CN112742457B - Hydrocracking catalyst, and preparation method and application thereof - Google Patents

Hydrocracking catalyst, and preparation method and application thereof Download PDF

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Publication number
CN112742457B
CN112742457B CN201911046166.6A CN201911046166A CN112742457B CN 112742457 B CN112742457 B CN 112742457B CN 201911046166 A CN201911046166 A CN 201911046166A CN 112742457 B CN112742457 B CN 112742457B
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molecular sieve
catalyst
hydrocracking catalyst
hydrocracking
carrier
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CN112742457A (en
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杨平
胡志海
王轶凡
董松涛
许双辰
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • 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
    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J35/394—
    • B01J35/61—
    • 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
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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

Abstract

The invention provides a hydrocracking catalyst, a preparation method and application thereof. The hydrocracking catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier comprises a matrix and a composite molecular sieve, the composite molecular sieve comprises a Y1 molecular sieve, a Y2 molecular sieve and a molecular sieve with an MFI structure, the proportion of pores with the pore diameter of more than 2nm and less than 100nm on the Y1 molecular sieve in the total pores is less than 30%, the proportion of pores with the pore diameter of more than 2nm and less than 100nm on the Y2 molecular sieve in the total pores is 30% -70%, the ratio of the B acid amount of the Y1 molecular sieve per unit weight to the B acid amount of the Y2 molecular sieve per unit weight is 1.1:1-4:1, and the content of the molecular sieve with the MFI structure in the composite molecular sieve is 5% -40%. The invention regulates and controls the pore structure and acid property of the catalyst through the molecular sieve, so that the catalyst has high polycyclic aromatic hydrocarbon ring opening activity, high alkyl aromatic hydrocarbon side chain breaking performance and high monocyclic aromatic hydrocarbon retention, and can improve C in the polycyclic aromatic hydrocarbon hydrocracking reaction 6 ‑C 10 Light aromatic hydrocarbon and C 6 ‑C 8 Yield of light aromatic hydrocarbons.

