CN114471670A - 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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CN114471670A
CN114471670A CN202011163452.3A CN202011163452A CN114471670A CN 114471670 A CN114471670 A CN 114471670A CN 202011163452 A CN202011163452 A CN 202011163452A CN 114471670 A CN114471670 A CN 114471670A
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molecular sieve
group metal
metal
catalyst
hydrocracking catalyst
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CN114471670B (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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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J29/166—Y-type faujasite
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • 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
    • C10G47/16—Crystalline alumino-silicate carriers
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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 and 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 dosage of the VIII group metal solution is 20-90% of the weight of the acidic cracking material by weight, and preferably 30-70%; secondly, the mixed material is mixed with VIB group metal, a binder and a nitric acid solution and is subjected to forming treatment, and the final hydrocracking catalyst is prepared after drying and roasting, wherein the mass content of nitrate radicals 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 preparation process of the catalyst is greatly shortened, the dosage of nitric acid is reduced, and the preparation cost of the catalyst is reduced.

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 technology is a process of converting macromolecular substances in petroleum into small molecular substances under the conditions of high temperature, high pressure and hydrogen existence. 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 requirement of clean oil refining in the world at present. By adopting different process flows, selecting different operation modes, selecting different catalysts and adjusting different reaction conditions, the hydrocracking product can be regulated and controlled within a wider range, and the method has the characteristics of high operation flexibility and high liquid yield.
The hydrocracking reaction follows a two-site catalytic mechanism. The catalytic active center comprises an acid center and a metal center, and the two active centers have synergistic effect to ensure the smooth operation of the hydrocracking process. The cracking and isomerization reactions are carried out on acid centers and the acidic supports which are common in industry today mainly comprise amorphous silica-aluminas, molecular sieves (Y, β) and mixtures of amorphous silica-aluminas and molecular sieves. The amorphous silica-alumina carrier has moderate acidity and larger pore size and pore volume, and macromolecules in reactants easily enter the inside of a pore passage to contact with an acid center. Compared with amorphous silica-alumina, the molecular sieve carrier has strong acidity but small pore size, and often needs to be subjected to pore-expanding treatment. The metal loaded on the carrier mainly plays a role in hydrogenation and dehydrogenation, and comprises noble metal (Pt and Pd) and non-noble metal (Mo, W, Co and Ni). The metal has great influence on the hydrogenation and dehydrogenation of raw material molecules and the removal of heteroatoms, and plays a role in reducing the generation rate of carbon deposit. The reaction activity and product distribution can be adjusted by adjusting the hydrogenation performance and cracking performance of the catalyst. For a highly efficient hydrocracking catalyst, it is important that the reactant molecules are able to rapidly convert at the acid and metal centers, avoiding secondary reactions.
CN105709803A discloses a catalyst preparation process for selective hydrogenation of heavy naphtha and tail oil. The method needs two impregnation processes, firstly, a Mo-Co salt solution is impregnated on a carrier, the carrier is placed into an organic solvent for unsaturated spray impregnation after drying and roasting, then, a metal salt solution is impregnated again, and finally, the finished catalyst is obtained through drying and roasting. The method has the advantages of complex process flow and high cost.
CN108722473A discloses a preparation method of a hydrocracking catalyst, which bonds new functional groups on the surface of a carrier, and then impregnates a metal salt solution. The method can weaken the interaction between the metal and the carrier and improve the metal addition/dehydrogenation performance.
Marizhi et al, volume 12, No. 3, P9-16, used a hydrocracking catalyst prepared by Fushu petrochemical research institute and using molybdenum oxide, nickel nitrate and an adhesive as raw materials, and examined the influence of Ni and Mo atoms on the acting force between the metal and the carrier,
the hydrocracking catalyst has a plurality of preparation methods, at present, an impregnation method and a kneading method are mainly used in industry, and the preparation method is usually selected by considering the industrial manufacturing cost and the physical and chemical properties of the catalyst. The impregnation method can lead the metal to be dispersed on the surface of the carrier more uniformly, but the preparation process flow is complex and the cost is higher. The kneading method has the advantages of simple preparation and low cost. However, in order to ensure the strength of the catalyst, a large amount of acid (generally adopting nitric acid) is often added as a peptizing agent in the preparation process, so that the prepared catalyst has small aperture and high emission of nitride.
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 preparation process of the catalyst is greatly shortened, the dosage of nitric acid is reduced, and the preparation cost of the catalyst is reduced.
