CN107790161B - Process for preparing hydroprocessing catalysts - Google Patents

Process for preparing hydroprocessing catalysts Download PDF

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CN107790161B
CN107790161B CN201610735700.4A CN201610735700A CN107790161B CN 107790161 B CN107790161 B CN 107790161B CN 201610735700 A CN201610735700 A CN 201610735700A CN 107790161 B CN107790161 B CN 107790161B
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oxide precursor
preparing
catalyst
precursor slurry
salt
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CN107790161A (en
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冯小萍
刘东香
徐学军
王海涛
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun 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
    • B01J27/19—Molybdenum
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a preparation method of a hydrotreating catalyst. The method comprises the following steps: preparing oxide precursor slurry A of Al; preparing oxide precursor slurry B of Mo and Co; preparing oxide precursor slurry C of Mo and Ni; preparing an oxide slurry D of Ni; and mixing the slurry A, the slurry B, the slurry C and the slurry D, aging, filtering, drying, forming, washing, drying and roasting to obtain the hydrotreating catalyst. The hydrotreating catalyst prepared by the method can greatly improve the hydrodenitrogenation and hydrodesulfurization activity of the catalyst, and is suitable for hydrocracking, catalytic cracking raw material pretreatment, distillate oil hydrotreating and other processes.

Description

Process for preparing hydroprocessing catalysts
Technical Field
The invention relates to a preparation method of a hydrotreating catalyst, in particular to a preparation method of a hydrocracking pretreatment catalyst.
Background
The rapid development of the world economy drives the industry and the logistics transportation industry to consume fuel oil in large quantity, and accelerates the heavy and inferior trend of crude oil. The long-term property of processing heavy and poor raw materials in the future is expected. The heavy inferior raw material has high dry point and high carbon residue content, also contains a large amount of nitrogen-containing compounds, polycyclic aromatic hydrocarbons, heavy metals thereof and the like, can accelerate the poisoning and coking of the catalyst, and shortens the service cycle of the catalyst.
The nitrogen-containing compound, especially the basic nitride, has strong adsorbability in the acid center of the cracking catalyst, can be condensed and coked on the surface of the catalyst when the nitrogen-containing compound is not removed in time, so that the catalyst is poisoned and inactivated, the service life of the catalyst is shortened, and the nitrogen-containing compound is a strong retarder for hydrogenation reactions, especially cracking, isomerization and hydrogenolysis reactions.
The raw material with higher nitrogen content is subjected to one-stage series or two-stage process hydrotreating, so that nitrogen in the organic nitride is hydrogenated and converted into ammonia, and before the raw material is contacted with the hydrocracking catalyst, the nitrogen content is reduced to the range which can enable the activity of the hydrocracking catalyst to be well exerted, so that the coking speed of the cracking catalyst can be reduced, and the service life of the catalyst is prolonged.
In the reactions of hydrodesulfurization, denitrification, aromatic hydrocarbon saturation and the like in the pretreatment of the hydrocracking raw material, the hydrodenitrogenation reaction is slowest, the hydrodenitrogenation activity can measure the performance of the hydrocracking pretreatment catalyst, and the high denitrification activity of the hydrocracking catalyst is an important condition for ensuring the performance of the rear-stage hydrocracking catalyst to be well exerted.
The content of aliphatic nitrides in the raw material is small, and nitrogen exists in the form of heterocyclic aromatic compounds. Aliphatic nitrides are easy to generate C-N bond hydrogenolysis, are fast reaction steps in Hydrodenitrogenation (HDN) reaction, and cannot bring difficulty to the hydrodenitrogenation process. Many studies on denitrification reactions of nitrogen-containing heterocyclic compounds show that the hydrogenation saturation of heterocycles and the hydrogenolysis reaction of C-N bonds are indispensable reaction steps for removing nitrogen atoms from nitrogen-containing compounds, and when the hydrogenation saturation reaction of heterocycles and the hydrogenolysis reaction of C-N bonds are relatively fast and mutually promoted, the total HDN reaction rate is remarkably improved. This requires that the relative amounts of hydrogenation and hydrogenolysis reactive sites of the catalyst be high and reasonably matched.
The activity of the hydrotreating catalyst is related to a plurality of factors such as the composition of the catalyst, the proportion of components, the type and dispersion of an active phase, a pore structure, the shape and the size of particles, the properties of a carrier and an auxiliary agent and the like.
The general hydrotreating catalyst is prepared by using a conventional carrier impregnation method for loading active metal components, namely, the carrier is impregnated with aqueous solution of active metal compounds of the VIII family and the VIB family for one time or more times, and is loaded on the carrier in the form of oxides or sulfides, and then the final catalyst is obtained by drying and roasting. The preparation method of the catalyst can not break through the bottleneck that the loading capacity of metal components is limited, the activity of the catalyst is improved limitedly by modulation of an auxiliary agent and the like, and when heavy fractions such as VGO with the nitrogen content of 200-2000 mu g/g are treated, the requirement that the nitrogen content of the product is reduced to be below 20 mu g/g of the nitrogen content of the feed at the cracking section is difficult to finish.
