CN110038597B - Preparation method of hydrofining catalyst - Google Patents

Preparation method of hydrofining catalyst Download PDF

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CN110038597B
CN110038597B CN201810037435.1A CN201810037435A CN110038597B CN 110038597 B CN110038597 B CN 110038597B CN 201810037435 A CN201810037435 A CN 201810037435A CN 110038597 B CN110038597 B CN 110038597B
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catalyst
mixed solution
aging
acid
weight
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CN110038597A (en
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王海涛
徐学军
王继锋
刘东香
冯小萍
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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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a hydrofining catalyst. The hydrofining catalyst is prepared by the steps of adding a mixed solution A containing Ni and W, an organic assistant and a sodium metaaluminate alkaline solution into a reaction tank in a concurrent flow manner for gelling reaction, adding an organic template agent before gelling reaction, aging the obtained slurry, adding a mixed solution B containing W, Mo and Al and ammonia water into the aged slurry in a concurrent flow manner, aging, drying, forming and the like. The catalyst can be applied to ultra-deep hydrodesulfurization and denitrification reactions of diesel fractions, has higher hydrodesulfurization and hydrodenitrification reaction activities, and is particularly used for treating diesel raw materials with high nitrogen and high sulfur contents.

Description

Preparation method of hydrofining catalyst
Technical Field
The invention relates to a preparation method of a hydrogenation catalyst, in particular to a preparation method of a bulk phase hydrofining catalyst.
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. The traditional hydrodesulfurization catalyst can also realize deep desulfurization and even ultra-deep desulfurization of diesel by increasing the reaction severity, such as increasing the reaction temperature, hydrogen partial pressure or reducing the reaction space velocity, but the increase of the reaction temperature can cause the color of the product to be deteriorated and the service life of the catalyst to be shortened, and the reduction of the space velocity means the reduction of the treatment capacity. For the existing hydrogenation device, the design pressure is fixed, and the amplitude of increasing the hydrogen partial pressure is limited. Therefore, it is currently one of the important means of deep desulfurization by employing a catalyst having higher desulfurization activity.
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 traditional supported hydrogenation catalyst is limited by a carrier pore structure, the loading capacity of active metal is generally not more than 30wt%, the number of active centers which can be provided by the supported catalyst is limited, although the number and the type distribution of the active centers can be optimized and adjusted, the limit bottleneck of the number of the active centers can not be broken through, the space for greatly improving the hydrogenation activity is limited, and the requirement of a refinery on diesel oil products in the producing country V is difficult to meet. The hydrogenation catalyst prepared by the bulk phase method is mainly composed of active metal components, so that the limitation of metal content can be eliminated, the proportion of each active component in the catalyst can be adjusted at will, the hydrogenation performance of the catalyst is improved, the bulk phase catalyst has excellent hydrogenation activity, sulfur-free diesel oil products meeting national V standards can be directly produced under the condition of not improving the reaction severity of the device, the original device does not need to be modified, the treatment capacity of the device can be improved, the production cost of a refinery is reduced, and energy conservation and efficiency improvement are realized.
Bulk hydrogenation catalysts are divided into sulfided bulk hydrogenation catalysts and oxidic bulk hydrogenation catalysts. The oxidation state bulk phase catalyst is prepared by a coprecipitation method mainly by taking active metal components, which are usually VIB group metal elements (Mo and W) and VIII group metal elements (Ni), wherein active metal atoms are staggered with each other to provide a reaction space for reactant molecules, and the active metal is exposed on the surface of the catalyst to provide a reaction activity center for the reactant molecules. The supported catalyst is formed by mixing a lower activity type active center and a higher activity type active center, and the bulk phase catalysis is carried outThe active centers of the catalyst are basically all the two types of active centers, and the bulk phase catalyst greatly improves the catalytic activity of the catalyst mainly by increasing the density of the active centers on the catalyst. Chianelli et al proposed a spoke-edge model to explain the generation of unsupported catalyst active centers, which model models MoS2/WS2The active sites at the edges of the outer layers of the grains are called the spoke sites, provide hydrogenation centers and convert MoS2/WS2The edge active sites of the inner layers of the grains are called edge sites and provide hydrogenolysis centers. Thus, the hydrogenation and hydrogenolysis activities of the catalyst are closely related to the distribution of active sites.
In the reaction process, reactant molecules only react on the surface of the catalyst close to the reactant molecules, active metal on the surface of the catalyst prepared by the existing coprecipitation method is not uniformly dispersed, and meanwhile, the disordered distribution of different hydrogenation active metals causes no good coordination effect among the active metals, so that high-content metal in the bulk phase catalyst is easy to excessively stack metal particles, the generation of an active phase is reduced, the active metal cannot become a hydrogenation active center, the utilization rate of the active metal of the catalyst is influenced, and the use cost of the catalyst is also improved.
CN1951561A discloses a method for preparing a hydrogenation catalyst by coprecipitation, wherein the catalyst adopts active metal Ni, W components and a precipitator for cocurrent coprecipitation to generate NixWyOzThe composite oxide precursor may be added with aluminum salt solution or colloid, added with aluminum hydroxide and mixed with MoO3Pulping, mixing, filtering, shaping and activating to obtain the final catalyst. In the process of preparing bulk catalyst by the method, molybdenum oxide and NixWyOzThe composite oxide is directly pulped and mixed, so that the active metal is excessively accumulated, the number of active phases is reduced, and the utilization rate of the active metal is reduced.
CN201410062726.8 discloses a preparation method of a non-supported high-activity hydrogenation catalyst. The method comprises the steps of firstly preparing an acidic solution A containing at least one VIII group metal compound and at least one VIB group metal compound and an alkaline solution B containing at least one silicon source or aluminum source, slowly mixing the two solutions, putting the two solutions into a precipitation reactor, carrying out coprecipitation reaction at the temperature of 20-120 ℃ and the pH value of 7-12 to obtain slurry, and carrying out aging, suction filtration, washing, drying, molding and roasting on the slurry to obtain the catalyst. The method does not adopt a conventional alkaline precipitant, but adopts an alkaline solution B containing a silicon source or an aluminum source as the precipitant, changes the precipitant, but does not change the active metal dispersibility of a bulk phase catalyst, does not obviously increase the number of active phases, and does not improve the utilization rate of metals.
The bulk phase hydrogenation catalyst disclosed in CN102049265A is added with ammonium bicarbonate during the coprecipitation process, the bulk phase hydrogenation catalyst disclosed in CN102451703A is added with carbon dioxide during the coprecipitation process to generate carbonate or bicarbonate, and the methods utilize a certain amount of gas released during the roasting process to increase the pore volume and the specific surface area of the catalyst under the impact of the gas. Although part of the metal active sites are exposed on the surface of the catalyst while expanding pores under the impact of gas, the catalyst pores are easy to collapse under the action of gas, so that the effect of improving the dispersibility of the active metal is limited.