A process for preparing a hydrocracking catalyst, said process comprising the steps of:
firstly, mixing a solution containing VIII group metal with an acidic cracking material, wherein the dosage of the VIII group metal solution is 20-90% of the weight of the acidic cracking material by weight, and preferably 30-70%;
secondly, the mixed material is mixed with VIB group metal, a binder and a nitric acid solution and is subjected to forming treatment, and the final hydrocracking catalyst is prepared after drying and roasting, wherein the mass content of nitrate radicals in the dried material is 1.0-15.0%, preferably 2.5-10.0%.
In the above method, the group VIII metal is at least one of Co and Ni, the acidic cracking material is a Y-type molecular sieve and/or a β -type molecular sieve, the solution of the group VIII metal is an aqueous solution, and the group VIII metal precursor is a nitrate thereof. The particle size range of the Y-type molecular sieve and/or the beta molecular sieve is 0.1-1.5 mu m, preferably 0.1-1.0 mu m, and the specific surface area is 350-1000 m2Per g, preferably 380 to 950m2Per g, pore volume of 0.25-0.60 cm3Per g, preferably 0.30 to 0.55cm3In the formula,/g, wherein, molecular sieve SiO of Y type2/Al2O38 to 50, preferably 10 to 30, beta molecular sieve SiO2/Al2O340 to 95, preferably 50 to 85.
In the above process, the group VIII metal-containing solution is added to the acidic cracking material in 1 to 7, preferably 2 to 5, portions, preferably with stirring, 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 silicon-aluminum, and the VIB group metal is a metal salt and/or a metal oxide. Of the said aluminaThe specific surface area is 300-850 m2Per g, preferably 350 to 700 m2The pore volume is 0.40-1.2 ml/g, preferably 0.60-1.05 ml/g; the amorphous silica-alumina specific surface area is 200-600 m2Per g, preferably 230 to 500 m2The pore volume 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 in the embodiment of the invention comprises the following steps:
(1) dissolving one or more group VIII metal nitrates in a quantity of deionized water;
(2) weighing a certain amount of acid cracking materials, mixing the acid cracking materials with the VIII group metal solution obtained in the step (1), and recording the mixture as a mixture 1, wherein the VIII group metal solution is used in an amount of 20-90% by weight, preferably 30-70% by weight, of the weight of the acid cracking materials;
(3) uniformly mixing a VIB group metal, a 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 at 100-150 ℃ for 12-24 hours, wherein the mass content of nitrate 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), the acidic cracking material is a Y-type molecular sieve and/or a beta molecular sieve, the particle size range of the Y-type molecular sieve and the beta molecular sieve is 0.1-1.5 μm, preferably 0.1-1.0 μm, and the specific surface area is 350-1000 m2Per g, preferably 380 to 950m2Per g, pore volume of 0.25-0.60 cm3Per g, preferably 0.30 to 0.55cm3In the formula,/g, wherein, molecular sieve SiO of Y type2/Al2O38 to 50, preferably 10 to 30, beta molecular sieve SiO2/Al2O340 to 95, preferably 50 to 85.
In the step (2), the solution containing the VIII group metal is added to the acidic cracking material in 1-7 times, preferably 3-5 times, under the stirring condition, and the material obtained after the acidic cracking material is mixed with the VIII group metal solution is controlled to be in a uniform small particle aggregation state, wherein the diameter of each small particle is 1-4 mm.
In the step (3), the group VIB metal and the binder are sequentially added into the mixture 1, and the group VIB metal is added into the mixture 1, mixed uniformly, and then added with the binder and mixed uniformly.
In the step (3), the binder is alumina and/or amorphous silicon-aluminum, and the specific surface area of the alumina powder is 300-850 m2Per g, preferably 350 to 700 m2The pore volume is 0.40-1.2 ml/g, preferably 0.60-1.05 ml/g; the amorphous silica-alumina specific surface area is 200-600 m2Per g, preferably 230 to 500 m2The pore volume is 0.45-1.20 ml/g, preferably 0.55-1.00 ml/g.
In the step (3), other additives may be further added, and the additives may be one or more of structural additives, pore-expanding additives 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 substances and organic alcohols, and further preferably one or more of methylcellulose and polyethylene glycol.
In the step (4), the mass concentration of the nitric acid solution is 1 to 12wt%, preferably 2 to 10wt%, and more preferably 2 to 6 wt%.