CN1854260A discloses a heavy distillate oil hydrotreating catalyst and a preparation method thereof. The catalyst is prepared by step-by-step gelatinizing and dispersing silicon and boron on the surface of alumina, and loading metals of VIII family and VIB family by an impregnation method, so that the catalyst has proper acid property, the pore structure of the catalyst is improved, and the HDN activity of the catalyst is improved. CN1488716A discloses a hydrotreating catalyst and its preparation method. According to the preparation method of the catalyst, molybdenum, nickel and phosphorus are loaded on the silicon-containing alumina carrier prepared by a special method, active metals are enriched on the surface, the catalyst has high total acid content, and the HDN activity of treating heavy distillate oil is improved. However, the preparation method of the catalyst is a conventional impregnation method, the carrier and the active metal are difficult to be uniformly dispersed, the bottleneck of limited metal loading capacity cannot be broken through, the improvement of the hydrogenation activity of the catalyst is limited only by the modes of improving the interaction between the metal and the carrier, the dispersibility of the active metal on the carrier and the like through the additive, and in addition, the increase of the strong acid content of the hydrogenation catalyst can reduce the liquid yield and shorten the service life of the catalyst while improving the hydrodenitrification.
The bulk phase catalyst can get rid of the bottleneck that the loading amount of the active metal is limited; the proportion of each active component can be adjusted randomly according to different processing raw materials and target products of the catalyst; through proper preparation conditions, the active metal forms a precursor with a better matching mode and is uniformly distributed; can greatly improve the performance of the catalyst such as hydrodesulfurization, denitrification, aromatic saturation and the like.
CN101172261A discloses a W-Mo-Ni hydrogenation catalyst prepared by a bulk phase method. The catalyst adopts salt mixed solution of active metal Ni, W components and auxiliary agent and sodium metaaluminate solution for parallel-flow coprecipitation to generate NixWyOzComposite oxide precursor, then with MoO3Pulping, mixing, filtering, forming and activating to obtain the final catalyst, wherein the loading capacity of the active metal is not limited, and more total active metal can be provided. However, the catalyst W-Ni-Mo active metal has good hydrogenation performance, so that some easy-to-perform desulfurization and denitrification reactions are realized through a hydrogenation path, thereby excessively consuming hydrogen and increasing the processing cost. In addition, the coprecipitation of W-Mo-Ni and Al can cause some active metals and Al to form aluminate with stronger action, so that the reduction and vulcanization are difficult, and the utilization rate of the active metals is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing a hydrotreating catalyst. The hydrotreating catalyst prepared by the method can greatly improve the hydrodenitrogenation and hydrodesulfurization activity of the catalyst, and is suitable for hydrocracking, catalytic cracking raw material pretreatment, distillate oil hydrotreating and other processes.
The preparation method of the hydrotreating catalyst of the invention comprises the following steps:
(1) preparing oxide precursor slurry A of Al;
(2) preparing oxide precursor slurry B of Mo and Co;
(3) preparing oxide precursor slurry C of Mo and Ni;
(4) preparing oxide precursor slurry D of Ni;
(5) mixing the slurries obtained in the steps (1), (2), (3) and (4), then aging, filtering and drying;
(6) and (5) forming, washing, drying and roasting the material obtained in the step (5) to obtain the hydrotreating catalyst.
In the preparation method of the hydrotreating catalyst of the present invention, the slurry a of the oxide precursor of Al (i.e., aluminum hydroxide) prepared in step (1) can be prepared by a conventional method such as neutralization precipitation, aluminum alkoxide hydrolysis, etc., and the oxide precursor of Al is preferably pseudo-boehmite.
In the preparation method of the hydrotreating catalyst of the present invention, when preparing the oxide precursor slurry a of Al in step (1), the auxiliary agent Si is added in an amount of SiO2The amount of the catalyst is less than 10.0wt%, preferably 2.0wt% to 8.0wt% of the hydrotreating catalyst.
In the method for producing a hydrotreating catalyst of the present invention, in the step (2) and/or the step (3), 1/20 to 1/10 by volume of the Al oxide precursor slurry a produced in the step (1) is preferably introduced.
In the preparation method of the hydrotreating catalyst, the oxide precursor slurry B of Mo and Co prepared in the step (2) adopts a precipitation method, namely cobalt salt is prepared into an acidic solution B1, molybdenum salt is prepared into an alkaline solution B2, the acidic solution B1 and the alkaline solution B2 are gelatinized, the reaction temperature is 75-90 ℃, and the pH value is 4-6. In the step (2), the molar ratio of Mo to Co is 1: 1.0 to 1.2.
In the preparation method of the hydrotreating catalyst, the oxide precursor slurry C of Mo and Ni prepared in the step (3) adopts a precipitation method, namely nickel salt is prepared into an acidic solution C1, molybdenum salt is prepared into an alkaline solution C2, the acidic solution C1 and the alkaline solution C2 are gelatinized, the reaction temperature is 65-85 ℃, and the pH value is 4-6; wherein the molar ratio of Mo to Ni is 1: 1.0 to 1.2.