CN201510212110.9 discloses a bulk phase hydrofining catalyst and a preparation method thereof. The method comprises the steps of preparing a nickel-aluminum mixed precipitate by a positive addition method, preparing a tungsten, molybdenum and aluminum mixed precipitate by a cocurrent flow precipitation method, mixing the nickel and aluminum mixed precipitate, aging and filtering to obtain a metal mixture, carrying out steam treatment on the metal mixture under proper conditions, adding urea, drying, forming and roasting the material after the hydrothermal treatment to obtain the catalyst. The bulk phase catalyst obtained by the method has high content of surface phase active metal, and is easy to excessively stack, so that the appearance and the dispersity of an active phase stack layer are influenced.
In the existing coprecipitation method bulk phase catalyst preparation technology, different precipitation modes and gelling conditions can have great influence on the matching mode of the active metals of the catalyst, the distribution of the hydrogenation active metals and the interaction relationship among different hydrogenation active metals, and MoS in the vulcanized bulk phase catalyst can also be caused2/WS2The appearance of (A) is obviously different.
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 phase hydrofining catalyst, has more effective active phases, stronger promotion function among the active phases and higher hydrodesulfurization and hydrodenitrogenation reaction performances, is suitable for application in ultra-deep hydrodesulfurization and denitrogenation reactions of diesel fractions, and is particularly used for treating diesel raw materials with high nitrogen and high sulfur content.
Under the condition of the ultra-deep hydrodesulfurization reaction of the distillate oil, the organic nitrogen-containing compounds in the distillate oil have obvious inhibiting effect on the hydrodesulfurization reaction, the hydrodesulfurization activity is reduced along with the increase of the nitrogen content in the raw material, the reason is that the nitrogen-containing compound and the sulfur-containing compound in the distillate oil are competitively adsorbed on the active site of the catalyst, the nitrogen-containing compound has stronger adsorption capacity and occupies the active site on the catalyst, so that the sulfur-containing compound is difficult to approach, the hydrodesulfurization reaction is inhibited, therefore, when the heavy diesel oil with high nitrogen content is treated to produce ultra-low sulfur products, the catalyst needs to have excellent hydrodenitrogenation activity, the hydrodenitrogenation activity of the catalyst is improved, and after the nitrogen content is reduced, the nitrogen-containing compounds which are competitively adsorbed with the sulfur-containing compounds are reduced, and the sulfur-containing compounds are more easily and more adsorbed on the active sites of the catalyst, thereby promoting the hydrodesulfurization reaction. Therefore, improving the hydrodenitrogenation activity of the catalyst plays an extremely important role in improving the ultra-deep hydrodesulfurization activity of the bulk catalyst.
The preparation method of the hydrofining catalyst provided by the invention comprises the following steps:
(1) preparing a mixed solution A containing Ni and W components, and preparing a mixed solution B containing W, Mo and Al components;
(2) adding the mixed solution A, the organic assistant and the sodium metaaluminate alkaline solution into a reaction tank in a concurrent flow manner to carry out gelling reaction to generate precipitate slurry I containing nickel, aluminum and tungsten, and aging the obtained slurry I;
(3) adding the mixed solution B and ammonia water into the aged slurry I in a cocurrent flow manner to perform a gelling reaction to generate precipitate slurry II containing nickel, molybdenum, tungsten and aluminum, and then aging;
(4) drying, forming and washing the material obtained in the step (3), and then drying and roasting to obtain a hydrofining catalyst;
wherein, an organic template agent is added before the gelling reaction in the step (2).
In the step (2), the organic auxiliary agent is a carboxylic acid polymer and/or an organic phosphonic acid. The molecular weight of the carboxylic acid polymer is 400-5000, the carboxylic acid polymer is selected from one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyepoxysuccinic acid, acrylic acid-hydroxypropyl acrylate copolymer and maleic acid-acrylic acid copolymer, and preferably one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid and polyepoxysuccinic acid. The organic phosphonic acid may be selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylene diphosphonic acid, polyol phosphonates, polyaminopolyether methylene phosphonic acid, 1,2, 4-tricarboxylic acid-2-phosphonobutane, hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, preferably from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylene diphosphonic acid, aminotrimethylene phosphonic acid. The molar ratio of the added amount of the organic auxiliary agent to W in the mixed solution A is 0.8: 1-3: 1, preferably 1: 1-2.5: 1.
and (3) adding an organic template agent before the gel forming reaction in the step (2), wherein the organic template agent is added into the reaction tank before the reaction, namely before the mixed solution A, the organic auxiliary agent and the sodium metaaluminate alkaline solution are added into the reaction tank in a concurrent flow manner.
The organic template in the step (2) is quaternary ammonium salt template, preferably one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide and dodecyltrimethylammonium chloride.
The molar ratio of the added amount of the organic template agent to W in the mixed solution A added in the step (2) is 0.3: 1-5: 1, preferably 0.5: 1-4: 1.
in the step (2), the organic auxiliary agent may be added separately in parallel, or may be added during the preparation of the mixed solution a, or may be added in combination of the above two ways.
The mixed solution A in the step (1) is an acid solution, wherein the weight concentration of Ni calculated as NiO is 5-100 g/L, preferably 10-80 g/L, and W is WO3The weight concentration is 2-60 g/L, preferably 10-50 g/L. The mixed solution B is an acid solution, wherein W is WO3The weight concentration is 2-70 g/L, preferably 4-60 g/L, Mo is MoO3The weight concentration is 5-80 g/L, preferably 10-60 g/L, Al is Al2O3The weight concentration is 2-60 g/L, preferably 5-40 g/L. When preparing the mixed solution A, the commonly adopted nickel source can be one or more of nickel sulfate, nickel nitrate and nickel chloride; the tungsten source generally employed is ammonium metatungstate. When preparing the mixed solution B, the tungsten source generally used is ammonium metatungstate, the molybdenum source is ammonium molybdate, and the aluminum source may be one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, and the like.
The weight of W introduced by the mixed solution A in the step (2) accounts for 40-80%, preferably 51-75% of the weight of W in the hydrofining catalyst obtained in the step (4). In the step (3), the weight of W introduced through the mixed solution B accounts for 20-60%, preferably 25-49% of the weight of W in the hydrofining catalyst obtained in the step (4), and the weight of Al introduced through the mixed solution B accounts for 15-60%, preferably 25-49% of the weight of Al in the hydrofining catalyst obtained in the step (4).
The concentration of the sodium metaaluminate alkaline solution in the step (2) is Al2O3The amount is 5 to 80g/L, preferably 10 to 60 g/L. In the step (2), the reaction temperature for gelling is 20-90 ℃, preferably 30-70 ℃, the pH value is controlled to be 6.0-10.0, preferably 7.0-9.0, and the gelling time is 0.2-2.0 hours, preferably 0.3-1.5 hours.
The weight concentration of the ammonia water in the step (3) is 5-15%.
And (3) adding the mixed solution B and ammonia water into the aged slurry I in a cocurrent manner to perform gelling reaction under the following reaction conditions: the reaction temperature is 20-90 ℃, preferably 30-80 ℃, the pH value is controlled to be 6.0-11.0, preferably 6.5-9.0, and the gelling time is 0.5-4.0 hours, preferably 1.0-3.0 hours.
The aging conditions in step (2) 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 0.1-1.0 hour, preferably 0.2-0.8 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.