A hydrocracking catalyst is prepared by the method, and comprises hydrogenation active metal and an acidic cracking material, wherein the hydrogenation active metal 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 acidic cracking material is a Y-type molecular sieve and/or a beta molecular sieve, the mass content of the Y-type molecular sieve and/or the beta molecular sieve is 10-80% based on the weight of the final hydrocracking catalyst, the mass content of the VIB group metal is 5-30% by weight calculated on oxides, and the content of the oxides of the VIII group metal is 2-20% by weight calculated on oxides.
In the catalyst, the hydrocracking catalyst further contains a binder, the binder is alumina and/or amorphous silicon-aluminum, and the weight content of the alumina and/or amorphous silicon-aluminum is 10-80% based on the weight of the final hydrocracking catalyst.
In the above catalyst, the hydrocracking catalyst has the following properties: the specific surface area is 280-480 m2A concentration of 300 to 450m is preferred2Per g, 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/cm3Preferably 0.69 to 0.75g/cm3。
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--1And the volume ratio of the hydrogen to the oil is 700-1800.
Compared with the existing hydrocracking catalyst, the method has the following advantages: the VIII group metal is mixed with the acidic cracking material, so that the utilization rate of the VIII group metal and the dispersion degree of the VIII group metal in the acidic cracking material can be improved, and the metal consumption is reduced; in addition, the invention can greatly reduce the dosage of nitric acid under the condition that the hydrocracking catalyst achieves the same strength, and the preparation process with less nitride emission is environment-friendly.
Detailed Description
The effects and advantages of the process of the present invention will be further illustrated by the following examples and comparative examples, but the following examples are not intended to limit the process of the present invention, and% are by mass unless otherwise specified in the context of the present invention.
The Y-type molecular sieve adopted in the inventive example and the comparative example has the following properties: the total pore volume is 0.36-0.60 ml/g, and the specific surface area is 650-1000 m2(iv) g; the beta molecular sieve has the following properties: the total pore volume is 0.35-0.50 ml/g, and the specific surface area is 600-800 m2(ii)/g; the properties of the alumina are as follows: the pore volume is 0.60-1.10 ml/g, the specific surface area is 300-480 m2(ii)/g; the properties of amorphous silica-alumina are as follows: the pore volume is 0.50-0.95 ml/g, the specific surface area is 260-450 m2/g。
The Y-type molecular sieve adopted in the inventive example and the comparative example has the following properties: the total pore volume is 0.45ml/g and the specific surface area is 821m2(ii)/g; the beta molecular sieve has the following properties: the total pore volume is 0.40ml/g, the specific surface area is 673m2(ii)/g; the properties of the alumina are as follows: pore volume of 0.87ml/g and specific surface area of 443m2(ii)/g; the properties of amorphous silica-alumina are as follows: pore volume of 0.76ml/g and specific surface area of 359m2/g。
Example 1
Adding nickel nitrate into 70ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in 4 times of equal amount under stirring according to the proportion that the mass of the nickel active metal solution is 50% of that of the Y molecular sieve to form a small-particle aggregation material which is marked as a mixture 1, wherein the diameter of each small particle is 1-4 mm; adding molybdenum oxide, alumina powder and amorphous silica-alumina into the mixture 1 in sequence for mixing 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 material and placing the material into a muffle furnace for roasting at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises 5.6% of nickel nitrate, 18.4% of molybdenum oxide, 45% of Y-type molecular sieve, 20% of alumina and 11% of amorphous silica-alumina, and the properties of the final hydrocracking catalyst are shown in Table 1.
Example 2
Adding nickel nitrate into 40ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in an equal amount of 3 times under a stirring state according to the proportion that the mass of the nickel active metal solution is 60% of that of the Y molecular sieve to form a small-particle aggregation material which is marked as a mixture 1, wherein the diameter of each small particle is 1-4 mm; adding molybdenum oxide, alumina powder and amorphous silica-alumina into the mixture 1 in sequence for mixing to obtain a mixture 2, rolling the mixture 2, adding 150ml of 2wt% nitric acid solution 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 the material at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises 5.6% of nickel nitrate, 18.4% of molybdenum oxide, 25% of Y-type molecular sieve, 21% of alumina and 30% of amorphous silicon-aluminum, and the properties of the final hydrocracking catalyst are shown in Table 1.
