CN114471670B - Catalyst for hydrocracking and preparation method and application thereof - Google Patents

Catalyst for hydrocracking and preparation method and application thereof Download PDF

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CN114471670B
CN114471670B CN202011163452.3A CN202011163452A CN114471670B CN 114471670 B CN114471670 B CN 114471670B CN 202011163452 A CN202011163452 A CN 202011163452A CN 114471670 B CN114471670 B CN 114471670B
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molecular sieve
catalyst
hydrocracking catalyst
metal
type molecular
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CN114471670A (en
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高杭
柳伟
秦波
黄新露
杜艳泽
彭冲
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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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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/615—100-500 m2/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01J37/08—Heat treatment
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a hydrocracking catalyst, a preparation method and application thereof, wherein the method comprises the following steps: firstly, mixing a solution containing VIII group metal with an acidic cracking material, wherein the use amount of the VIII group metal solution is 20% -90%, preferably 30% -70% of the weight of the acidic cracking material by weight; secondly, mixing the mixed material with a VIB metal, a binder and a nitric acid solution, forming, drying and roasting to obtain the final hydrocracking catalyst, wherein the mass content of nitrate in the dried material is 1.0% -15.0%, preferably 2.5% -10.0%. The catalyst for hydrocracking is prepared by adopting a kneading method, so that the catalyst preparation flow is greatly shortened, the consumption of nitric acid is reduced, the catalyst preparation cost is reduced, and the catalyst has the characteristics of low metal consumption and high heavy naphtha selectivity.

Description

Catalyst for hydrocracking and preparation method and application thereof
Technical Field
The invention relates to a catalyst for hydrocracking and a preparation method and application thereof, in particular to a high-performance catalyst for hydrocracking and a preparation method and application thereof.
Background
Hydrocracking is a process of converting macromolecular substances in petroleum into small molecular substances at high temperature and pressure in the presence of hydrogen. The hydrogenation process converts heavy oil into ideal light oil components, improves the hydrogen-carbon ratio of reaction effluent, removes sulfur, nitrogen and metal impurities, and can meet the requirements of clean oil refining in the current world. By adopting different technological processes, selecting different operation modes, selecting different catalysts and adjusting different reaction conditions, the hydrocracking product can be regulated and controlled within a larger width range, and has the characteristics of high operation flexibility and high liquid yield.
The hydrocracking reaction follows a double-centered catalytic mechanism. The catalytic active center comprises an acid center and a metal center, and the synergistic effect of the two active centers ensures the smooth hydrocracking process. The cracking reaction and the isomerisation reaction are carried out on acid centres, and the acid carriers commonly used in industry today mainly comprise amorphous silica alumina, molecular sieves (Y, β) and mixtures of amorphous silica alumina and molecular sieves. The amorphous silica-alumina carrier has moderate strength acidity and larger pore diameter and pore volume, and macromolecules in the reactant easily enter the pore canal to contact with the acid center. Compared with amorphous silica-alumina, molecular sieve carriers are more acidic, but have smaller pore diameters, often requiring pore-expanding treatments. The metals supported on the support mainly play a role in hydrodeoxygenation, including noble metals (Pt, pd) and non-noble metals (Mo, W, co, ni). The metal has great influence on hydrogenation and dehydrogenation of raw material molecules and heteroatom removal, and plays a role in reducing the carbon deposition generation rate. The reactivity and product distribution can be adjusted by adjusting the hydrogenation and cracking properties of the catalyst. For a highly efficient hydrocracking catalyst, it is important that the reactant molecules be able to rapidly convert both at the acid center and at the metal center, avoiding secondary reactions.
CN105709803a discloses a catalyst preparation process for selective hydrogenation of heavy naphtha and tail oil. The method comprises the steps of impregnating a Mo-Co salt solution on a carrier for two times, drying and roasting, then putting the carrier into an organic solvent for unsaturated spray impregnation, then impregnating a metal salt solution again, and finally drying and roasting to obtain the finished catalyst. The method has complex process flow and high cost.
