove a surface passivation layer to obtain a fresh hydrofining catalyst. Catalyst activity evaluation process conditions: the hydrogen partial pressure is 6.4MPa, the reaction temperature is 360 ℃, and the liquid hourly space velocity is 1.8h -1 The hydrogen-oil volume ratio was 500:1, and the evaluation results are shown in Table 3. The types of sulfide and nitride in the hydrorefined oil were measured by a gas chromatography-atomic emission spectrometry detector (GC-AED), and the results are shown in tables 4 and 5.
As seen from the evaluation results in tables 2 to 5, the catalyst of the present invention has excellent hydrodenitrogenation activity, and after the dispersion degree of the phosphide catalyst is increased, the catalyst shows high hydrogenation activity when removing 1, 8-DMCB and 1, 4, 8-TMCB macromolecular nitrides, which is beneficial to improving the hydrodesulfurization activity of the catalyst. The catalyst of the invention is used for processing and treating light distillate oil, particularly for processing inferior diesel oil fraction with high nitrogen content and high processing difficulty, has excellent ultra-deep hydrodesulfurization and denitrification performance, and improves the cetane number of the diesel oil.
TABLE 1 compositions and Properties of catalysts prepared in examples and comparative examples
Catalyst numbering A B C D E F
Ni 2 P，wt% 69 - 53 39 69 69
WP，wt% - 67 18 29 - -
Al 2 O 3 ，wt% Balance of Balance of Balance of Balance of Balance of Balance of
Specific surface area, m 2 /g 282 276 273 271 201 209
Pore volume, mL/g 0.405 0.388 0.383 0.380 0.292 0.298
Hole distribution,%
＜3nm 6.18 6.74 6.98 7.17 38.17 40.18
3nm~10nm 44.87 45.45 45.54 45.95 40.28 39.74
10nm~15nm 38.75 38.21 37.68 37.42 13.02 12.85
＞15nm 10.20 9.60 9.80 9.46 8.53 7.23
Degree of dispersion of transition metal phosphide,% 27.8 27.2 27.5 27.3 12.2 11.9
Average diameter of transition metal phosphide particlesDiameter, nm 5.3 5.4 5.3 5.5 18.2 20.1
TABLE 2 Primary Properties of the base oils
Item Analysis results
Density (20 ℃ C.), g/cm 3 0.8728
Range of distillation range, deg.C 167-376
S，µg/g 14120
N，µg/g 629
Cetane number 46.9
TABLE 3 evaluation results of catalyst Activity
Catalyst numbering A B C D E F
Density of the resulting oil (20 ℃ C.), g/cm 3 0.8604 0.8605 0.8607 0.8606 0.8686 0.8684
Range of distillation range, deg.C 157-368 159-368 160-369 158-369 165-373 164-374
S，µg/g 7.4 7.6 7.8 7.9 219.3 208.7
N，µg/g 6.3 6.6 6.5 6.8 63.4 59.3
TABLE 4 content of different sulfides in hydrorefined oils
Catalyst numbering A B C D E F
Sulphur content in hydrofined oil, microgram/g 7.4 7.6 7.8 7.9 219.3 208.7
C 1 -DBT，µg/g 0 0 0 0 38.9 35.9
4-MDBT，µg/g 1.6 1.7 1.6 1.5 50.4 48.7
6-MDBT，µg/g 1.8 1.8 1.9 2.0 59.1 57.1
4，6-DMDBT，µg/g 4.0 4.1 4.3 4.4 70.9 67.0
TABLE 5 content of different nitrides in hydrorefined oils
Catalyst numbering A B C D E F
Nitrogen content in hydrofined oil, mug/g 6.3 6.6 6.5 6.8 63.4 59.3
1- MCB，µg/g 1.6 1.6 1.5 1.7 25.6 24.3
1，8-DMCB，µg/g 1.6 1.7 1.6 1.6 25.3 23.7
1，4，8-TMCB，µg/g 3.1 3.3 3.4 3.5 12.5 11.3
Note: the main nitrogen-containing compounds difficult to remove by hydrogenation and denitrification are Carbazole (CB), 1-methylcarbazole (1-MCB), 1, 8-dimethylcarbazole (1, 8-DMCB), 1, 4, 8-trimethylcarbazole (1, 4, 8-TMCB) and the like which have larger molecules and steric hindrance.