Example 3
Adding nickel nitrate into 30ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, and adding the nickel active metal solution into a Y molecular sieve in an equal amount of 2 times under a stirring state according to the proportion that the mass of the nickel active metal solution is 65% of that of the Y molecular sieve to form a small-particle aggregation material which is marked as a mixture 1, wherein the diameter of each small particle is 1-3 mm; adding molybdenum oxide, alumina powder and amorphous silica-alumina into the mixture 1 in sequence for mixing to obtain a mixture 2, rolling the mixture 2, adding 170ml of 2wt% nitric acid solution 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 the material at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst is 2.5% of nickel nitrate, 18.5% of molybdenum oxide, 15% of Y-type molecular sieve, 34% of alumina and 30% of amorphous silica-alumina, and the properties of the final hydrocracking catalyst are shown in Table 1.
Example 4
Adding nickel nitrate into 30ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, adding the nickel active metal solution into a Y molecular sieve in an equal amount for 2 times under a stirring state according to the proportion that the mass of the nickel active metal solution is 50% of that of the Y molecular sieve to form a small-particle aggregation-state material which is marked as a mixture 1, 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 for mixing 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, and roasting the material at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst with the following compositions of 4.5% of nickel nitrate, 25.5% of molybdenum oxide, 20% of Y-type molecular sieve and 50% of aluminum oxide, wherein the properties of the final hydrocracking catalyst are shown in Table 1.
Example 5
Adding nickel nitrate into 100ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, adding the nickel active metal solution into a Y molecular sieve in 5 times of equal amount under stirring according to the proportion that the mass of the nickel active metal solution is 50% of that of the Y molecular sieve to form a small-particle aggregation material which is marked as a mixture 1, 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 for mixing 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, and roasting the material at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst with the following components of 7.0% of nickel nitrate, 8.0% of molybdenum oxide, 65% of Y-type molecular sieve and 20% of aluminum oxide, wherein the properties of the final hydrocracking catalyst are shown in Table 1.
Example 6
Adding nickel nitrate into 100ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, adding the nickel active metal solution into a Y molecular sieve in 5 times of equal amount under stirring according to the proportion that the mass of the nickel active metal solution is 40% of that of the Y molecular sieve to form a small-particle aggregation material which is marked as a mixture 1, 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 for mixing 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 the material at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst, wherein the composition of the final hydrocracking catalyst comprises 6.0% of nickel nitrate, 6.0% of molybdenum oxide, 80% of Y-type molecular sieve and 8.0% of aluminum oxide, and the properties of the final hydrocracking catalyst are shown in Table 1.
Example 7
Adding nickel nitrate into 30ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, adding the nickel active metal solution into a Y molecular sieve in an equal amount for 2 times under a stirring state according to the proportion that the mass of the nickel active metal solution is 85% of that of the Y molecular sieve to form a small-particle aggregation-state material which is marked as a mixture 1, wherein the mixture 1 is in a partial aggregation state and forms small particles, and the diameter of the small particles is 1-4 mm; adding molybdenum oxide and aluminum oxide powder into the mixture 1 in sequence for mixing 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 material, placing the material into a muffle furnace, and roasting the material at 500 ℃ for 4 hours to obtain the final hydrocracking catalyst with the following components of 9.5% of nickel nitrate, 20.5% of molybdenum oxide, 20% of Y-type molecular sieve and 50% of aluminum oxide, wherein the properties of the final hydrocracking catalyst are shown in Table 1.
Example 8
Adding nickel nitrate into 80ml of deionized water, fully dissolving to obtain a solution containing nickel active metal, adding the nickel active metal solution into a Y molecular sieve and a Beta molecular sieve in an equal amount of 4 times under 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 mixing to form a small-particle aggregation material which is recorded as a mixture 1, wherein the diameter of each small particle is 1-4 mm. And adding molybdenum oxide, alumina 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 120 ℃ oven for 12 hours, the mass content of nitrate in the dried material is 3.8%, the dried material is taken out and placed in a muffle furnace to be roasted for 4 hours at 500 ℃, and the final hydrocracking catalyst is obtained, and the composition of the catalyst comprises 3.5% of nickel nitrate, 13.5% of molybdenum oxide, 25% of Y-type molecular sieve, 15% of Beta molecular sieve, 33% of aluminum oxide and 10% of amorphous silicon aluminum, and the properties of the catalyst are shown in table 1.
Comparative example 1
The catalyst is prepared according to the existing hydrocracking catalyst kneading method preparation process. The material components of the molecular sieve, the alumina and/or the amorphous silicon-aluminum, the nickel nitrate, the molybdenum oxide, the auxiliary agent and the like used in the example 2 are all put into a roller mill. In the rolling process, adding 6wt% nitric acid solution for multiple times, adding 200ml, rolling until the mixture is rolled to obtain a hydrocracking catalyst, putting the hydrocracking catalyst into a 120 ℃ oven for 24 hours, taking out the hydrocracking catalyst and putting the hydrocracking catalyst into a muffle furnace, drying the hydrocracking catalyst to obtain a material with the mass content of nitrate radical of 5.9%, and roasting the material at 500 ℃ for 4 hours to obtain a final product.