CN108722473a discloses a preparation method of a hydrocracking catalyst, wherein a new functional group is bonded to the surface of a carrier, and then a metal salt solution is impregnated. The method can weaken the interaction between the metal and the carrier and improve the metal dehydrogenation performance.
Ma Zhi et al, in the journal of Petroleum (Petroleum processing) volume 12, phase 3, P9-16, used a hydrocracking catalyst prepared by kneading method provided by the Fushun petrochemical institute and using molybdenum oxide, nickel nitrate and binder as raw materials, examined the influence of Ni-Mo atomic ratio on the acting force between metal and carrier,
there are many preparation methods of hydrocracking catalysts, and at present, an impregnation method and a kneading method are mainly used in industry, and industrial manufacturing cost and physical and chemical properties of the catalysts are generally considered when the preparation methods are selected. The impregnation method can lead the metal to be dispersed more uniformly on the surface of the carrier, but the preparation process flow is complex and the cost is higher. The kneading method has the advantages of simple and convenient preparation and lower cost. However, to ensure the strength of the catalyst, a large amount of acid (generally nitric acid) is often added in the preparation process to serve as a peptizing agent, so that the prepared catalyst has smaller pore diameter and higher nitride emission.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for hydrocracking and a preparation method and application thereof. The catalyst for hydrocracking is prepared by adopting a kneading method, so that the catalyst preparation flow is greatly shortened, the consumption of nitric acid is reduced, the catalyst preparation cost is reduced, and the catalyst has the characteristics of low metal consumption and high heavy naphtha selectivity.
A method of preparing a hydrocracking catalyst, the method comprising:
firstly, mixing a solution containing VIII group metal with an acidic cracking material, wherein the use amount of the VIII group metal solution is 20% -90%, preferably 30% -70% of the weight of the acidic cracking material by weight;
secondly, mixing the mixed material with a VIB metal, a binder and a nitric acid solution, forming, drying and roasting to obtain the final hydrocracking catalyst, wherein the mass content of nitrate in the dried material is 1.0% -15.0%, preferably 2.5% -10.0%.
In the method, the VIII metal is at least one of Co and Ni, the acidic cracking material is a Y-type molecular sieve and/or a beta-type molecular sieve, the solution of the VIII metal is an aqueous solution, and the VIII metal precursor is nitrate. The particle size range of the Y-type molecular sieve and/or the beta-type molecular sieve is 0.1-1.5 mu m, preferably 0.1-1.0 mu m, and the specific surface area is 350-1000 m 2 Preferably 380 to 950 m/g 2 Per gram, pore volume of 0.25-0.60 cm 3 Preferably 0.30 to 0.55 cm/g 3 /g, wherein the Y-type molecular sieve SiO 2 /Al 2 O 3 Beta molecular sieve SiO of 8-50, preferably 10-30 2 /Al 2 O 3 40 to 95, preferably 50 to 85.
In the above method, the solution containing the group VIII metal is added to the acid cracking material in 1 to 7, preferably 2 to 5 times, and stirring is preferably carried out during the addition.
In the method, the VIB group metal is at least one of Mo and W, the binder is alumina and/or amorphous silica-alumina, and the VIB group metal is metal salt and/or metal oxide. The specific surface area of the alumina is 300-850 m 2 Preferably 350 to 700 m 2 Per gram, the pore volume is 0.40-1.2 ml/g, preferably 0.60-1.05 ml/g; amorphous silicon aluminum with specific surface area of 200-600 m 2 Preferably 230 to 500 m 2 The pore volume per gram is 0.45-1.20 ml/g, preferably 0.55-1.00 ml/g.
In the method, the mass concentration of the nitric acid solution is 1-12 wt%, preferably 2-10 wt%, and more preferably 2-6 wt%.
In the method, the drying temperature is 100-150 ℃, the drying time is 12-24 hours, the roasting temperature is 400-600 ℃, and the roasting time is 2-6 hours.