Description

Hydrocracking catalyst, and preparation method and application thereof
Technical Field
The invention relates to the field of catalysis, in particular to a hydrocracking catalyst, a preparation method and application thereof.
Background
With the increasing of the heavy and inferior degree of crude oil and the application of catalytic cracking technology such as improving the quality of gasoline or increasing the yield of propylene, the quality of the catalytic cracking diesel oil fraction is increasingly deteriorated. The characteristics of high density, high nitrogen content, high aromatic hydrocarbon content and low cetane number are presented. Meanwhile, the upgrading steps of fuel oil quality are accelerated, and for the vehicle diesel, the index requirements of sulfur content, polycyclic aromatic hydrocarbon content, cetane number and the like are more and more harsh. Obviously, the composition characteristics of catalytic diesel accounting for one third of the diesel pool in China cannot meet the increasingly strict fuel standards. On the other hand, with the adjustment of the economic structure in China, the demand structure of the oil product consumer market is changed, the diesel oil demand is increased and slowed down, and the diesel oil ratio is continuously reduced. Inferior secondary processing diesel oil, especially catalytic diesel oil, becomes the first choice of refinery pressure reduction diesel oil. Based on the composition characteristics rich in polycyclic aromatic hydrocarbon and the hydrocracking reaction mechanism of polycyclic aromatic hydrocarbon, the research of producing high-octane gasoline or light aromatic hydrocarbon by catalytic diesel oil hydrocracking is paid attention to.
In the prior art, hydrocracking of catalytic diesel oil to produce high-octane gasoline or aromatic hydrocarbon is reported more, for example:
CN105542849a discloses a method for producing clean diesel oil and light aromatic hydrocarbon from inferior diesel oil, which is characterized in that the inferior diesel oil is hydrofined, then aromatic hydrocarbon and sulfide are removed through simulated moving bed adsorption analysis, wherein the separated heavy aromatic hydrocarbon is subjected to hydro-upgrading to produce BTX light aromatic hydrocarbon, gasoline component and small amount of light hydrocarbon. The hydro-upgrading catalyst is a molecular sieve catalyst loaded with noble metals Pt, pd and Re.
CN103120955a discloses a catalyst and process for converting polycyclic aromatic hydrocarbons to monocyclic aromatic hydrocarbons, the catalyst comprising a mixture of 34.5 to 60wt% fau-type zeolite and at least one molecular sieve selected from MOR, BEA, MFI or MCM-22, 39.5 to 65wt% of at least one selected from gamma-alumina, eta-alumina or pseudo-boehmite as binder and 0.05 to 0.9wt% of at least one metal selected from Pt, pd or Ir.
CN103221131a discloses a hydrocracking catalyst for converting polycyclic aromatic hydrocarbons into light aromatic hydrocarbons of high valence, i.e. monocyclic aromatic hydrocarbons. The catalyst selects one or more of VIII group and VIB group metals, and simultaneously, metal auxiliary agents such as tin (Sn) are introduced to control the hydrogenation capacity of transition metal sulfides so as to avoid over-saturation of polycyclic aromatic hydrocarbon to cycloparaffin and continuous hydrogenation saturation of generated monocyclic aromatic hydrocarbon to cycloparaffin, thereby improving the selectivity of the monocyclic aromatic hydrocarbon in the product. To ensure hydrogenation activity of the catalyst to maximize BTX production, the total amount of transition metal is preferably 1 to 10wt%.
Although various catalysts for diesel hydrocracking are disclosed at present, the yield and selectivity of light aromatic hydrocarbon such as BTX produced by diesel hydrocracking are low. The catalyst properties are critical and therefore the performance of the catalyst still needs to be improved.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a catalyst with high polycyclic aromatic hydrocarbon ring opening activity, high alkyl aromatic hydrocarbon side chain breaking performance and high monocyclic aromatic hydrocarbon retention, so as to improve the yield of light aromatic hydrocarbon in the diesel hydrocracking process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a hydrocracking catalyst comprising a carrier and an active metal component supported on the carrier, the carrier comprising a matrix and a composite molecular sieve,
the composite molecular sieve comprises a Y1 molecular sieve, a Y2 molecular sieve and a molecular sieve with an MFI structure, wherein the proportion of pores with the pore diameter of more than 2nm and less than 100nm on the Y1 molecular sieve in the total pores is less than 30%, the proportion of pores with the pore diameter of more than 2nm and less than 100nm on the Y2 molecular sieve in the total pores is 30-70%, the ratio of the B acid amount of the Y1 molecular sieve per unit weight to the B acid amount of the Y2 molecular sieve per unit weight is 1.1:1-4:1, and the content of the molecular sieve with the MFI structure in the composite molecular sieve is 5-40 wt%.
In some embodiments, the pores of the Y1 molecular sieve having a pore size greater than 2nm and less than 100nm comprise from 5% to 25% of the total pores.