Comparative example 2
The catalyst is prepared according to the existing hydrocracking catalyst impregnation method preparation process. Weighing 25% of Y-type molecular sieve, 45% of alumina and 30% of amorphous silicon-aluminum, and rolling all the material components in a rolling machine. In the rolling process, 6wt% nitric acid solution is added for multiple times, 400ml is added in total, the mixture is rolled to be formed, and the catalyst carrier is obtained. And (3) putting the catalyst carrier into a 120 ℃ oven for 12 hours, taking out the catalyst carrier, putting the catalyst carrier into a muffle furnace, and roasting the catalyst carrier for 4 hours at 550 ℃ to obtain the catalyst carrier.
The catalyst carrier is impregnated according to the existing impregnation method preparation process, and a molybdenum-nickel metal impregnation solution is prepared according to the proportion of 8% of nickel nitrate and 20% of molybdenum oxide. And (3) soaking the roasted catalyst carrier in the metal solution for 24 hours to obtain a hydrocracking catalyst, putting the hydrocracking catalyst into a 120 ℃ oven for 24 hours, taking out the hydrocracking catalyst with the mass content of nitrate radical being 22% in the dried hydrocracking catalyst, putting the hydrocracking catalyst into a muffle furnace, and roasting the hydrocracking catalyst for 6 hours at 500 ℃ 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 auxiliaries used in example 6 were all put into a roller mill. In the rolling process, 10wt% nitric acid solution is added for multiple times, 200ml is added in total, the mixture is rolled until the mixture is rolled to obtain a hydrocracking catalyst, the hydrocracking catalyst is placed in a 120 ℃ oven for 24 hours, the hydrocracking catalyst is taken out and placed in a muffle furnace, the mass content of nitrate in the dried material is 9.9%, and the mixture is roasted at 500 ℃ for 4 hours to obtain a final product.
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 auxiliaries used in example 7 were all charged to a roller mill. In the rolling process, 10wt% hydrochloric acid solution is added for multiple times, 200ml is added in total, the mixture is rolled until the mixture is rolled to obtain a hydrocracking catalyst, the hydrocracking catalyst is placed in a 120 ℃ oven for 24 hours, the mass content of nitrate radical in the dried material is 5.9%, the dried material is taken out and placed in a muffle furnace, and the mixture is roasted for 4 hours at 500 ℃ to obtain the final product.
TABLE 1 hydrocracking catalyst physicochemical Properties
Figure DEST_PATH_IMAGE001
And (3) evaluating the catalytic performance of the hydrocracking catalyst:
after the catalyst is presulfurized, a 200ml small hydrogenation device is adopted for evaluation, wherein the properties of the raw oil are shown in table 1, the reaction process conditions are shown in table 2, and the reaction performance comparison results of the catalyst are shown in table 3. When the series of catalysts are evaluated, raw oil passes through a hydrofining catalyst bed layer and a hydrocracking catalyst bed layer in sequence. After the raw oil is hydrorefined, the content of organic nitrogen is controlled to be less than 5 ppm.
TABLE 2 Properties of the starting oil
Figure 31597DEST_PATH_IMAGE002
TABLE 3 Process conditions and catalyst reactivity
Figure DEST_PATH_IMAGE003
The evaluation results in table 3 show that when the reaction conversion rate is controlled to be 75%, the reaction temperature of the hydrocracking catalyst continuously prepared by the method of the present invention is substantially the same as the reaction performance of the hydrocracking catalyst prepared by the conventional kneading method and the dipping method, and the yields of heavy naphtha and aviation kerosene fractions of the catalyst of example 2 prepared by the method of the present invention and the yield of comparative example 2 prepared by the dipping method are substantially the same, slightly because of comparative example 1 prepared by the conventional kneading method. The results show that the hydrocracking catalyst prepared by the method has reaction performance basically consistent with that of the catalyst obtained by the existing impregnation method.

Claims (17)

1. A preparation method of a hydrocracking catalyst is characterized by comprising the following steps: the method comprises the following steps:
mixing a solution containing VIII group metal with the acidic cracking material, wherein the dosage of the VIII group metal solution is 20-90% by weight, preferably 30-70% by weight of the acidic cracking material;
and mixing the mixed material with a VIB group 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%.