In the preparation method of the hydrotreating catalyst, the cobalt amount is introduced in the step (2) and the nickel amount is introduced in the step (3), and the molar ratio of Co to Ni is 1: 1-1: 10 preferably 1: 3-1: 8.
in the preparation method of the hydrotreating catalyst, ammonium carbonate salt and/or alkali metal carbonate salt, such as one or more of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, is/are added in the gelling process in the step (2) and/or the step (3). When ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (2), the addition amount is CO2The molar ratio of the Mo to the Mo used in the step (2) is 0.05-1.0, preferably 0.08-0.80. When ammonium carbonate and/or alkali metal carbonate is/are added in the step (3), the molar ratio of the added amount to Mo used in the step (3) is 0.05-1.0, preferably 0.08-0.80.
Preparing Ni oxide precursor slurry D in the step (4) by adopting a precipitation method, namely preparing nickel salt into an acidic solution D1, neutralizing the acidic solution D1 with an alkaline precipitator to form gel, wherein the reaction temperature is 40-65 ℃, and the pH value is 7-9; the alkaline precipitating agent may be one or more of ammonia, sodium hydroxide, potassium hydroxide, etc., and ammonia gas is preferred. The molar ratio of the addition amount of Ni in the step (4) to Mo in the hydrotreating catalyst is 1-6: 1, and preferably 1-4: 1.
In the step (5), the slurries obtained in the steps (1), (2), (3) and (4) are mixed, the pH value is controlled to be 7-9, the temperature of the slurry is 65-90 ℃, and the mixture is stirred for 10-30 minutes; the aging conditions in the step (5) are as follows: the pH value is 7-9, the aging temperature is 70-90 ℃, and the aging time is 0.5-3.0 hours.
The step (5) of the preparation method of the hydrotreating catalyst can be added according to the proportioning composition of the catalyst orWithout addition of MoO3Adding molybdenum in MoO3Accounts for the total MoO in the hydroprocessing catalyst3Less than 30% by weight.
The forming in step (6) can adopt a conventional forming method, such as extrusion forming and the like. The catalyst can be made into tablet, sphere, cylindrical strip and special-shaped strip (such as clover and clover) according to the requirement, preferably cylindrical strip and special-shaped strip. In the forming process, a proper amount of forming aids, such as extrusion aids and the like, can be added. The washing can be carried out by pure water washing at normal temperature, and the drying and roasting can be carried out by conventional drying and roasting modes. Wherein the drying and roasting conditions are as follows: drying at 50-120 ℃ for 2.0-6.0 hours, and calcining at 450-600 ℃ for 3.0-6.0 hours.
In the method for producing the hydrotreating catalyst of the present invention, a catalyst auxiliary may be added as needed in at least one of the steps (1), (2), (3), (4), and (5), (6). The auxiliary agent generally comprises one or more of Si, P, F, B, Zr, Ti and the like, and Si and/or P are preferred. The method for adding the auxiliary agent adopts the conventional method in the field. The addition amount of the auxiliary agent is less than 25 percent of the weight of the hydrotreating catalyst calculated by oxide, and is preferably 1 to 15 percent.
In the hydrotreating catalyst prepared by the method of the invention, the total weight content of the hydrogenation active metals Mo, Ni and Co calculated by oxides is 25-65%, preferably 30-55%, and the content of alumina is 35-75%, preferably 45-70%, based on the weight of the hydrotreating catalyst.
The hydrotreating catalyst of the present invention preferably contains a promoter P, based on the weight of the hydrotreating catalyst, P2O5The content is 5.0% or less, preferably 0.3% to 5.0%, and more preferably 0.5% to 3.0%.
The hydrotreating catalyst of the present invention preferably contains an auxiliary agent Si in terms of SiO based on the weight of the hydrotreating catalyst2The content is 10.0% or less, preferably 2.0% to 8.0%.
The properties of the hydroprocessing catalyst of the invention are as follows: the pore volume is 0.25-1.0 mL/g, the specific surface area is 180-410 m2/g。
In the preparation method of the hydrotreating catalyst, the precipitation form of the hydrogenation active metal is controlled, namely molybdenum is mainly precipitated in the form of cobalt molybdate and nickel molybdate, and carbonate added in the precipitation process can slowly and uniformly release carbon dioxide in a weak acid reaction environment, so that the growth of nickel molybdate and cobalt molybdate precipitate particles is prevented, the pore structure is enriched, and the surface area is increased; the other part of nickel is precipitated in the form of hydroxide, ammonia gas is preferably used as a precipitator, and the ammonia gas reacts with the nickel to generate nickel hydroxide and simultaneously prevents the growth of particles, so that the pore structure and the surface area of the nickel hydroxide are improved; this is advantageous for the formation of Mo, Co and Mo, Ni active phases on the one hand and for the number of empty orbitals which can be made available for the reaction of partially undersulfided nickel to accommodate the adsorption of hydrogen and undissociated H on the other hand2S, forming a reaction site for mutual promotion of desulfurization and denitrification, simultaneously having rich pore structure and active surface, and promoting ring opening of cycloalkane by synergistic effect of each advantage to accelerate denitrification reaction speed. The hydrotreating catalyst prepared by the method can greatly improve the HDN and HDS activity of the catalyst, and is suitable for the processes of hydrocracking raw materials pretreatment, catalytic cracking raw materials pretreatment, distillate oil hydrotreating and the like. When the catalyst is used for raw material pretreatment, the catalyst has the application advantages of low coking speed, long service life, good regenerability and the like.