Claims (37)

1. A preparation method of a hydrofining catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a mixed solution A containing transition metal, and preparing a mixed solution B containing transition metal;
(2) Adding the mixed solution A and the sodium metaaluminate alkaline solution into a reaction tank in a cocurrent flow manner for gelling reaction to obtain slurry I, and aging the slurry I;
(3) adding the mixed solution B and the sodium metaaluminate alkaline solution into the aged slurry I in a cocurrent flow manner to perform a gelling reaction to obtain slurry II, adding an organic phosphine compound into the slurry II, and then aging;
(4) drying, molding and roasting the material obtained in the step (3) to obtain a phosphide catalyst precursor;
(5) carrying out programmed temperature rise reduction on the material obtained in the step (4) by using hydrogen to obtain a hydrofining catalyst;
wherein the organic assistant P1 is added in the step (2), and the organic assistant P2 is added in the step (3);
the organic auxiliary agent P1 is a quaternary ammonium salt compound, and the quaternary ammonium salt compound is selected from one or more of tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, hexadecyltrimethylammonium bromide or dodecyltrimethylammonium chloride; the organic auxiliary agent P2 is organic amine, and the organic amine is selected from one or more of hexamethylenetetramine, pyridine, aniline, benzylamine, methyldiethanolamine, N-methyldiethanolamine, ethanolamine, dimethylethanolamine, N-butylamine, cyclohexylamine, phenethylamine, phenylpropanolamine, isobutylamine or sec-butylamine.
2. The method of claim 1, wherein: in the step (2), the organic assistant P1 is added into a reaction tank before gelling reaction, namely the organic assistant P1 is added into the reaction tank before the mixed solution A and the sodium metaaluminate alkaline solution are added into the reaction tank in parallel; adding the organic assistant P2 in the step (3) during the gelling reaction, namely adding the organic assistant P2 into the mixed solution B and the sodium metaaluminate alkaline solution independently in parallel flow and/or adding the organic assistant P2 into the mixed solution B during the preparation of the mixed solution B.
3. The method of claim 2, wherein: and (3) adding an organic assistant P2, the mixed solution B and the sodium metaaluminate alkaline solution into the mixture separately in parallel.
4. The method of claim 1, wherein: the molar ratio of the added amount of the organic auxiliary agent P1 to the transition metal in the mixed solution A added in the step (1) is 0.2: 1-3: 1.
5. the method of claim 4, wherein: the molar ratio of the added amount of the organic auxiliary agent P1 to the transition metal in the mixed solution A added in the step (1) is 0.3: 1-2.5: 1.
6. the method of claim 1, wherein: the molar ratio of the added amount of the organic auxiliary agent P2 to the transition metal in the mixed solution B is 0.1-2.5.
7. The method of claim 6, wherein: the molar ratio of the added amount of the organic auxiliary agent P2 to the transition metal in the mixed solution B is 0.2-2.0.
8. The method of claim 1, wherein: in the step (1), the transition metal in the mixed solution A is Ni and/or W, and the transition metal in the mixed solution B is Ni or W.
9. The method of claim 8, wherein: the mixed solution A in the step (1) is an acid solution, wherein the weight concentration of Ni in NiO is 5-110 g/L, and the weight concentration of W in WO 3 The calculated weight concentration is 10-80 g/L; the mixed solution B is an acid solution, wherein the weight concentration of Ni in NiO is 5-90 g/L, and the weight concentration of W in WO 3 The calculated weight concentration is 5-70 g/L; when preparing the mixed solution A and the mixed solution B, the adopted nickel source is one or more of nickel sulfate, nickel nitrate and nickel chloride, and the adopted tungsten source is ammonium metatungstate.
10. The method of claim 9, wherein: the mixed solution A in the step (1) is an acid solution, wherein the weight concentration of Ni in NiO is 10-90 g/L, and the weight concentration of W in WO 3 The calculated weight concentration is 12-70 g/L; the mixed solution B is an acid solution, wherein the weight concentration of Ni in NiO is 10-80 g/L, and the weight concentration of W in WO 3 The weight concentration is 8-60 g/L.