The preparation method of the hydrocracking catalyst comprises the following steps:
(1) Dissolving one or more of the group VIII metal nitrates in an amount of deionized water;
(2) Weighing a certain amount of acid cracking material, mixing the acid cracking material with the VIII family metal solution obtained in the step (1), and recording the mixture as a mixture 1, wherein the amount of the VIII family metal solution is 20% -90%, preferably 30% -70% of the weight of the acid cracking material by weight;
(3) Uniformly mixing the VIB metal, the binder and the mixture 1, and marking as a mixture 2;
(4) In the rolling process of the mixture 2, adding a nitric acid solution, forming, drying at 100-150 ℃ for 12-24 hours, wherein the mass content of nitrate radical in the dried material is 1.0-15.0%, preferably 2.5-10.0%, and roasting at 400-500 ℃ for 2-6 hours to obtain the final hydrocracking catalyst.
In the step (1) of the method, the acidic cracking material is a Y-type molecular sieve and/or a beta-type molecular sieve, the particle size range of the Y-type molecular sieve and the beta-type molecular sieve is 0.1-1.5 mu m, preferably 0.1-1.0 mu m, and the specific surface area is 350-1000 m 2 Preferably 380 to 950 m/g 2 Per gram, pore volume of 0.25-0.60 cm 3 Preferably 0.30 to 0.55 cm/g 3 /g, wherein the Y-type molecular sieve SiO 2 /Al 2 O 3 Beta molecular sieve SiO of 8-50, preferably 10-30 2 /Al 2 O 3 40 to 95, preferably 50 to 85.
In the step (2) of the method, the solution containing the VIII family metal is added into the acid cracking material for 1-7 times, preferably 3-5 times under the stirring condition, and the material mixed by the acid cracking material and the VIII family metal solution is controlled to be in a uniform small particle aggregation state, and the small particle diameter is 1-4 mm.
And (3) in the method step, the VIB metal and the binder are sequentially added into the mixture 1, the VIB metal is added into the mixture 1 and then uniformly mixed, and then the binder is added and uniformly mixed.
In the step (3), the binder is alumina and/or amorphous silica-alumina, and the specific surface area of the alumina powder is 300-850 m 2 Preferably 350 to 700 m 2 Per gram, the pore volume is 0.40-1.2 ml/g, preferably 0.60-1.05 ml/g; amorphous silicon aluminum with specific surface area of 200-600 m 2 Preferably 230 to 500 m 2 The pore volume per gram is 0.45-1.20 ml/g, preferably 0.55-1.00 ml/g.
In the step (3), other auxiliary agents may be further added, and the auxiliary agents may be one or more of structure auxiliary agents, hole enlarging auxiliary agents and the like, and are used for adjusting the interaction between the active metal and the carrier, so as to facilitate the metal to generate an active phase with better dispersion, preferably one or more of macromolecular organic matters and organic alcohols, and further preferably one or more of methylcellulose and polyethylene glycol.
In the method step (4), the mass concentration of the nitric acid solution is 1-12 wt%, preferably 2-10 wt%, and more preferably 2-6 wt%.
The hydrocracking catalyst is prepared by adopting the method, and comprises hydrogenation active metal and an acid cracking material, wherein the hydrogenation active metal component is VIB group metal and/or VIII group metal, the VIB group metal is one or more of Mo and W, the VIII group metal is one or more of Co and Ni, the acid cracking material is a Y-type molecular sieve and/or a beta-type molecular sieve, the weight of the final hydrocracking catalyst is taken as a reference, the mass content of the Y-type molecular sieve and/or the beta-type molecular sieve is 10-80%, the weight content of the VIB group metal is 5-30% in terms of oxide, and the content of the VIII group metal is 2-20% in terms of oxide.
In the above catalyst, the hydrocracking catalyst further contains a binder, wherein the binder is alumina and/or amorphous silica-alumina, and the weight content of the alumina and/or amorphous silica-alumina is 10-80% based on the weight of the final hydrocracking catalyst.