2. The method of claim 1, wherein: the dosage of the VIII group metal solution is 30-70% of the weight of the acidic cracking material; the mass content of nitrate radicals in the dried material is 2.5% -10.0%.
3. The method of claim 1, wherein: the VIII group metal is at least one of Co and Ni, the acidic cracking material is a Y-type molecular sieve and/or a beta molecular sieve, the solution of the VIII group metal is an aqueous solution, and the VIII group metal precursor is nitrate of the VIII group metal.
4. The method of claim 3, wherein: the particle size range of the Y-type molecular sieve and/or the beta molecular sieve is 0.1-1.5 mu m, and the specific surface area is 350-1000 m2Per g, pore volume of 0.25-0.60 cm3In the formula,/g, wherein, molecular sieve SiO of Y type2/Al2O3Is 8 to 50, beta molecular sieve SiO2/Al2O340 to 95.
5. The method of claim 4, wherein: the particle size range of the Y-type molecular sieve and/or the beta molecular sieve is 0.1-1.0 mu m, and the specific surface area is 380-950 m2/g，The pore volume is 0.30-0.55 cm3In the formula,/g, wherein, molecular sieve SiO of Y type2/Al2O310-30, beta molecular sieve SiO2/Al2O3 50~85。
6. The method of claim 1, wherein: the group VIII metal-containing solution is added to the acidic cracking material in one or more portions, preferably 1 to 7, and more preferably 2 to 5 portions, with stirring during the addition.
7. The method of claim 1, wherein: the group VIB metal is at least one of Mo and W, the binder is aluminum oxide and/or amorphous silicon-aluminum, and the group VIB metal is metal salt and/or metal oxide.
8. The method of claim 7, wherein: the specific surface area of the alumina is 300-850 m2The pore volume is 0.40-1.2 ml/g; the amorphous silica-alumina specific surface area is 200-600 m2The pore volume is 0.45-1.20 ml/g.
9. The method of claim 8, wherein: the specific surface area of the alumina is 350-700 m2The pore volume is 0.60-1.05 ml/g; the amorphous silica-alumina specific surface area is 230-500 m2The pore volume is 0.55-1.00 ml/g.
10. The method of claim 1, wherein: the mass concentration of the nitric acid solution is 1-12 wt%, preferably 2-10 wt%, and more preferably 2-6 wt%.
11. The method of claim 1, wherein: 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.
12. The method of claim 1, wherein: the method comprises the following steps:
(1) dissolving one or more group VIII metal nitrates in a quantity of deionized water;
(2) weighing a certain amount of acid cracking materials, mixing the acid cracking materials with the VIII group metal solution obtained in the step (1), and recording the mixture as a mixture 1, wherein the VIII group metal solution is used in an amount of 20-90% by weight, preferably 30-70% by weight, of the weight of the acid cracking materials;
(3) uniformly mixing a VIB group metal, a 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 at 100-150 ℃ for 12-24 hours, wherein the mass content of nitrate 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.
13. A hydrocracking catalyst characterized by: prepared by the process of any one of claims 1 to 12.
14. The catalyst of claim 1, wherein: the hydrocracking catalyst contains hydrogenation active metal and an acidic cracking material, wherein the hydrogenation active metal 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 acidic cracking material is a Y-type molecular sieve and/or a beta molecular sieve, the mass content of the Y-type molecular sieve and/or the beta molecular sieve is 10-80% by weight of the final hydrocracking catalyst, the weight content of the VIB group metal is 5-30% by weight of oxides, and the content of the VIII group metal is 2-20% by weight of oxides.
15. The catalyst of claim 14, wherein: the hydrocracking catalyst contains a binder, the binder is alumina and/or amorphous silicon-aluminum, and the weight content of the alumina and/or amorphous silicon-aluminum is 10-80% based on the weight of the final hydrocracking catalyst.
16. The catalyst of claim 14, wherein: the hydrocracking catalyst had the following properties: the specific surface area is 280-480 m2A concentration of 300 to 450m is preferred2Per g, 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/cm3Preferably 0.69 to 0.75g/cm3。
17. Use of a hydrocracking catalyst according to any one of claims 13 to 16 for hydrocracking reactions, characterized in that: the reaction conditions were as follows: the reaction pressure is 7-16 MPa, the reaction temperature is 300--1And the volume ratio of the hydrogen to the oil is 700-1800.
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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
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