11. The method of claim 1, wherein: in the step (2), the weight of the transition metal introduced by the mixed solution A accounts for 20-80% of the weight of the transition metal in the hydrofining catalyst obtained in the step (5); in the step (3), the weight of the transition metal introduced by the mixed solution B accounts for 20-80% of the weight of the transition metal in the hydrofining catalyst obtained in the step (5); and (3) the weight of Al in the precipitate slurry I accounts for 25-80% of the weight of Al in the hydrofining catalyst obtained in the step (5).
12. The method of claim 11, wherein: in the step (2), the weight of the transition metal introduced by the mixed solution A accounts for 25-75% of the weight of the transition metal in the hydrofining catalyst obtained in the step (5); in the step (3), the weight of the transition metal introduced by the mixed solution B accounts for 25-75% of the weight of the transition metal in the hydrofining catalyst obtained in the step (5); the weight of Al in the precipitate slurry I accounts for 30-75% of the weight of Al in the hydrofining catalyst obtained in the step (5).
13. The method of claim 1, wherein: in the step (2), the concentration of the sodium metaaluminate alkaline solution is Al 2 O 3 The weight is 3-80 g/L; in the step (3), the concentration of the sodium metaaluminate alkaline solution is Al 2 O 3 The amount is 2-60 g/L.
14. The method of claim 13, wherein: in the step (2), the concentration of the sodium metaaluminate alkaline solution is Al 2 O 3 5-60 g/L; in the step (3), the concentration of the sodium metaaluminate alkaline solution is Al 2 O 3 The amount is 3-50 g/L.
15. The method of claim 1, wherein: in the step (2), the reaction conditions for gelling are as follows: the reaction temperature is 20-90 ℃, the pH value is controlled to be 6.0-9.0, and the gelling time is 0.2-2.0 hours; in the step (3), the reaction conditions of the gelling reaction are as follows: the reaction temperature is 20-90 ℃, the pH value is controlled to be 7.5-10.0, and the gelling time is 1.5-4.0 hours.
16. The method of claim 15, wherein: in the step (2), the reaction conditions for gelling are as follows: the reaction temperature is 30-70 ℃, the pH value is controlled to be 6.5-8.0, and the gelling time is 0.3-1.5 hours; in the step (3), the reaction conditions of the gelling reaction are as follows: the reaction temperature is 30-80 ℃, the pH value is controlled to be 7.8-9.5, and the gelling time is 1.7-3.5 hours.
17. The method of claim 15, wherein: the gelling reaction conditions in step (3) are higher than the gelling reaction conditions in step (2) by at least 0.5 of the pH value.
18. The method of claim 17, wherein: the gelling reaction conditions in step (3) are higher than the gelling reaction conditions in step (2) by at least 1.0.
19. The method of claim 1, wherein: in the step (2), the aging conditions are as follows: the aging temperature is 40-90 ℃, the pH value during aging is controlled to be 6.0-8.0, and the aging time is 0.2-1.0 hour; the aging is carried out under stirring, and the stirring speed is 100-300 r/min.
20. The method of claim 19, wherein: in the step (2), the aging conditions are as follows: the aging temperature is 50-80 ℃, the pH value during aging is controlled to be 6.5-7.5, and the aging time is 0.3-0.8 hours; the stirring speed is 150-250 rpm.
21. The method of claim 1, wherein: in the step (3), the aging conditions are as follows: the aging temperature is 40-90 ℃, the pH value during aging is controlled to be 7.5-11.5, and the aging time is 1.5-6.0 hours; aging is carried out under stirring, and the stirring speed is 300-500 rpm; the aged pH of step (3) is at least 0.5 higher than the aged pH of step (2).
22. The method of claim 21, wherein: in the step (3), the aging conditions are as follows: the aging temperature is 50-80 ℃, the pH value during aging is controlled to be 8.5-11.0, and the aging time is 2.0-5.0 hours; the stirring speed is 300-450 rpm; the aged pH of step (3) is at least 1.0 higher than the aged pH of step (2).
23. The method of claim 1, wherein: in the step (3), the organophosphine compound is selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 2-hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid, polyaminopolyether methylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acid.