Among the above catalysts, the hydrocracking catalyst has the following properties: specific surface area of 280-480 m 2 Preferably 300 to 450m 2 Per gram, the pore volume is 0.25 to 0.50ml/g, preferably 0.35 to 0.48ml/g, the mechanical strength is 130 to 350N/mm, preferably 150 to 280N/mm, and the bulk density is 0.65 to 0.78g/cm 3 Preferably 0.69 to 0.75g/cm 3 。
The hydrocracking catalyst is used for hydrocracking reaction, and the reaction conditions are as follows: the reaction pressure is 7-16 MPa, the reaction temperature is 300-500 ℃ and the volume space velocity is 0.7-2.0 h -1 The volume ratio of hydrogen to oil is 700-1800.
Compared with the existing hydrocracking catalyst, the method has the following advantages: the VIII family metal is firstly mixed with the acid cracking material, so that the utilization rate of the VIII family metal can be improved, the dispersity of the VIII family metal in the acid cracking material can be improved, and the metal consumption can be reduced; in addition, the invention can greatly reduce the consumption of nitric acid and reduce the emission of nitride under the condition that the hydrocracking catalyst reaches the same strength, thereby being an environment-friendly preparation process.
Detailed Description
The effects and advantages of the process according to the invention are further illustrated by the following examples and comparative examples, which are not to be construed as limiting the process according to the invention, in which the percentages are by mass unless otherwise specified.
The Y-type molecular sieves used in the examples and comparative examples of the present invention have the following properties: the total pore volume is 0.36-0.60 ml/g, and the specific surface area is 650-1000 m 2 /g; the beta molecular sieve properties are as follows: the total pore volume is 0.35-0.50 ml/g, and the specific surface area is 600-800 m 2 /g; the properties of alumina are as follows: pore volume of 0.60-1.10 ml/g and specific surface area of 300-480 m 2 /g; the amorphous silicon aluminum has the following properties: the pore volume is 0.50-0.95 ml/g, and the specific surface area is 260-450 m 2 /g。
The Y-type molecular sieves used in the examples and comparative examples of the present invention have the following properties: the total pore volume was 0.45ml/g, and the specific surface area was 821m 2 /g; the beta molecular sieve properties are as follows: the total pore volume was 0.40ml/g and the specific surface area was 673m 2 /g; the properties of alumina are as follows: pore volume of 0.87ml/g, specific surface area of 443m 2 /g; the amorphous silicon aluminum has the following properties: pore volume of 0.76ml/g, specific surface area of 359m 2 /g。
Example 1
Adding nickel nitrate into 70ml of deionized water for full dissolution to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in a stirring state for 4 times in an equivalent manner according to the proportion that the mass of the nickel active metal solution is 50% of the mass of the Y molecular sieve to form a small particle aggregation state material which is recorded as a mixture 1, wherein the small particle diameter is 1-4 mm; adding molybdenum oxide, aluminum oxide powder and amorphous silicon aluminum into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 130ml of 2.5wt% nitric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the dried material, placing the dried material into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises nickel nitrate 5.6%, molybdenum oxide 18.4%, Y-type molecular sieve 45%, aluminum oxide 20%, amorphous silicon aluminum 11%, and the properties are shown in table 1.
Example 2
Adding nickel nitrate into 40ml of deionized water for full dissolution to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in a stirring state for 3 times in an equivalent manner according to the proportion that the mass of the nickel active metal solution is 60% of the mass of the Y molecular sieve to form a small particle aggregation state material which is recorded as a mixture 1, wherein the small particle diameter is 1-4 mm; adding molybdenum oxide, aluminum oxide powder and amorphous silicon aluminum into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 150ml of 2wt% nitric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the dried material, placing the dried material into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises nickel nitrate 5.6%, molybdenum oxide 18.4%, Y-type molecular sieve 25%, aluminum oxide 21% and amorphous silicon aluminum 30%, and the properties of the final hydrocracking catalyst are shown in table 1.