Detailed Description
The preparation method of the hydrotreating catalyst provided by the invention specifically comprises the following steps:
(1) preparation of oxide precursor slurry A of Al
The method preferably adopts a neutralization precipitation method, namely, an aluminum salt solution and ammonia water are subjected to neutralization precipitation in a parallel flow manner to obtain the pseudo-boehmite slurry, wherein the gelling temperature is 65-85 ℃, and the gelling pH value is 8-10. The aluminum salt can be one or more of aluminum chloride, aluminum nitrate, aluminum sulfate and the like. The concentration of ammonia can be in any feasible proportion, preferably from 15% to 25% by weight. The auxiliary agent Si can be introduced into the aluminum salt solution according to the requirement of the catalyst, and the silicon source can be one or more of water glass, silica sol and the like.
(2) Preparation of oxide precursor slurry B of Mo and Co
Preparing cobalt salt into an acidic solution B1, preparing molybdenum salt into an alkaline solution B2, and then gelling the acidic solution B1 and the alkaline solution B2, wherein ammonium carbonate salt and/or alkali metal carbonate salt can be added into the alkaline solution B2 to introduce a reaction system, or can be prepared into a solution to introduce the reaction system separately, and the gelling can be performed by adopting a parallel-flow gelling method or a dropwise gelling method, preferably by adopting a method of dropwise adding the alkaline solution B2 into the acidic solution B1 to gel; the gelling conditions are as follows: the reaction temperature is 75-90 ℃, and the pH value is 4-6; in the gelling process in the step (2), 1/20-1/10 of the volume of the Al oxide precursor slurry A prepared in the step (1) is preferably introduced. In the step (2), the cobalt salt is one or more of cobalt nitrate and cobalt chloride, the molybdenum salt is ammonium molybdate, the ammonium carbonate salt is one or more of ammonium carbonate and ammonium bicarbonate, the alkali metal carbonate salt is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and preferably the ammonium carbonate salt. In the acidic solution B1, the concentration of cobalt salt is 3.5-15.0 g/L in terms of CoO, and in the alkaline solution B2, the concentration of molybdenum salt is MoO3The concentration is 10-30 g/L.
(3) Preparation of Mo, Ni oxide precursor slurry C
Preparing nickel salt into an acidic solution C1, preparing molybdenum salt into an alkaline solution C2, adding ammonium carbonate salt and/or alkali carbonate salt into the alkaline solution C2, introducing the ammonium carbonate salt and/or alkali carbonate salt into a reaction system, independently preparing a solution, introducing the solution into the reaction system, and gelatinizing the acidic solution C1 and the alkaline solution C2 by adopting a parallel-flow gelatinizing method or a dropwise gelatinizing method, preferably, adding the alkaline solution C2 into the acidic solution C1 by dropwise adding to gelatinize; the gelling conditions are as follows: the reaction temperature is 65-85 ℃, and the pH value is 4-6; in the gelling process in the step (3), 1/20-1/10 of the volume of the Al oxide precursor slurry A prepared in the step (1) is preferably introduced. In the step (3), the nickel salt can be one or more of nickel sulfate, nickel nitrate, nickel chloride, basic nickel carbonate, nickel oxalate and the like, the Mo salt is ammonium molybdate, the ammonium carbonate salt is one or more of ammonium carbonate and ammonium bicarbonate, and the alkali carbonate is goldThe metal salt is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, preferably ammonium carbonate salt. The assistant P can be introduced into the molybdenum salt solution according to the requirement, and the phosphorus source can be one or more of ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and the like. In the acidic solution C1, the concentration of nickel salt in NiO is 15-45 g/L. In the alkaline solution C2, the molybdenum salt is MoO3The concentration is 10-30 g/L.
(4) Preparation of Ni oxide precursor slurry D
Taking ammonia gas as a precipitator for example, the process is as follows: preparing nickel salt into an acidic solution D1, adding a certain amount of water into a reaction tank, heating to 40-65 ℃, dropwise adding the nickel salt into the water, introducing ammonia gas, controlling the flow rate of the nickel salt and the ammonia gas to enable the pH value to be within 6-8, and completing the reaction within 30-40 minutes;
(5) mixing the slurry obtained in the steps (1), (2), (3) and (4), controlling the pH value to be 7-9, controlling the temperature of the slurry to be 65-90 ℃, and stirring for 10-30 minutes; heating the slurry to 70-90 ℃, controlling the pH value to be 7-9, and aging for 0.5-3.0 hours.
(6) And (5) forming, washing, drying and roasting the material obtained in the step (5) to obtain the hydrotreating catalyst. Wherein the drying and roasting conditions are as follows: drying at 50-120 ℃ for 2.0-6.0 hours, and calcining at 450-600 ℃ for 3.0-6.0 hours.