The aging conditions in step (3) are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the pH value during aging is controlled to be 7.5-11.0, preferably 7.5-9.5, 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 drying, shaping and washing of step (4) may be carried out by methods conventional in the art. The drying conditions before molding were as follows: drying at 40-250 ℃ for 1-48 hours, preferably at 50-180 ℃ for 4-36 hours. 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 washing is generally carried out by washing with deionized water or a solution containing decomposable salts (such as ammonium acetate, ammonium chloride, ammonium nitrate, etc.) until the solution is neutral.
After the molding in the step (4), the drying and baking may be performed by using the conditions conventional in the art, and the drying conditions are as follows: drying for 1-48 hours at 40-250 ℃, wherein the roasting conditions are as follows: roasting at 350-650 ℃ for 1-24 hours, preferably drying under the following conditions: drying for 4-36 hours at 50-180 ℃, wherein the roasting conditions are as follows: roasting at 400-600 ℃ for 2-12 hours.
In the hydrofining catalyst of the present invention, the preferred auxiliary component is Ti and/or Zr. In the production of the hydrorefining catalyst of the present invention, it is preferable to add a compound containing an auxiliary component, i.e., a titanium source and/or a zirconium source, during the production of the mixed solution a. The titanium source may be one or more of titanium nitrate, titanium sulfate, titanium chloride, etc., and the zirconium source may be one or more of zirconium nitrate, zirconium chloride, zirconium oxychloride, etc.
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 obtained in the step (4) of the invention is an oxidation state bulk hydrofining catalyst, and can be vulcanized by a conventional method before use. The sulfidation is the conversion of the active metal W, Ni and Mo oxide to the corresponding sulfide. The vulcanization method can adopt wet vulcanization or dry vulcanization. The sulfurization method adopted in the invention is wet sulfurization, the sulfurization agent is a sulfur-containing substance used in conventional sulfurization, can be an organic sulfur-containing substance, and can also be an inorganic sulfur-containing substance, such as one or more of sulfur, carbon disulfide, dimethyl disulfide and the like, the sulfurized oil is hydrocarbon and/or distillate oil, wherein the hydrocarbon is one or more of cyclohexane, cyclopentane, cycloheptane and the like, and the distillate oil is one or more of kerosene, common first-line diesel oil, common second-line diesel oil and the like. The dosage of the vulcanizing agent is that the vulcanization degree of each active metal in the hydrofining catalyst is not less than 80%, and can be adjusted according to the actual situation, and the dosage of the vulcanizing agent can be 80-200%, preferably 100-150% of the theoretical sulfur demand of each active metal in the hydrofining catalyst for complete vulcanization. The prevulcanization conditions are as follows: the temperature is 230-370 ℃, the hydrogen pressure is 2.0-10 MPa, and the liquid hourly space velocity is 0.3-6.0 h-1The vulcanization time is 3-24 h, and the preferable selection is as follows: the temperature is 250-350 ℃, the hydrogen pressure is 3.0-8.0 MPa, and the liquid hourly space velocity is 1.0-3.0 h-1And the vulcanization time is 5-16 h.
In the vulcanization, active metal components W, Ni and oxides of Mo are converted into corresponding sulfides, and the vulcanized hydrofining catalyst is obtained; the sulfuration degree of each active metal in the catalyst is not less than 80%.
The hydrofining catalyst prepared by the method takes the weight of the hydrofining catalyst as a reference, NiO and WO3And MoO3The total content of the alumina is 40-95%, preferably 50-85%, and the content of the alumina is 5-60%, preferably 15-50%.
In the hydrofining catalyst prepared by the method, the molar ratio of W/Mo is 1: 10-8: 1, preferably 1: 8-5: 1, the molar ratio of Ni/(Mo + W) is 1: 12-12: 1, preferably 1: 8-8: 1.
the hydrofining catalyst prepared by the method of the invention is a bulk hydrofining catalyst, and the composition of the hydrofining catalyst comprises a hydrogenation active metal component WO3NiO and MoO3And alumina, after sulfidation, MoS2/WS2The average number of stacked layers of (2) is 6.0 to 9.0 layers, preferably 6.5 to 9.0 layers, MoS2/WS2The average wafer length of the wafer is 4.0 to 6.5nm, preferably 4.5 to 6.0 nm.
The pore size distribution of the hydrofining catalyst prepared by the method of the invention is as follows: the pore volume of pores with the diameter of less than 3nm accounts for 5-30% of the total pore volume, the pore volume of pores with the diameter of 3-10 nm accounts for 50-80% of the total pore volume, the pore volume of pores with the diameter of 10-15 nm accounts for 7-25% of the total pore volume, and the pore volume of pores with the diameter of more than 15nm accounts for 5-20% of the total pore volume.
The hydrogenation refining catalyst prepared by the method of the invention is sulfurized and then MoS2/WS2The number of stacked layers is distributed as follows: the average stacking layer number is 6.0-9.0 layers, preferably 6.5-9.0 layers, and the number of the laminated layers with 7.0-9.0 accounts for 55-85% of the total laminated layers, preferably 61-80%; the average length of the lamella is 4.0-6.5 nm, preferably 4.5-6.0 nm, and the number of the lamella with the lamella length of 4.0-6.0 nm accounts for 55.0% -85.0%, preferably 65.0% -80.0% of the total number of the lamellae.
The hydrogenation refining catalyst prepared by the method of the invention is sulfurized and then MoS2/WS2The distribution of the number of stacked layers is specifically as follows: the number of the layers less than 4.0 accounts for the total number of the layers1-8%, the number of the sheets with the number of layers of 4.0-7.0 accounts for 3-20% of the total number of the sheets, the number of the sheets with the number of layers of 7.0-9.0 accounts for 55-85% of the total number of the sheets, and the number of the sheets with the number of layers more than 9.0 accounts for 5-20% of the total number of the sheets.
The hydrogenation refining catalyst prepared by the method of the invention is sulfurized and then MoS2/WS2The lamella length distribution is specifically as follows: the number of the lamella with the length of less than 2.0nm accounts for 1.0-12.0% of the total number of the lamellae, the number of the lamella with the length of 2.0-4.0 nm accounts for 5.0-25.0% of the total number of the lamellae, the number of the lamella with the length of 4.0-6.0 nm accounts for 55.0-85.0% of the total number of the lamellae, the number of the lamella with the length of more than 6.0-8.0 nm accounts for 3.0-15.0% of the total number of the lamellae, and the number of the lamella with the length of more than 8.0nm accounts for 0.2-4.0% of the total number of the lamellae.
The hydrorefining catalyst prepared by the method has the following properties: the specific surface area is 180-500 m2The pore volume is 0.20-0.80 mL/g.
The hydrofining catalyst prepared by the method of the invention can contain an auxiliary component according to requirements, the auxiliary component is titanium and/or zirconium, and the weight content of the auxiliary component in the hydrofining catalyst calculated by element is less than 20%, preferably less than 15%.