Example 3
Adding nickel nitrate into 30ml of deionized water for full dissolution to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in a stirring state for 2 times in an equivalent manner according to the proportion that the mass of the nickel active metal solution is 65% of the mass of the Y molecular sieve to form a small particle aggregation state material which is recorded as a mixture 1, wherein the small particle diameter is 1-3 mm; adding molybdenum oxide, aluminum oxide powder and amorphous silicon aluminum into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 170ml of 2wt% nitric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the material after drying, placing the material into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst is nickel nitrate 2.5%, molybdenum oxide 18.5%, Y-type molecular sieve 15%, aluminum oxide 34% and amorphous silicon aluminum 30%, and the properties of the final hydrocracking catalyst are shown in table 1.
Example 4
Adding nickel nitrate into 30ml of deionized water to fully dissolve to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in 2 times of equal amount under the stirring state according to the proportion that the mass of the nickel active metal solution is 50% of the mass of the Y molecular sieve to form a small particle aggregation state material, wherein the mixture 1 is in a partial aggregation state and forms small particles, and the diameter of the small particles is 1-3 mm; adding molybdenum oxide and aluminum oxide powder into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 170ml of 1wt% nitric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the material, placing the material into a muffle furnace, roasting at 500 ℃ for 4 hours, and obtaining the final hydrocracking catalyst with the following composition of nickel nitrate 4.5%, molybdenum oxide 25.5%, Y-type molecular sieve 20%, aluminum oxide 50%, and properties shown in table 1.
Example 5
Adding nickel nitrate into 100ml of deionized water to fully dissolve to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in 5 times of equal amount under the stirring state according to the proportion that the mass of the nickel active metal solution is 50% of the mass of the Y molecular sieve to form a small particle aggregation state material, wherein the mixture 1 is in a partial aggregation state and forms small particles, and the diameter of the small particles is 2-4 mm; adding molybdenum oxide and aluminum oxide powder into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 100ml of 3wt% nitric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the material, placing the material into a muffle furnace, roasting at 500 ℃ for 4 hours, and obtaining the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises 7.0% of nickel nitrate, 8.0% of molybdenum oxide, 65% of Y-type molecular sieve and 20% of aluminum oxide, and the properties of the final hydrocracking catalyst are shown in table 1.
Example 6
Adding nickel nitrate into 100ml of deionized water to fully dissolve to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in 5 times of equal amount under the stirring state according to the proportion that the mass of the nickel active metal solution is 40% of the mass of the Y molecular sieve to form a small particle aggregation state material, wherein the mixture 1 is in a partial aggregation state and forms small particles, and the diameter of the small particles is 1-3 mm; adding molybdenum oxide and aluminum oxide powder into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 100ml of 7wt% nitric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the material, placing the material into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises nickel nitrate 6.0%, molybdenum oxide 6.0%, Y-type molecular sieve 80%, aluminum oxide 8.0%, and the properties of the final hydrocracking catalyst are shown in table 1.
Example 7
Adding nickel nitrate into 30ml of deionized water to fully dissolve to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in 2 times of equal amount under the stirring state according to the proportion that the mass of the nickel active metal solution is 85% of the mass of the Y molecular sieve to form a small particle aggregation state material, namely a mixture 1, wherein the mixture 1 is in a partial aggregation state, small particles are formed, and the diameter of the small particles is 1-4 mm; adding molybdenum oxide and aluminum oxide powder into the mixture 1 in sequence to mix to obtain a mixture 2, rolling the mixture 2, adding 200ml of 7wt% hydrochloric acid solution in total in the rolling process, placing the formed material into a 120 ℃ oven for 12 hours, taking out the dried material, placing the dried material into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises 9.5% of nickel nitrate, 20.5% of molybdenum oxide, 20% of Y-type molecular sieve and 50% of aluminum oxide, and the properties of the final hydrocracking catalyst are shown in table 1.