MoO can be added or not added in the step (5) according to the proportioning composition of the catalyst3Adding molybdenum in MoO3Accounts for the total MoO in the hydroprocessing catalyst3Less than 30% by weight.
In the method of the present invention, the pH value of the slurry in steps (1), (2), (3), (4) and (5) can be adjusted by using acid or alkali, the acid can be one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, etc., and the alkali can be one or more of sodium hydroxide, potassium hydroxide, ammonia water, etc.
The embodiments and effects of the present invention are further illustrated by the following specific examples. In the present invention, wt% is a mass fraction. In the method, the pore volume and the specific surface area of the catalyst are measured by adopting a low-temperature liquid nitrogen adsorption method.
Example 1
(1) Preparation of Al oxide precursor slurry A
600mL of purified water and 120g of aluminum nitrate were added to a vessel, stirred to dissolve, and SiO-containing solution was added dropwise2100mL of 40g/L dilute water glass solution to obtain salt solution containing Al and Si; 2000mL of 20wt% aqueous ammonia solution was prepared in a container; adding 500mL of purified water into a gelling tank, heating to 75 ℃, adding a salt solution containing Al and Si and a 20wt% ammonia solution into a reaction tank in a cocurrent flow manner under the condition of continuous stirring to gel, controlling the reaction temperature to be about 75 ℃, controlling the pH of slurry to be 8.5 +/-0.2, and controlling the reaction time to be about 60min to obtain an Al oxide precursor slurry A;
(2) preparation of oxide precursor slurry B of Mo and Co
Adding 500mL of purified water, 10g of ammonium paramolybdate and 1.2g of ammonium bicarbonate into a container, heating to 75 ℃, and stirring to dissolve; adding 600mL of purified water and 11g of cobalt nitrate into a colloid forming tank, stirring to dissolve the purified water and the cobalt nitrate, adding 170mL of Al oxide precursor slurry prepared in the step (1), uniformly stirring, heating to 75 ℃, slowly adding ammonium paramolybdate solution into the colloid forming tank under continuous stirring, adjusting the pH value of the slurry to be 5 +/-0.2 by using ammonia water, keeping the temperature to be 75 ℃, and reacting for about 30min to obtain Mo and Co oxide precursor slurry B;
(3) preparation of Mo, Ni oxide precursor slurry C
Adding 800mL of purified water, 9.1g of ammonium paramolybdate, 1.1g of ammonium bicarbonate and 2.5g of ammonium dihydrogen phosphate into a container, heating to 75 ℃, and stirring to dissolve; adding 600mL of purified water and 10g of nickel nitrate into a gelling tank, stirring to dissolve the purified water and the nickel nitrate, adding 170mL of Al oxide precursor slurry prepared in the step (1), uniformly stirring, heating to 75 ℃, slowly adding ammonium paramolybdate solution into the gelling tank under continuous stirring, adjusting the pH value of the slurry to 5 +/-0.2 by using ammonia water, keeping the temperature at 75 ℃, and reacting for about 30min to obtain Mo and Ni oxide precursor slurry C;
(4) preparation of Ni oxide precursor slurry D
Adding 1000mL of purified water into a container, adding 49g of nickel nitrate, stirring to dissolve the nickel nitrate to obtain an acidic solution D1, adding 1000mL of purified water into a gelling tank, heating to 50 ℃, dropwise adding the acidic solution D1 into the gelling tank, introducing ammonia gas, controlling the flow rate of the acidic solution and the ammonia gas, keeping the pH value of the slurry at 6.8 +/-0.2, keeping the reaction temperature at about 50 ℃, and completing gelling within 30 minutes to obtain Ni oxide precursor slurry D;
(5) mixing the slurries obtained in the steps (1), (2), (3) and (4), controlling the pH value of the slurry to be 7.5 +/-0.2, stirring for 20 minutes, heating to about 75 ℃, controlling the pH value of the slurry to be 7.5 +/-0.2, aging for 1 hour, filtering and drying;
(6) and (3) forming and washing the material obtained in the step (5), drying at 90 ℃ for 3.0 hours, and roasting at 500 ℃ for 4.0 hours to obtain the hydrotreating catalyst A.
Example 2
The preparation method of the catalyst B of the invention is the same as that of the example 1, except that when the oxide precursor slurry B of Mo and Co is prepared in the step (2), 7.6g of ammonium paramolybdate, 1.1g of ammonium bicarbonate and 2.5g of ammonium dihydrogen phosphate are added into the alkaline solution B2, and 8.4g of cobalt nitrate is added into the acidic solution B1; when preparing oxide precursor slurry C of Mo and Ni in the step (3), adding 14.3g of nickel nitrate into an acidic solution C1, and adding 13.0g of ammonium paramolybdate and 1.8g of ammonium bicarbonate into an alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 43.9g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1, whereby catalyst B of the present invention was obtained.