In the hydrofining catalyst prepared by the method of the invention, MoS2/WS2The stacking is high in layer number and small in length, particularly the stacking is concentrated on 6.0-9.0 layers, the length of each layer is 4.0-6.5 nm, more effective active phases are generated, the promotion effect between the layers is stronger, the activity is higher, meanwhile, the pore distribution is proper, the mechanical strength is high, the hydrodesulfurization and hydrodenitrogenation reaction performances are higher, and the method is suitable for being applied to ultra-deep hydrodesulfurization and denitrogenation reactions of diesel fractions, especially for treating diesel raw materials with high nitrogen content.
The method for preparing hydrofining catalyst of the invention is characterized by that the previous precipitation is implemented under the condition of using partial W and Ni in sodium metaaluminate alkaline solution as aluminium source and precipitant and adding organic adjuvant and organic template agent, the active metal and organic adjuvant are chelated to form macromolecular network complex compound, so that the granules of precipitate containing W, Ni and Al after first primary ageing are large and regular in arrangement, and have a certain anchoring action for the hydrogenation active metal which is subsequently precipitated, and the active metal which is subsequently precipitated is larger in sizeAmmonia water is used as precipitant, so that the post-precipitation process is more uniform and mild, different hydrogenation active metals are orderly precipitated in the catalyst, the growth speed of metal oxide particles and the probability of mutual contact between the active metals are controlled, and WO3And MoO3The product has proper particle size and well-controlled distribution, and increases MoS in the vulcanized bulk catalyst2/WS2The stacking layer number, the lamella length are reduced, the morphology of the active phase is optimized, more effective active phases are generated, the mutual promotion effect is stronger, and the activity is higher. Meanwhile, the addition of the organic template agent leads the pore channel of the catalyst to be regular and smooth, the method also leads the catalyst to form a more suitable pore structure, the pore distribution is reasonable, and the specific surface area and the pore volume of the catalyst are improved.
The catalyst is particularly suitable for ultra-deep hydrodesulfurization and denitrification reactions of light distillate oil, has higher hydrodesulfurization and hydrodenitrogenation activities, and particularly has higher hydrodenitrogenation and desulfurization activities when processing heavy diesel oil with high nitrogen and high sulfur content. The sulfur content in the heavy diesel fraction is 1000-20000 mug/g, wherein the sulfur content in thiophene and derivatives thereof accounts for 60-85 wt% of the total sulfur content of the raw material, the nitrogen content is 200-2000 mug/g, and the nitrogen content in carbazole and derivatives thereof accounts for 60-80 wt% of the total nitrogen content of the raw material.
Detailed Description
In the present invention, the specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method, and the mechanical strength is measured by a side pressure method. In the present invention, MoS in bulk catalyst2/WS2The number of stacked layers and the length of the lamella are measured by a transmission electron microscope, wherein in the case of the W-Ni-Mo catalyst, after being vulcanized, the active phase MoS can form the stacked layers2And WS2In the invention, MoS is used2/WS2Formally representing the active phase. The hydrofining catalyst is vulcanized, namely a non-vulcanized hydrofining catalyst is vulcanized into a vulcanized hydrofining catalyst, namely a vulcanized hydrofining catalyst.
In the present invention, wt% is a mass fraction and v% is a volume fraction. In the invention, the degree of vulcanization is measured by an X-ray photoelectron spectrometer (XPS), and the percentage of the content of the active metal in a vulcanized state in the total content of the active metal is the degree of vulcanization of the active metal.
Example 1
Respectively adding nickel chloride and ammonium metatungstate into a dissolving tank 1 filled with deionized water, adding 54 g of ethylenediamine tetramethylenephosphonic acid and 123 g of polyaspartic acid (molecular weight is 3000) to prepare a mixed solution A, wherein the weight concentration of Ni in the mixed solution A is 28g/L calculated by NiO, and W is WO3The weight concentration was 27 g/L. Respectively adding ammonium metatungstate, ammonium molybdate and aluminum chloride into a dissolving tank 2 filled with deionized water to prepare a mixed solution B, wherein W in the mixed solution B is WO3The weight concentration is 30g/L, Mo is MoO3The weight concentration is 36g/L, Al is Al2O3The weight concentration is 26 g/L. Adding 20 g of tetraethylammonium bromide and deionized water into a reaction tank, and adding Al in a weight concentration2O3And (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 60 ℃, controlling the pH value at 7.8 in the concurrent flow gelling reaction process, and controlling the gelling time at 60 minutes to generate precipitate slurry I containing nickel, tungsten and aluminum. And ageing the obtained precipitate slurry I under stirring, wherein the stirring speed is 170 rpm, the ageing temperature is 75 ℃, the ageing pH value is controlled to be 7.2, and the ageing time is 0.6 hour. After ageing, adding the mixed solution B and 10wt% ammonia water into the slurry I in a cocurrent manner, keeping the gelling temperature at 63 ℃, controlling the pH value to be 7.8 in the cocurrent gelling reaction process, controlling the gelling time to be 2.0 hours, obtaining nickel, tungsten, molybdenum and aluminum precipitate slurry II, ageing the precipitate slurry II under the stirring condition, controlling the stirring speed to be 440 r/min, the ageing temperature to be 75 ℃, controlling the pH value to be 8.4, ageing for 3.0 hours, filtering the aged slurry, drying a filter cake at 120 ℃ for 8 hours, rolling, extruding and forming. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst A. The catalyst composition, pore distribution and main properties are shown in table 1.
Example 2
The method according to example 1, as per the table1, adding a nickel chloride solution, an ammonium metatungstate solution and a zirconium oxychloride solution into a dissolving tank 1, adding 286 g of polyacrylic acid (with the molecular weight of 3000) to prepare a mixed solution A, and adding ammonium metatungstate, ammonium molybdate and aluminum nitrate into a dissolving tank 2 to prepare a mixed solution B. 25 grams of tetraethylammonium hydroxide and deionized water were added to the reaction tank, the weight concentration being Al2O3Adding 42g/L sodium metaaluminate solution and the mixed solution A into a reaction tank in parallel, keeping the gelling temperature at 55 ℃, controlling the pH value at 7.8 in the process of parallel-flow gelling reaction, and controlling the gelling time at 1.2 hours to generate precipitate slurry I containing nickel, tungsten, aluminum and zirconium. 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 at 6.6, and the ageing time is 0.5 hour. After ageing, adding ammonia water with the weight concentration of 8wt% and the mixed solution B into the slurry I in a cocurrent manner, keeping the gelling temperature at 45 ℃, controlling the pH value to be 7.8 in the cocurrent gelling reaction process, controlling the gelling time to be 2.2 hours, obtaining nickel, tungsten, molybdenum, aluminum and zirconium precipitate slurry II after the reaction is finished, aging the precipitate slurry II under the stirring condition, wherein the stirring speed is 430 revolutions per minute, the aging time is 4.0 hours, the aging temperature is 80 ℃, and the aging pH value is controlled to be 7.9. Filtering the aged slurry, drying the filter cake at 110 ℃ for 10 hours, extruding into strips for forming, washing with deionized water for 6 times, drying wet strips at 90 ℃ for 12 hours, and roasting at 510 ℃ for 5 hours to obtain the final catalyst B, wherein the composition, pore distribution and main properties are shown in Table 1.