Example 8
Adding nickel nitrate into 80ml of deionized water for full dissolution to obtain a solution containing nickel active metal, adding the nickel active metal solution into a Y molecular sieve and a Beta molecular sieve for mixing in an equal amount for 4 times in a stirring state according to the proportion that the mass of the nickel active metal solution is 60% of the mass of the molecular sieve, and marking the mixture as a mixture 1, wherein the small particle aggregation state material is formed, and the small particle diameter is 1-4 mm. Adding all molybdenum oxide, aluminum oxide powder and amorphous silicon aluminum into the mixture 1, mixing, and rolling. In the rolling process, 90ml of 4wt% nitric acid solution is added in total, the formed material is placed in a baking oven at 120 ℃ for 12 hours, the nitrate mass content in the dried material is 3.8%, the dried material is taken out and placed in a muffle furnace for roasting at 500 ℃ for 4 hours, and the final hydrocracking catalyst is obtained, wherein the composition of the final hydrocracking catalyst comprises 3.5% of nickel nitrate, 13.5% of molybdenum oxide, 25% of Y-type molecular sieve, 15% of Beta-type molecular sieve, 33% of alumina and 10% of amorphous silica-alumina, and the properties are shown in Table 1.
Comparative example 1
The catalyst is prepared according to the existing hydrocracking catalyst kneading method preparation process. The molecular sieve, alumina and/or amorphous silica-alumina, nickel nitrate, molybdenum oxide and other material components used in example 2 were all charged into the mill. In the rolling process, adding 6wt% nitric acid solution for multiple times, adding 200ml in total, rolling until the mixture is rolled and molded to obtain the hydrocracking catalyst, putting the hydrocracking catalyst into a baking oven at 120 ℃ for 24 hours, taking out the hydrocracking catalyst, putting the hydrocracking catalyst into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final product, wherein the mass content of nitrate in the dried material is 5.9%.
Comparative example 2
The catalyst is prepared according to the existing preparation process of the hydrocracking catalyst by an impregnation method. Weighing 25% of the Y-type molecular sieve, 45% of the alumina and 30% of the amorphous silicon aluminum, and putting all the material components into a rolling machine for rolling. In the rolling process, adding 6wt% nitric acid solution for multiple times, adding 400ml in total, and rolling until the mixture is rolled and molded to obtain the catalyst carrier. And (3) placing the catalyst carrier into a baking oven at 120 ℃ for 12 hours, taking out, placing into a muffle furnace, and roasting at 550 ℃ for 4 hours to obtain the catalyst carrier.
The catalyst carrier is impregnated according to the existing impregnation process, and a molybdenum-nickel metal impregnation liquid is prepared according to the proportion of 8% of nickel nitrate and 20% of molybdenum oxide. And (3) excessively soaking the roasted catalyst carrier in the metal solution for 24 hours to obtain a hydrocracking catalyst, putting the hydrocracking catalyst in a baking oven at 120 ℃ for 24 hours, taking out the dried material, putting the dried material into a muffle furnace, and roasting at 500 ℃ for 6 hours to obtain a final product.
Comparative example 3
The catalyst is prepared according to the existing hydrocracking catalyst kneading method preparation process. The molecular sieve, alumina and/or amorphous silica-alumina, nickel nitrate, molybdenum oxide and other material components used in example 6 were all charged into the mill. In the rolling process, adding 10wt% nitric acid solution for multiple times, adding 200ml in total, rolling until the mixture is rolled and molded to obtain the hydrocracking catalyst, putting the hydrocracking catalyst into a baking oven at 120 ℃ for 24 hours, taking out the hydrocracking catalyst, putting the hydrocracking catalyst into a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final product, wherein the mass content of nitrate in the dried material is 9.9%.