Example 3
The preparation method of the catalyst C of the invention is the same as that of the example 1, except that 8.3g of ammonium paramolybdate, 1.2g of ammonium bicarbonate and 2.5g of ammonium dihydrogen phosphate are added into the alkaline solution B2, and 9.1g of cobalt nitrate is added into the acidic solution B1 when the oxide precursor slurry B of Mo and Co is prepared in the step (2); when preparing oxide precursor slurry C of Mo and Ni in the step (3), adding 17.5g of nickel nitrate into an acidic solution C1, and adding 16g of ammonium paramolybdate and 2.3g of ammonium bicarbonate into an alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 31.8g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1 to obtain catalyst C of the present invention.
Example 4
The preparation method of the catalyst D of the invention is the same as that of the example 1, except that when the oxide precursor slurry B of Mo and Co is prepared in the step (2), 11.5g of ammonium paramolybdate, 2.2g of ammonium bicarbonate and 2.5g of ammonium dihydrogen phosphate are added into the alkaline solution B2, and 12.6g of cobalt nitrate is added into the acidic solution B1; when preparing oxide precursor slurry C of Mo and Ni in the step (3), adding 10g of nickel nitrate into an acidic solution C1, and adding 9.1g of ammonium paramolybdate and 1.7g of ammonium bicarbonate into an alkaline solution C2; step (4) in the preparation of Ni oxide precursor slurry D, 43.8g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1 to obtain catalyst D of the present invention.
Example 5
The preparation method of the catalyst E of the invention is the same as that of the example 1, except that when the oxide precursor slurry B of Mo and Co is prepared in the step (2), 9.8g of ammonium paramolybdate, 0.5g of ammonium bicarbonate and 2.5g of ammonium dihydrogen phosphate are added into the alkaline solution B2, and 10.8g of cobalt nitrate is added into the acidic solution B1; when preparing oxide precursor slurry C of Mo and Ni in the step (3), adding 6.8g of nickel nitrate into an acidic solution C1, and adding 6.2g of ammonium paramolybdate and 0.3g of ammonium bicarbonate into an alkaline solution C2; in the preparation of Ni oxide precursor slurry D in step (4), 58.5g of nickel nitrate was added to the acidic solution D1, and the procedure was otherwise as in example 1, to obtain catalyst E of the present invention.
Comparative example 1
Adding 500mL of purified water, 21g of nickel chloride, 24.5g of ammonium metatungstate and 2.5g of ammonium dihydrogen phosphate into a dissolving tank 1, stirring for dissolving, and dropwise adding SiO-containing solution2100mL of 40g/L dilute water glass solution is prepared into acidic working solution A; 500mL of purified water is added into the dissolving tank 2, and 72g of sodium metaaluminate is added for dissolving to prepare an alkaline working solution B. Adding 350mL of purified water into a reaction tank, heating to 50 ℃, adding the solution A and the solution B into the reaction tank in a cocurrent manner under the condition of continuous stirring to form gel, keeping the gel forming temperature at 50 ℃, wherein the gel forming time is 0.5 hour, and the pH value of the gel forming slurry is 7.5. Aging for 1 hour after cementing, filtering, adding 600mL of purified water and 9.2g of molybdenum trioxide into filter cakes, pulping, stirring uniformly, and passingFiltering, drying the filter cake at 80 ℃ for 5 hours, extruding into strips, washing with clean water for 3 times, drying the wet strips at 120 ℃ for 5 hours, and roasting at 500 ℃ for 4 hours to obtain the catalyst F of the comparative example.
Comparative example 2
Taking 180g of macroporous alumina produced by taking aluminum trichloride and ammonia water as raw materials and 230g of German SB alumina powder, uniformly mixing, wetting nano silicon dioxide (the content of silicon dioxide is 7 wt%) by peptizing acid, then preparing 340g of peptizing agent, mixing and kneading the above materials for 30 minutes, extruding and forming, drying the wet strip at 110 ℃ for 6 hours, and roasting at 500 ℃ for 4 hours to obtain the carrier strip.
Preparing MoO according to a conventional method for preparing molybdenum-nickel-phosphorus solution3The catalyst of the comparative example was obtained by preparing an impregnation solution with a content of 21G/100mL, a NiO content of 23G/100mL, and a P content of 0.5G/100mL, preparing a basic cobalt carbonate solution with a CoO content of 12G/100mL, weighing 100G of the above carrier strip, mixing 250mL of a molybdenum-nickel-phosphorus solution and 50mL of the basic cobalt carbonate solution, stirring the mixture uniformly, impregnating the carrier strip for 2 hours, removing the mother liquor, drying the impregnated strip at 110 ℃ for 4 hours, calcining the impregnated strip at 500 ℃ for 4 hours, and repeating the impregnation, drying, and calcining processes for 2 times to obtain the catalyst G of the comparative example.
Table 1 shows the physicochemical properties of the catalysts of the invention and those of the comparative examples.