Example 3
According to the method of example 1, nickel nitrate, an ammonium metatungstate solution, 42g of hydroxyethylidene diphosphonic acid, and 26g of polymaleic acid (molecular weight 450) were added to a dissolution tank 1 in accordance with the component content ratio of catalyst C in table 1 to prepare a mixed solution a, and ammonium metatungstate, ammonium molybdate, and aluminum chloride were added to a dissolution tank 2 to prepare a mixed solution B. 22 g of tetrapropylammonium bromide are added into a reaction tank, and the weight concentration is Al2O3Adding 39g/L sodium metaaluminate solution and mixed solution A into a reaction tank in parallel, keeping the gelling temperature at 50 ℃, controlling the pH value at 7.8 in the process of parallel-flow gelling reaction, and controlling the gelling time at 1.0 hThen, the slurry I containing nickel, tungsten and aluminum precipitates is generated. And ageing the obtained precipitate slurry I under stirring, wherein the stirring speed is 200 rpm, the ageing temperature is 75 ℃, the ageing pH value is controlled at 7.0, and the ageing time is 0.7 hour. After ageing, adding ammonia water with the weight concentration of 12wt% and the mixed solution B into the slurry I in a cocurrent manner, keeping the gelling temperature at 55 ℃, controlling the pH value to be 7.8 in the cocurrent gelling reaction process, controlling the gelling time to be 2.0 hours, obtaining nickel, tungsten, molybdenum and aluminum precipitate slurry II after the reaction is finished, aging the precipitate slurry II under the stirring condition, wherein the stirring speed is 410 r/min, the aging time is 4.2 hours, the aging temperature is 78 ℃, and the aging pH value is controlled to be 8.3. Filtering the aged slurry, drying the filter cake at 90 ℃ for 15 hours, extruding into strips for forming, washing with water for 5 times, drying wet strips at 120 ℃ for 8 hours, and roasting at 550 ℃ for 4 hours to obtain the final catalyst C, wherein the composition, pore distribution and main properties are shown in Table 1.
Example 4
According to the method of example 1, nickel chloride, ammonium metatungstate, and 68 g of polymaleic acid (molecular weight 450) were added to a dissolution tank 1 to prepare a mixed solution a, and ammonium metatungstate, ammonium molybdate, and aluminum chloride were added to a dissolution tank 2 to prepare a mixed solution B, in accordance with the component content ratio of the catalyst D in table 1. 41 g of cetyltrimethylammonium bromide and deionized water were added to a reaction tank, the weight concentration being Al2O3And (3) adding 44g/L of sodium metaaluminate solution and the mixed solution A into a reaction tank in parallel, keeping the gelling temperature at 55 ℃, controlling the pH value at 7.6 in the process of parallel-flow gelling reaction, and controlling the gelling time at 0.9 hour to generate nickel, tungsten and aluminum containing precipitate slurry I. And aging the obtained precipitate slurry I under stirring at the stirring speed of 170 rpm, the aging temperature of 78 ℃, the aging pH value of 7.1 and the aging time of 0.6 hour. After ageing, adding an ammonia water solution with the weight concentration of 12wt% and a mixed solution B into the slurry I in a concurrent flow mode, keeping the gelling temperature at 50 ℃, controlling the pH value to be 8.1 in the concurrent flow gelling reaction process, controlling the gelling time to be 2.4 hours, obtaining a nickel, tungsten, molybdenum and aluminum precipitate slurry II after the reaction is finished, ageing the precipitate slurry II under stirring at the stirring speed of 430 revolutions per minute for 4.4 hours, controlling the ageing temperature to be 77 ℃ and the ageing pH value to be at8.4. Filtering the aged slurry, drying the filter cake at 95 ℃ for 10 hours, extruding into strips for forming, washing with deionized water for 6 times, drying wet strips at 80 ℃ for 13 hours, and roasting at 570 ℃ for 4 hours to obtain the final catalyst D, wherein the composition, pore distribution and main properties are shown in Table 1.
Comparative example 1
Reference E, having the same composition as the catalyst of example 1, was prepared according to the method disclosed in CN1951561A, by the following procedure:
according to the catalyst composition of example 1, nickel chloride and ammonium metatungstate are prepared and dissolved in deionized water to prepare a mixed solution, wherein the weight concentration of Ni calculated as NiO is 28g/L, and W calculated as WO is3The weight concentration is 46g/L, Al is Al2O3The weight concentration was 38 g/L. Adding 500mL of deionized water into a reaction tank, adding 10wt% ammonia water and the mixed solution into the reaction tank in parallel for gelling, keeping the gelling temperature at 60 ℃, controlling the pH value at 7.8 when gelling is finished, and controlling the gelling time at 3.0 hours to generate nickel-tungsten-containing precipitate slurry. And then aging for 3.8 hours at 75 ℃, controlling the pH value at 7.8 during aging, filtering, adding deionized water, aluminum hydroxide and molybdenum trioxide into a filter cake, pulping, uniformly mixing, filtering, drying the filter cake for 8 hours at 120 ℃, rolling, extruding and forming. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst E. The catalyst composition, pore distribution and main properties are shown in table 1.
Comparative example 2
According to the catalyst composition of example 1, aluminum chloride, nickel chloride, ammonium molybdate and ammonium metatungstate are prepared and dissolved in deionized water to prepare a mixed solution, wherein the weight concentration of Ni calculated as NiO is 28g/L, and W calculated as WO is3The weight concentration is 46g/L, Mo is MoO3The weight concentration is 27g/L, Al is Al2O3The weight concentration was 38 g/L. And (3) adding ammonia water with the concentration of 10wt% and the mixed solution into a reaction tank in a concurrent flow manner to carry out gelling, wherein the gelling temperature is kept at 60 ℃, the pH value is controlled at 7.8 when gelling is finished, and the gelling time is controlled at 3.0 hours, so that precipitate slurry containing tungsten, nickel, molybdenum and aluminum is generated. Then, the mixture is fed to a reactorAging at 75 deg.C for 3.8 hr, controlling pH at 8.0, filtering, drying at 120 deg.C for 8 hr, rolling, extruding to obtain strip, and shaping. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst F. The catalyst composition, pore distribution and main properties are shown in table 1.