Comparative example 4
The catalyst is prepared according to the existing hydrocracking catalyst kneading method preparation process. The molecular sieve, alumina and/or amorphous silica alumina, nickel nitrate, molybdenum oxide and other material components used in example 7 were all charged into the mill. In the rolling process, adding 10wt% hydrochloric acid solution for multiple times, adding 200ml in total, rolling until the mixture is rolled and molded to obtain the hydrocracking catalyst, placing the hydrocracking catalyst in a 120 ℃ oven for 24 hours, taking out the dried material, placing the dried material in a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain the final product.
TABLE 1 physical and chemical Properties of hydrocracking catalyst
Catalytic performance evaluation of hydrocracking catalyst:
after the catalyst was presulfided, it was evaluated using a 200ml small hydrogenation apparatus, wherein the properties of the feedstock oil used are shown in Table 1, the reaction process conditions are shown in Table 2, and the comparative results of the catalyst reactivity are shown in Table 3. When evaluating the series of catalysts, raw oil passes through a hydrofining catalyst bed layer and a hydrocracking catalyst bed layer in sequence. After the raw oil is hydrofined, the organic nitrogen content is controlled to be less than 5ppm.
TABLE 2 Properties of raw oil
TABLE 3 Process conditions and catalyst reactivity
The evaluation results in table 3 show that when the reaction conversion rate is controlled to be 75%, compared with the reaction performance of the hydrocracking catalyst prepared by the traditional kneading method and the soaking method, the reaction temperature of the hydrocracking catalyst prepared continuously in the method is basically consistent, and the yields of the heavy naphtha and aviation kerosene product fractions of the catalyst prepared by the method of the invention are basically consistent with those of the comparative example 2 prepared by the soaking method, and slightly due to the comparative example 1 prepared by the traditional kneading method. The results show that the reaction performance of the hydrocracking catalyst prepared by the method is basically consistent with that of the catalyst obtained by the existing impregnation method.

Claims (15)

1. A preparation method of a hydrocracking catalyst is characterized in that: the method comprises the following steps:
(1) Dissolving one or more of the group VIII metal nitrates in an amount of deionized water;
(2) Weighing a certain amount of acid cracking material, mixing the acid cracking material with the VIII family metal solution obtained in the step (1), and marking the mixture as a mixture 1, wherein the amount of the VIII family metal solution is 20% -90% of the weight of the acid cracking material by weight;
(3) Uniformly mixing the VIB group metal oxide, the binder and the mixture 1, and marking as a mixture 2;
(4) Adding a nitric acid solution in the rolling process of the mixture 2, forming, drying and roasting to obtain a final hydrocracking catalyst, wherein the mass content of nitrate in the dried material is 1.0% -15.0%;
the VIII metal is at least one of Co and Ni, and the acidic cracking material is a Y-type molecular sieve or a Y-type molecular sieve and a beta-molecular sieve;
the VIB metal is at least one of Mo and W, and the binder is alumina and/or amorphous silica-alumina.
2. The method according to claim 1, characterized in that: the use amount of the VIII group metal solution is 30% -70% of the weight of the acidic cracking material by weight; the mass content of nitrate radical in the dried material is 2.5% -10.0%.
3. The method according to claim 1, characterized in that: the particle size range of the Y-type molecular sieve or the beta-type molecular sieve is 0.1-1.5 mu m, and the specific surface area is 350-1000 m 2 Per gram, pore volume of 0.25-0.60 cm 3 /g, wherein the Y-type molecular sieve SiO 2 /Al 2 O 3 8-50, beta molecular sieve SiO 2 /Al 2 O 3 40-95.
4. A method according to claim 3, characterized in that: the particle size range of the Y-type molecular sieve or the beta-type molecular sieve is 0.1-1.0 mu m, and the specific surface area is 380-950 m 2 Per gram, a pore volume of 0.30 to 0.55cm 3 /g, wherein the Y-type molecular sieve SiO 2 /Al 2 O 3 10-30 of beta molecular sieve SiO 2 /Al 2 O 3 50-85.
5. The method according to claim 1, characterized in that: the group VIII metal solution is added to the acid cracking material in one or more portions and is agitated during the addition.