TABLE 1 catalyst compositions and physicochemical Properties of the inventive and comparative examples
Catalyst numbering MoO3，wt% NiO，wt% CoO，wt% SiO2，wt% P2O5，wt% Al2O3，wt% Specific surface area, m2/g Pore volume, mL/g
A 16.6 24.3 4.5 4.0 1.5 Balance of 252 0.357
B 18.0 23.8 3.3 4.1 1.5 Balance of 258 0.361
C 21.0 20.3 3.9 4.0 1.5 Balance of 255 0.358
D 17.9 22.1 5.2 3.9 1.4 Balance of 251 0.382
E 13.8 26.7 4.5 4.1 1.5 Balance of 245 0.355
F 10.2 13.3 22.6* 4.0 1.5 Balance of 170 0.288
G 17.8 22.2 5.1 4.0 1.5 Balance of 119 0.130
In Table 1, WO represents the catalyst F3In wt%.
Example 6
For the catalyst of the invention and the catalyst of the comparative example, the initial activity evaluation is carried out on a 200mL small hydrogenation device, the presulfurization is carried out before the catalyst evaluation, the presulfurization of the catalyst adopts a common sulfidization method, and the catalyst evaluation conditions are as follows: the pressure is 9.5MPa, and the volume space velocity is 1.1h-1The volume ratio of hydrogen to oil is 950:1, and the reaction temperature is 370 ℃. The main properties of the feed oil are shown in Table 2, and the results of the evaluation of the initial activity of the catalyst are shown in Table 3.
TABLE 2 Primary Properties of the base oils
Raw oil Iran VGO
Density (20 ℃ C.), g/cm3 0.9100
Distillation range, deg.C
IBP 325
EBP 526
S，wt% 1.44
N，µg/g 1356
TABLE 3 initial Activity evaluation results of catalysts of the present invention and comparative examples
Catalyst numbering A B C D E F G
Nitrogen content of the resulting oil, μ g/g 4.2 3.9 3.5 4.4 4.8 17.0 78.4
Sulfur content of the resulting oil, μ g/g 38 34 30 36 41 112 540
The data in Table 3 show that the hydrodenitrogenation activity of the catalyst of the present invention is greatly improved as compared to that of the comparative catalyst.

Claims (24)

1. A method of preparing a hydroprocessing catalyst, comprising:
(1) preparing oxide precursor slurry A of Al;
(2) preparing oxide precursor slurry B of Mo and Co;
(3) preparing oxide precursor slurry C of Mo and Ni;
(4) preparing oxide precursor slurry D of Ni;
(5) mixing the slurries obtained in the steps (1), (2), (3) and (4), then aging, filtering and drying;
(6) forming, washing, drying and roasting the material obtained in the step (5) to obtain a hydrotreating catalyst;
preparing oxide precursor slurry B of Mo and Co in the step (2) by adopting a precipitation method, namely preparing cobalt salt into an acidic solution B1, preparing molybdenum salt into an alkaline solution B2, and gelatinizing the acidic solution B1 and the alkaline solution B2 to obtain the oxide precursor slurry B;
preparing oxide precursor slurry C of Mo and Ni by adopting a precipitation method in the step (3), namely preparing nickel salt into an acidic solution C1, preparing molybdenum salt into an alkaline solution C2, and gelatinizing the acidic solution C1 and the alkaline solution C2 to obtain the oxide precursor slurry C;
in the step (2) and/or the step (3), ammonium carbonate and/or alkali metal carbonate are/is added in the gelling process;
and (4) preparing Ni oxide precursor slurry D by adopting a precipitation method, namely preparing nickel salt into an acidic solution D1, and neutralizing the acidic solution D1 with alkaline precipitator ammonia gas to form gel.
2. The method of claim 1, wherein: the Al oxide precursor in the step (1) is pseudo-boehmite.
3. The production method according to claim 1 or 2, characterized in that: the preparation method of the Al oxide precursor slurry A in the step (1) comprises the following steps: and (3) carrying out neutralization and precipitation by using aluminum salt solution and ammonia water in parallel flow to obtain slurry A, wherein the gelling temperature is 65-85 ℃, and the gelling pH value is 8-10.
4. The production method according to claim 1 or 2, characterized in that: the reaction conditions of the precipitation method for preparing the oxide precursor slurry B of Mo and Co in the step (2) are as follows: the reaction temperature is 75-90 ℃, the pH value is 4-6, and the molar ratio of Mo to Co is 1: 1.0 to 1.2.
5. The method of claim 1, wherein: the reaction conditions of the precipitation method for preparing the oxide precursor slurry C of Mo and Ni in the step (3) are as follows: the reaction temperature is 65-85 ℃, and the pH value is 4-6; wherein the molar ratio of Mo to Ni is 1: 1.0 to 1.2.
6. The method of claim 1, wherein: and (3) introducing 1/20-1/10 of the volume of the Al oxide precursor slurry A prepared in the step (1) in the step (2) and/or the step (3), wherein the volume of the Al oxide precursor slurry A accounts for the volume of the Al oxide precursor slurry A prepared in the step (1).
7. The method of claim 1, wherein: introducing cobalt in the step (2) and introducing nickel in the step (3), wherein the molar ratio of Co to Ni is 1: 1-1: 10.