Comparative example 3
Reference G, having the same composition as the catalyst of example 1, was prepared according to the catalyst preparation method disclosed in CN 201510212110.9. Adding aluminum chloride and nickel chloride solution into the dissolving tank 1 to prepare working solution A, wherein the weight concentration of Ni in the mixed solution A is 28g/L in terms of NiO, and Al is Al2O3The weight concentration was 19 g/L. Adding aluminum chloride, ammonium metatungstate and ammonium molybdate into the dissolving tank 2 to prepare a working solution B, and mixing W in the solution B with WO3The weight concentration is 30g/L, Mo is MoO3The weight concentration is 36g/L, Al is Al2O3The weight concentration is 26 g/L. Adding 10wt% ammonia water into the solution A under stirring, keeping the gelling temperature at 60 ℃, controlling the pH value at 7.8 when the gelling is finished, and controlling the gelling time at 50 minutes to generate nickel-aluminum-containing precipitate slurry I. Adding 500mL of deionized water into a reaction tank, adding 10wt% ammonia water and the solution B into the reaction tank in a cocurrent manner, keeping the gelling temperature at 60 ℃, controlling the pH value to be 7.8 in the cocurrent gelling reaction process, and controlling the gelling time to be 2.0 hours to generate precipitate slurry II containing tungsten, molybdenum and aluminum. Mixing the two types of slurry containing the precipitate, aging for 3.8 hours at 75 ℃, controlling the pH value at 7.8 after aging, then filtering, and carrying out hydrothermal treatment on a filter cake under the water vapor containing urea, wherein the hydrothermal treatment conditions are as follows: the mol ratio of the total amount of the urea and the active metal atoms is 3:1, the temperature is 230 ℃, the pressure is 3.5MPa, the processing time is 4 hours, the materials after the hydro-thermal treatment are dried for 8 hours at the temperature of 120 ℃, rolled and extruded into strips for forming. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst G. The catalyst composition, pore distribution and main properties are shown in table 1.
Comparative example 4
Reference H, having the same composition as the catalyst of example 1, was prepared according to the catalyst preparation method disclosed in CN 102049265A. Adding aluminum chloride, nickel chloride and ammonium metatungstate into a dissolving tank to prepare an acidic working solution A, and preparing 100g of ammonium bicarbonate into a solution with the molar concentration of 2.0 mol/L. 500mL of water was added to the reaction tank and the temperature was raised to 60 ℃. Under the condition of stirring, the solution A, an ammonium bicarbonate aqueous solution and ammonia water with the concentration of 10wt% are added into a reaction tank in parallel to form gel, the gelling temperature is 60 ℃, the gelling time is 3.0 hours, and the pH value of slurry in the gelling process is 7.8. Aging for 3.8 hours after gelling, and the pH value is 8.0 after aging. Then filtering to obtain a filter cake, adding molybdenum trioxide, pulping, stirring uniformly, filtering, drying the filter cake at 120 ℃ for 8 hours, rolling, extruding and forming. Washed 5 times with deionized water at room temperature. The wet strands were then dried at 80 ℃ for 10 hours and calcined at 500 ℃ for 4 hours to give catalyst H. The catalyst composition, pore distribution and main properties are shown in table 1.
Example 5
This example is WS in the sulfided catalyst2/MoS2Measurement of average length of sheet and average number of stacked layers. The TEM picture of the prepared bulk phase catalyst is subjected to statistical analysis, and the statistical area is about 20000nm2Statistical WS2/MoS2The total number of slices exceeds 400. Bulk phase catalyst WS according to the calculation formulae (1) and (2)2/MoS2The average length of the sheets and the average number of stacked layers were statistically calculated and the results are shown in Table 3.
Figure DEST_PATH_IMAGE002
（1）
Figure DEST_PATH_IMAGE004
（2）
In the formulas (1) and (2),L A is WS2/MoS2The average length of the sheets is,L i is WS2/MoS2Lamella length, nm;n i is of length ofL i WS (A) of2/MoS2The number of the sheets is equal to the number of the sheets,N A is WS2/MoS2The average number of stacked layers;N i is WS2/MoS2The number of layers is stacked,m i is stacked with the number of layers ofN i WS (A) of2/MoS2Number of slices.
The catalyst A, B, C, D of the invention and the catalyst E, F, G, H of the comparative example were used to perform sulfidation on a hydrogenation microreactor, the catalyst loading volume was 10mL, and the sulfiding agent was CS2The sulfurized oil being cyclohexane, CS2The amount of sulfur used is 110% of the theoretical amount of sulfur required. The prevulcanization conditions are as follows: the temperature is 320 ℃, the hydrogen pressure is 6.0MPa, and the space velocity is 2.0h-1And the time is 10 h.
Example 6
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 carried out on a 200mL small-sized hydrogenation unit by using the catalyst A, B, C, D of the present invention and the catalyst E, F, G, H of the comparative example, and in order to further evaluate the denitrification capability of the catalysts, Hongkong catalytic diesel oil with high nitrogen content and high processing difficulty was selected as a test raw material, and the main properties of the raw material are shown in Table 4. Catalyst activity evaluation process conditions: the hydrogen partial pressure is 6.4MPa, the reaction temperature is 360 ℃, and the liquid hourly space velocity is 2.0h-1The hydrogen-oil volume ratio was 500:1, and the evaluation results are shown in Table 5. 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 6 and 7.
As can be seen from Table 2, the MoS of the catalyst of the present invention was obtained without substantially changing the amount of active metal as compared with the catalyst of the comparative example2/WS2The average stacking layer number is increased, the average lamella length is reduced, and the number of hydrogenation active centers is obviously increased. As can be seen from Table 3, the MoS of the catalyst of the invention after sulfidation2/WS2The number of stacked layers is mainly concentrated in 6.0-9.0 layers, and the length of the lamella is mainly concentrated in 4.0-6.5 nm. As can be seen from Table 4, the use of a high feedstock nitrogen content for catalyst activity evaluation will also increase ultra-deep hydrodeoxygenation of the feedstockThe difficulty of sulfur. As seen from the evaluation results in tables 5 to 7, the catalyst of the present invention has excellent hydrodenitrogenation activity, and exhibits high hydrogenation activity in 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 G H
NiO，wt% 19 22 18 20 19 19 19 19
WO3，wt% 35 32 36 37 35 35 35 35
MoO3，wt% 18 16 16 12 18 18 18 18
Al2O3，wt% Balance of Balance of Balance of Balance of Balance of Balance of Balance of Balance of
Others/wt% - ZrO2/3.0 - - - - - -
Specific surface area, m2/g 219 214 213 215 175 179 219 225
Pore volume, mL/g 0.328 0.324 0.320 0.322 0.271 0.273 0.325 0.334
Mechanical Strength, N/mm 18.2 18.4 18.6 18.1 16.7 17.2 15.8 14.7
Hole distribution,%
＜3nm 6.15 6.68 6.55 6.52 65.16 63.81 11.51 20.18