24. The method of claim 23, wherein: in the step (3), the organic phosphine compound is selected from one or more of ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, polyaminopolyether methylene phosphonic acid and hexamethylenediamine tetramethylene phosphonic acid.
25. The method of claim 1, wherein: the molar ratio of the added amount of the organic phosphine compound to the transition metal in the hydrofining catalyst obtained in the step (5) is 0.8: 1-6.0: 1.
26. the method of claim 25, wherein: the molar ratio of the added amount of the organic phosphine compound to the transition metal in the hydrofining catalyst obtained in the step (5) is 1.5: 1-5.0: 1.
27. The method of claim 1, wherein: the drying conditions in the step (4) are as follows: drying for 1-48 hours at 40-250 ℃; the roasting conditions were as follows: roasting at 350-700 ℃ for 1-24 hours.
28. The method of claim 27, wherein: the drying conditions in the step (4) are as follows: drying for 4-36 hours at 50-200 ℃; the roasting conditions were as follows: roasting at 400-650 ℃ for 2-12 hours.
29. The method of claim 1, wherein: in the temperature programming reduction process in the step (5), the purity of hydrogen of the precursor is more than 99 v% in a hydrogen atmosphere; the hydrogen flow rate is 150-700 mL/min, the heating rate is 3-10 ℃/min, the temperature is increased from room temperature to 300-550 ℃, the temperature is kept constant for 1-5 hours, then the temperature is increased to 600-750 ℃ at the heating rate of 0.5-5 ℃/min, the temperature is kept constant for 2-8 hours, and the heating rate of the second stage is at least 1 ℃/min lower than that of the first stage.
30. The method of claim 29, wherein: the hydrogen flow rate is 250-600 mL/min; the temperature rise rate in the second stage is at least 2 ℃/min lower than that in the first stage.
31. A hydrorefining catalyst characterized by: the catalyst is prepared by the process of any one of claims 1-30.
32. The catalyst of claim 31, wherein: the catalyst is a transition metal phosphide-containing catalyst, the catalyst comprises transition metal phosphide and alumina, the total content of the transition metal phosphide is 40% -95%, the content of the alumina is 5% -45%, the dispersion degree of the transition metal phosphide is 17% -42%, and the average particle diameter of the transition metal phosphide is 3-8 nm.
33. The catalyst of claim 32, wherein: based on the weight of the catalyst, the total content of the transition metal phosphide is 60-90%, the content of the alumina is 10-40%, the dispersion degree of the transition metal phosphide is 20-38%, and the average particle diameter of the transition metal phosphide is 3-7 nm.
34. The catalyst of claim 31, wherein: the specific surface area of the catalyst is 150-600 m 2 The pore volume is 0.25 to 0.90 mL/g.
35. The catalyst of claim 31, wherein: the pore size distribution of the hydrofining catalyst is as follows: the pore volume of pores with the diameter of less than 3nm accounts for 2-18% of the total pore volume, the pore volume of pores with the diameter of 3-10 nm accounts for 15-55% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 13-40% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 3-15% of the total pore volume.
36. The catalyst of claim 32, wherein: the transition metal phosphide is WP and Ni 2 P, Ni/W molar ratio of 0.1: 1-10: 1.
37. the catalyst of claim 36, wherein: the molar ratio of Ni/W is 0.3: 1-8: 1.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106179386A (en) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 The preparation method of Hydrobon catalyst
CN106179381A (en) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 The preparation method of Hydrobon catalyst
CN108067246A (en) * 2016-11-16 2018-05-25 中国石油天然气股份有限公司 A kind of preparation method of body phase hydrogenation catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106179386A (en) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 The preparation method of Hydrobon catalyst
CN106179381A (en) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 The preparation method of Hydrobon catalyst
CN108067246A (en) * 2016-11-16 2018-05-25 中国石油天然气股份有限公司 A kind of preparation method of body phase hydrogenation catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Effect of ZrO2 in Ni2P/ZrO2–Al2O3 catalysts on hydrotreating reactions;Junen Wang, et al.;《RSC Advances》;20150825;第5卷;第74312-74319页 *

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