8. the method of claim 1, wherein: introducing cobalt in the step (2) and introducing nickel in the step (3), wherein the molar ratio of Co to Ni is 1: 3-1: 8.
9. the method of claim 1, wherein: when ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (2), the addition amount is CO2The molar ratio of Mo used in the step (2) is 0.05-1.0; when ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (3), the addition amount is CO2The molar ratio of the Mo to the Mo used in the step (3) is 0.05-1.0.
10. The method of claim 1, wherein: when ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (2), the addition amount is CO2The molar ratio of Mo used in the step (2) is calculated to be 0.08-0.80; when ammonium carbonate salt and/or alkali metal carbonate salt is added in the step (3), the addition amount is CO2The molar ratio of Mo used in the step (3) is 0.08-0.80.
11. The production method according to claim 1 or 8, characterized in that: the ammonium carbonate salt and/or the alkali metal carbonate salt is one or more of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
12. The method of claim 1, wherein: the reaction conditions of the precipitation method for preparing the Ni oxide precursor slurry D in the step (4) are as follows: the reaction temperature is 40-65 ℃, and the pH value is 7-9; the molar ratio of the addition amount of Ni in the step (4) to Mo in the hydrotreating catalyst is 1-6: 1.
13. The method of claim 1, wherein: the molar ratio of the addition amount of Ni in the step (4) to Mo in the hydrotreating catalyst is 1-4: 1.
14. The method of claim 1, wherein: in the step (5), the slurries obtained in the steps (1), (2), (3) and (4) are mixed, the pH value is controlled to be 7-9, the temperature of the slurry is 65-90 ℃, the mixture is stirred for 10-30 minutes, and then aging is carried out.
15. The method of claim 1, wherein: aging in the step (5) under the following conditions: the pH value is 7-9, the aging temperature is 70-90 ℃, and the aging time is 0.5-3.0 hours.
16. The method of claim 1, wherein: the drying and baking conditions in step (6) are as follows: drying at 50-120 ℃ for 2.0-6.0 hours, and calcining at 450-600 ℃ for 3.0-6.0 hours.
17. The method of claim 1, wherein: introducing a catalyst promoter into at least one of the steps (1), (2), (3), (4), (5) and (6), wherein the promoter comprises one or more of Si, P, F, B, Zr and Ti, and the addition of the promoter is less than 25% of the weight of the hydrotreating catalyst calculated by oxide.
18. The method of claim 17, wherein: auxiliary agents Si and/or P.
19. The method of claim 17, wherein: the addition amount of the auxiliary agent is 1-15% of the weight of the hydrotreating catalyst calculated by oxide.
20. The method of claim 1, wherein: in the hydrotreating catalyst, the total weight content of the hydrogenation active metals Mo, Ni and Co calculated by oxides is 25-65 percent and the content of alumina is 35-75 percent on the basis of the weight of the hydrotreating catalyst.
21. The method of claim 1, wherein: in the hydrotreating catalyst, the total weight content of the hydrogenation active metals Mo, Ni and Co calculated by oxides is 30-55 percent and the content of alumina is 45-70 percent on the basis of the weight of the hydrotreating catalyst.
22. The production method according to claim 1 or 20, characterized in that: in the step (5), MoO is added3Molybdenum in MoO3Accounts for the total MoO in the hydroprocessing catalyst3Less than 30% by weight.
23. The method of claim 1, wherein: the hydrotreating catalyst contains an auxiliary agent P, and the weight of the hydrotreating catalyst is taken as a reference, and the auxiliary agent P is P2O5The content is 5.0% or less.
24. The method of claim 1, wherein: the hydrotreating catalyst contains an auxiliary agent Si, and takes the weight of the hydrotreating catalyst as a reference and takes SiO2The content is below 10.0%.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011072933A (en) * 2009-09-30 2011-04-14 Jgc Catalysts & Chemicals Ltd Hydrogenation catalyst of hydrocarbon and method for preparing the same
CN102268283A (en) * 2011-07-08 2011-12-07 中国石油天然气股份有限公司 Hydrorefining method of distillate oil
CN102319579A (en) * 2011-07-08 2012-01-18 中国石油天然气股份有限公司 Hydrofining catalyst and preparation method thereof
CN104841459A (en) * 2015-05-22 2015-08-19 中国海洋大学 Preparation method for nickel and cobalt molybdenum tungsten sulfide
CN104925757A (en) * 2015-05-21 2015-09-23 中国海洋大学 Coprecipitation preparation method for nickel-cobalt-tungsten-molybdenum composite oxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011072933A (en) * 2009-09-30 2011-04-14 Jgc Catalysts & Chemicals Ltd Hydrogenation catalyst of hydrocarbon and method for preparing the same
CN102268283A (en) * 2011-07-08 2011-12-07 中国石油天然气股份有限公司 Hydrorefining method of distillate oil
CN102319579A (en) * 2011-07-08 2012-01-18 中国石油天然气股份有限公司 Hydrofining catalyst and preparation method thereof
CN104925757A (en) * 2015-05-21 2015-09-23 中国海洋大学 Coprecipitation preparation method for nickel-cobalt-tungsten-molybdenum composite oxide
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