3nm~10nm 70.33 69.82 69.84 69.96 20.27 21.69 61.52 40.56
10nm~15nm 12.15 12.17 12.22 12.37 8.03 9.12 23.47 30.24
＞15nm 11.37 11.33 11.39 11.15 6.54 5.38 3.50 9.02
TABLE 2 MoS in bulk catalyst2/WS2Average number of stacked layers and average sheet length of
Catalyst numbering Average number of stacked layers NA Average length LA，nm
A 8.47 4.75
B 8.38 4.79
C 8.36 4.80
D 8.37 4.81
E 4.88 7.92
F 5.03 8.01
G 5.97 7. 85
H 5.93 7. 62
TABLE 3 MoS in bulk catalyst2/WS2Distribution of the number of stacked layers and the length of the sheet
Catalyst numbering A B C D E F G H
Distribution of number of lamellae,%
Layer < 4.0 3.06 3.63 3.57 3.39 30.22 32.56 24.98 20.56
4.0 to less than 7.0 layers 9.21 9.79 9.47 9.58 66.22 64.98 71.26 74.26
7.0 to 9.0 layers 75.69 75.36 75.41 75.29 3.56 2.46 3.76 5.18
Greater than 9.0 layers 12.04 11.22 11.55 11.74 - - - -
Length distribution of%
＜2.0nm 6.05 5.34 5.67 5.55 1.19 1.23 1.09 1.54
2.0 to less than 4.0nm 13.25 13.65 13.37 13.52 4.58 5.26 4.98 4.74
4.0~6.0nm 75.73 75.61 75.16 75.20 8.27 8.56 8.69 8.19
Greater than 6.0 to 8.0nm 4.24 4.42 4.87 4.82 65.17 64.21 65.59 66.58
＞8.0nm 0.73 0.98 0.93 0.91 20.79 20.74 19.65 18.95
TABLE 4 Primary Properties of the base oils
Item Analysis results
Density (20 ℃ C.), g/cm3 0.9025
Range of distillation range, deg.C 162-375
S，µg/g 5026
N，µg/g 1024
TABLE 5 evaluation results of catalyst Activity
Catalyst numbering A B C D
Density of the resulting oil (20 ℃ C.), g/cm3 0.8695 0.8698 0.8697 0.8696
Range of distillation range, deg.C 168-371 169-370 170-372 172-371
S，µg/g 6.6 6.9 7.0 6.8
N，µg/g 6.7 7.1 7.3 7.1
TABLE 5 evaluation results of catalyst Activity
Catalyst numbering E F G H
Density of the resulting oil (20 ℃ C.), g/cm3 0.8856 0.8883 0.8804 0.8812
Range of distillation range, deg.C 173-374 172-374 176-373 175-373
S，µg/g 265.6 260.2 217.5 228.6
N，µg/g 78.2 74.8 60.9 62.1
TABLE 6 content of different sulfides in hydrorefined oils
Catalyst numbering A B C D E
Sulphur content in hydrofined oil, microgram/g 6.6 6.9 7.0 6.8 265.6
C1-DBT，µg/g 0 0 0 0 48.3
4- BMDBT，µg/g 1.2 1.3 1.3 1.3 69.2
6-BMDBT，µg/g 1.8 1.8 1.8 1.8 65.6
4，6- BMDBT，µg/g 3.6 3.8 3.9 3.7 82.5
TABLE 6 continuation
Catalyst numbering F G H
Sulphur content in hydrofined oil, microgram/g 260.2 217.5 228.6
C1-DBT，µg/g 40.7 33.4 37.8
4- BMDBT，µg/g 61.5 54.9 56.5
6-BMDBT，µg/g 68.4 56.3 60.3
4，6- BMDBT，µg/g 89.6 72.9 74.0
TABLE 7 content of different nitrides in hydrorefined oils
Catalyst numbering A B C D E
Nitrogen content in hydrofined oil, mug/g 6.7 7.1 7.3 7.1 78.2
1- MCB，µg/g 1.3 1.4 1.4 1.3 28.3
1，8-BMCB，µg/g 1.9 2.0 2.1 2.1 34.9
1，4，8- TMCB，µg/g 3.5 3.7 3.8 3.7 15.0
TABLE 7
Catalyst numbering F G H
Nitrogen content in hydrofined oil, mug/g 74.8 60.9 62.1
1-MCB，µg/g 24.2 18.1 17.8
1，8-BMCB，µg/g 35.3 28.3 29.5
1，4，8-TMCB，µg/g 15.3 14.5 14.8
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-BMCB), 1, 4, 8-trimethylcarbazole (1, 4, 8-TMCB) and the like which have larger molecules and steric hindrance.

Claims (34)

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 Ni and W components, and preparing a mixed solution B containing W, Mo and Al components;
(2) adding the mixed solution A, the organic assistant and the sodium metaaluminate alkaline solution into a reaction tank in a concurrent flow manner to carry out gelling reaction to generate precipitate slurry I containing nickel, aluminum and tungsten, and aging the obtained slurry I;
(3) adding the mixed solution B and ammonia water into the aged slurry I in a cocurrent flow manner to react to generate precipitate slurry II containing nickel, molybdenum, tungsten and aluminum, and then aging;
(4) drying, forming and washing the material obtained in the step (3), and then drying and roasting to obtain a hydrofining catalyst;
wherein, an organic template agent is added before the gelling reaction in the step (2); the organic template is a quaternary ammonium salt template;
in the step (2), the organic auxiliary agent is a carboxylic acid polymer and/or an organic phosphonic acid, the molecular weight of the carboxylic acid polymer is 400-5000, and the carboxylic acid polymer is selected from one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyepoxysuccinic acid, acrylic acid-hydroxypropyl acrylate copolymer and maleic acid-acrylic acid copolymer; the organic phosphonic acid is selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid, polyol phosphonate, polyaminopolyether methylene phosphonic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane, hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acid.
2. The method of claim 1, wherein: the mixed solution A in the step (1) is an acid solution, wherein the weight concentration of Ni in NiO is 5-100 g/L, and the weight concentration of W in WO3The calculated weight concentration is 2-60 g/L; the mixed solution B is an acid solution, wherein W is WO3The weight concentration is 2-70 g/L, and Mo is MoO3The weight concentration is 5-80 g/L, Al is Al2O3The weight concentration is 2-60 g/L.
3. The method of claim 1, wherein: in the step (2), the weight of W introduced by the mixed solution A accounts for 40-80% of the weight of W in the hydrofining catalyst obtained in the step (4); in the step (3), the weight of W introduced through the mixed solution B accounts for 20-60% of the weight of W in the hydrofining catalyst obtained in the step (4), and the weight of Al introduced through the mixed solution B accounts for 15-60% of the weight of Al in the hydrofining catalyst obtained in the step (4).
4. The method of claim 1, wherein: in the step (2), the weight of W introduced by the mixed solution A accounts for 51-75% of the weight of W in the hydrofining catalyst obtained in the step (4); in the step (3), the weight of W introduced through the mixed solution B accounts for 25-49% of the weight of W in the hydrofining catalyst obtained in the step (4), and the weight of Al introduced through the mixed solution B accounts for 25-49% of the weight of Al in the hydrofining catalyst obtained in the step (4).
5. The method of claim 1, wherein: in the step (2), the molar ratio of the added amount of the organic auxiliary agent to W in the mixed solution A is 0.8: 1-3: 1.
6. the method of claim 5, wherein: in the step (2), the carboxylic acid polymer is one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid and polyepoxysuccinic acid; the organic phosphonic acid is selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid and aminotrimethylene phosphonic acid; the molar ratio of the added amount of the organic auxiliary agent to W in the mixed solution A is 1: 1-2.5: 1.
7. the method of claim 1 or 5, wherein: in the step (2), the organic auxiliary agent is added separately in parallel flow, or is added when the mixed solution A is prepared, or is added by combining the two modes.
8. The method of claim 1, wherein: the molar ratio of the added amount of the organic template agent to W in the mixed solution A in the step (2) is 0.3: 1-5: 1.
9. the method of claim 1, wherein: in the step (2), the organic template agent is one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide and dodecyltrimethylammonium chloride; the molar ratio of the added amount of the organic template agent to W in the mixed solution A in the step (2) is 0.5: 1-4: 1.