6. The method according to claim 1, characterized in that: the specific surface area of the alumina is 300-850 m 2 Per gram, the pore volume is 0.40-1.2 mL/g; amorphous silicon aluminum with specific surface area of 200-600 m 2 And/g, wherein the pore volume is 0.45-1.20 mL/g.
7. The method according to claim 6, wherein: the specific surface area of the alumina is 350-700 m 2 Per gram, the pore volume is 0.60-1.05 mL/g; the specific surface area of amorphous silicon aluminum is 230-500 m 2 And/g, wherein the pore volume is 0.55-1.00 mL/g.
8. The method according to claim 1, characterized in that: the mass concentration of the nitric acid solution is 1-12wt%.
9. The method according to claim 1, characterized in that: the drying temperature is 100-150 ℃, the drying time is 12-24 hours, the roasting temperature is 400-600 ℃, and the roasting time is 2-6 hours.
10. The method according to claim 1, characterized in that: and (4) drying at 100-150 ℃ for 12-24 hours, and roasting at 400-500 ℃ for 2-6 hours to obtain the final hydrocracking catalyst.
11. A hydrocracking catalyst characterized by: a preparation by the method of any one of claims 1 to 10.
12. The catalyst of claim 11, wherein: the hydrocracking catalyst comprises hydrogenation active metal and an acidic cracking material, wherein the hydrogenation active metal comprises VIB group metal and VIII group metal, the VIB group metal is one or more of Mo and W, the VIII group metal is one or more of Co and Ni, the acidic cracking material is a Y-type molecular sieve or a Y-type molecular sieve and a beta-molecular sieve, the weight content of the Y-type molecular sieve or the Y-type molecular sieve and the beta-molecular sieve is 10-80% based on the weight of the final hydrocracking catalyst, the weight content of the VIB group metal is 5-30% based on oxide, and the content of the VIII group metal is 2-20% based on oxide.
13. The catalyst of claim 12, wherein: the hydrocracking catalyst contains a binder, wherein the binder is alumina and/or amorphous silica-alumina, and the weight content of the alumina and/or amorphous silica-alumina is 10-80% based on the weight of the final hydrocracking catalyst.
14. The catalyst of claim 13, wherein: the hydrocracking catalyst has the following properties: specific surface area of 280-480 m 2 Per gram, the pore volume is 0.25 to 0.50mL/g, the mechanical strength is 130 to 350N/mm, and the bulk density is 0.65 to 0.78g/cm 3 。
15. The use of a hydrocracking catalyst according to any one of claims 11 to 14 for a hydrocracking reaction, characterized in that: the reaction conditions were as follows: the reaction pressure is 7-16 MPa, the reaction temperature is 300-500 ℃ and the volume space velocity is 0.7-2.0 h -1 The volume ratio of hydrogen to oil is 700-1800.
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Publication number Priority date Publication date Assignee Title
CN102786064A (en) * 2012-08-21 2012-11-21 中国海洋石油总公司 Hydrocracking catalyst carrier and preparation method thereof
CN103100402A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst
CN103100400A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst
CN105642337A (en) * 2014-12-04 2016-06-08 中国石油化工股份有限公司 Preparation technology of hydrocracking catalyst
CN105709808A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Hydro-cracking catalyst and preparation method thereof
CN110237856A (en) * 2018-03-08 2019-09-17 中国石油天然气股份有限公司 A kind of preparation method of poor quality/heavy diesel fuel hydrocracking catalyst

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Publication number Priority date Publication date Assignee Title
CN103100402A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst
CN103100400A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst
CN102786064A (en) * 2012-08-21 2012-11-21 中国海洋石油总公司 Hydrocracking catalyst carrier and preparation method thereof
CN105642337A (en) * 2014-12-04 2016-06-08 中国石油化工股份有限公司 Preparation technology of hydrocracking catalyst
CN105709808A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Hydro-cracking catalyst and preparation method thereof
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