10. the method of claim 1, wherein: adding an organic template agent before the gelling reaction in the step (2), wherein the organic template agent is added before the reaction, namely the organic template agent is added into the reaction tank before the mixed solution A, the organic auxiliary agent and the sodium metaaluminate alkaline solution are added into the reaction tank in a parallel flow manner.
11. The method of claim 1, wherein: deviation described in step (2)Concentration of sodium aluminate alkaline solution as Al2O35-80 g/L; in the step (2), the reaction temperature for gelling is 20-90 ℃, the pH value is controlled to be 6.0-10.0, and the gelling time is 0.2-2.0 hours.
12. The method of claim 1, wherein: the concentration of the sodium metaaluminate alkaline solution in the step (2) is Al2O310-60 g/L; in the step (2), the reaction temperature for gelling is 30-70 ℃, the pH value is controlled to be 7.0-9.0, and the gelling time is 0.3-1.5 hours.
13. The method of claim 1, wherein: the aging conditions in step (2) are as follows: the aging temperature is 40-90 ℃, the pH value during aging is controlled to be 6.0-8.0, the aging time is 0.1-1.0 hour, and the aging is carried out under stirring.
14. The method of claim 1, wherein: the aging conditions in step (2) are as follows: the aging temperature is 50-80 ℃, the pH value during aging is controlled to be 6.5-7.5, the aging time is 0.2-0.8 hours, the aging is carried out under stirring, and the stirring conditions are as follows: the stirring speed is 100-300 rpm.
15. The method of claim 1, wherein: the weight concentration of the ammonia water in the step (3) is 5-15%; the mixed solution B and ammonia water are added into the aged slurry I in a cocurrent manner to carry out gelling reaction under the following reaction conditions: the reaction temperature is 20-90 ℃, the pH value is controlled to be 6.0-11.0, and the gelling time is 0.5-4.0 hours.
16. The method of claim 1, wherein: the weight concentration of the ammonia water in the step (3) is 5-15%; the mixed solution B and ammonia water are added into the aged slurry I in a cocurrent manner to carry out gelling reaction under the following reaction conditions: the reaction temperature is 30-80 ℃, the pH value is controlled to be 6.5-9.0, and the gelling time is 1.0-3.0 hours.
17. The method of claim 1, wherein: the aging conditions in step (3) are as follows: the aging temperature is 40-90 ℃, the pH value during aging is controlled to be 7.5-11.0, the aging time is 1.5-6.0 hours, and the aging is carried out under stirring.
18. The method of claim 1, wherein: the aging conditions in step (3) are as follows: the aging temperature is 50-80 ℃, the pH value during aging is controlled to be 7.5-9.5, the aging time is 2.0-5.0 hours, the aging is carried out under stirring, and the stirring conditions are as follows: the stirring speed is 300-500 rpm.
19. The method of claim 17, wherein: the aged pH of step (3) is at least 0.5 higher than the aged pH of step (2).
20. The method of claim 17, wherein: the aged pH of step (3) is at least 1.0 higher than the aged pH of step (2).
21. The method of claim 1, wherein: the drying conditions before the molding in the step (4) are as follows: drying for 1-48 hours at 40-250 ℃; after the step (4) of molding, the adopted drying conditions are as follows: drying for 1-48 hours at 40-250 ℃, wherein the roasting conditions are as follows: roasting at 350-650 ℃ for 1-24 hours.
22. The method of claim 1, wherein: the hydrofining catalyst contains Ti and/or Zr as auxiliary components, and compounds containing the auxiliary components, namely a titanium source and/or a zirconium source, are added in the process of preparing the mixed solution A.
23. The method of claim 1, wherein: NiO and WO based on the weight of the hydrofining catalyst3And MoO3The total content of the alumina is 40-95 percent, and the content of the alumina is 5-60 percent.
24. The method of claim 1, wherein: NiO and WO based on the weight of the hydrofining catalyst3And MoO3The total content of the aluminum oxide is 50-85 percent, and the content of the aluminum oxide is 15-50 percent.
25. The method of claim 1 or 23, wherein: in the hydrofining catalyst, the molar ratio of W/Mo is 1: 10-8: 1, the molar ratio of Ni/(Mo + W) is 1: 12-12: 1.
26. the method of claim 1 or 23, wherein: in the hydrofining catalyst, the molar ratio of W/Mo is 1: 8-5: 1, the molar ratio of Ni/(Mo + W) is 1: 8-8: 1.
27. the process of claim 1, wherein the hydrofinishing catalyst of step (4) is sulfided to produce a sulfided hydrofinishing catalyst.
28. The method of claim 27, wherein: the sulfurization is to convert active metal W, Ni and Mo into corresponding sulfides, the sulfurization adopts wet sulfurization, and the sulfurization agent is an organic sulfur-containing substance and/or an inorganic sulfur-containing substance and is selected from one or more of sulfur, carbon disulfide and dimethyl disulfide; the sulfurized oil is hydrocarbon and/or distillate oil, preferably, the hydrocarbon is one or more of cyclohexane, cyclopentane and cycloheptane, and the distillate oil is one or more of kerosene, normal first-line diesel oil and normal second-line diesel oil; the prevulcanization conditions are as follows: the temperature is 230-370 ℃, the hydrogen pressure is 2.0-10 MPa, and the liquid hourly space velocity is 0.3-6.0 h-1And the vulcanization time is 3-24 h.
29. The method of claim 28, wherein: the prevulcanization conditions are as follows: the temperature is 250-350 ℃, the hydrogen pressure is 3.0-8.0 MPa, and the liquid hourly space velocity is 1.0-3.0 h-1And the vulcanization time is 5-16 h.
30. A method according to claim 27 or 28, wherein: in the vulcanized hydrofining catalyst, the vulcanization degree of each active metal is not less than 80%.
31. The process according to claim 27 or 28, wherein the hydrorefining catalyst is sulfurized, MoS2/WS2The average number of stacked layers of (2) is 6.0 to 9.0 layers, MoS2/WS2The average length of the lamella is 4.0-6.5 nm.
32. The process according to claim 27 or 28, wherein the hydrorefining catalyst is sulfurized, MoS2/WS2The average number of stacked layers of (2) is 6.5 to 9.0 layers, MoS2/WS2The average length of the lamella is 4.5-6.0 nm.
33. The process according to claim 27 or 28, wherein the hydrorefining catalyst is sulfurized, MoS2/WS2The number of stacked layers is distributed as follows: the number of the layers of 7.0-9.0 accounts for 55-85% of the total number of the layers of the sheets; the sheet length distribution is as follows: the number of the 4.0-6.0 nm long sheets accounts for 55-85% of the total number of the sheets.
34. The process according to claim 27 or 28, wherein the hydrorefining catalyst is sulfurized, MoS2/WS2The number of stacked layers is distributed as follows: the number of the laminated layers is 7.0-9.0 and accounts for 61-80% of the total laminated layers; the sheet length distribution is as follows: the number of the lamella with the length of 4.0-6.0 nm accounts for 65-80% of the total number of the lamella.
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