In some embodiments, the pores with a pore size greater than 2nm and less than 100nm on the Y2 molecular sieve comprise 35% to 60% of the total pores.
In some embodiments, the ratio of the amount of B acid per weight of the Y1 molecular sieve to the amount of B acid per weight of the Y2 molecular sieve is from 1.1:1 to 2.5:1.
In some embodiments, the Y1 molecular sieve has a mesoporous volume of 0.03 to 0.12cm 3 Preferably 0.06 to 0.11cm 3 /g。
In some embodiments, the mesoporous volume of the Y2 molecular sieve is from 0.12cm to 0.50cm 3 Preferably 0.15 to 0.40cm 3 /g。
In some embodiments, the molecular sieve having an MFI structure is ZSM-5, ZRP-5, or mixtures thereof.
In some embodiments, the molecular sieve having an MFI structure is present in an amount of 5wt% to 30wt% based on the composite molecular sieve.
In some embodiments, the weight ratio of the Y1 molecular sieve to the Y2 molecular sieve in the composite molecular sieve is from 1:9 to 9:1, preferably from 1:1 to 1:4.
In some embodiments, the hydrocracking catalyst comprises, in weight percent, 5% to 30% of the active metal component, 45% to 70% of the composite molecular sieve, and 10% to 25% of the matrix.
In some embodiments, the active metal component comprises at least one metal component selected from group VIII and at least one metal component selected from group VIB, and the atomic ratio of group VIII metal to group VIB metal is from 0.05 to 0.6, preferably from 0.2 to 0.5.
In some embodiments, the matrix is an inorganic oxide, preferably alumina.
In another aspect, the present invention also provides a method for preparing the hydrocracking catalyst, including:
uniformly mixing the molecular sieve and the matrix, molding, and roasting to obtain the carrier;
and impregnating the carrier with a solution containing the active metal component, and drying and roasting to obtain the hydrocracking catalyst.
In still another aspect, the invention also provides an application of the hydrocracking catalyst in the production of light aromatic hydrocarbon by the hydrocracking reaction of polycyclic aromatic hydrocarbon.
In some embodiments, the hydrocracking reaction is performed using a catalytic diesel as a feedstock, using a fixed bed sheet section series and light diesel recycle process. The single-stage tandem process comprises a hydrofining reaction zone and a hydrocracking reaction zone, catalytic diesel oil firstly enters the hydrofining reaction zone and then enters the hydrocracking reaction zone, and the reaction conditions of the hydrofining reaction zone and the hydrocracking reaction zone respectively and independently comprise: the reaction temperature is 300-450 ℃, the reaction pressure is 4.0-10.0 MPa, the hydrogen-oil volume ratio is 200-1500, and the volume airspeed is 0.5-2.5; the light diesel oil circulation ratio of the light diesel oil circulation process is 0-0.5.
In some embodiments, the catalytic diesel has a dry point greater than 330 ℃, preferably a dry point greater than 350 ℃.
The invention can effectively regulate the matching of the pore structure and the acid center of the catalyst by compounding molecular sieves with different properties, strengthen the synergistic effect of the hydrogenation function and the cracking function, ensure that the catalyst has high polycyclic aromatic hydrocarbon ring-opening activity, high alkyl aromatic hydrocarbon side chain breaking performance and high monocyclic aromatic hydrocarbon retention, and can improve C in the polycyclic aromatic hydrocarbon hydrocracking reaction 6 -C 10 Light aromatic hydrocarbon and C 6 -C 8 Yield of light aromatic hydrocarbons.
Detailed Description
The technical scheme of the invention is further described below according to specific embodiments. The scope of the invention is not limited to the following examples, which are given for illustrative purposes only and do not limit the invention in any way.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is understood to be disclosed or described in this invention unless the combination is obviously unreasonable by those skilled in the art. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention there is provided a hydrocracking catalyst comprising a support and an active metal oxide supported on the support, the support comprising a matrix and a composite molecular sieve.
The catalyst of the invention comprises 5 to 30 weight percent of active metal oxide, 45 to 70 weight percent of composite molecular sieve and 10 to 25 weight percent of matrix.
In the catalyst of the present invention, the substrate is a refractory inorganic oxide, preferably alumina. The alumina used in the invention is selected from one or more transition phase aluminas among gamma, eta, theta, delta and chi, and can also be one or more transition phase aluminas among gamma, eta, theta, delta and chi containing one or more additive components selected from silicon, titanium, magnesium, boron, zirconium, thorium, niobium and rare earth, and is preferably gamma-alumina and gamma-alumina containing one or more additive components selected from silicon, phosphorus, titanium, magnesium, boron, zirconium, thorium, niobium and rare earth. They may be commercially available or may be obtained by any of the existing methods.
In the catalyst of the invention, the composite molecular sieve comprises a plurality of molecular sieves, namely a Y1 molecular sieve, a Y2 molecular sieve and a molecular sieve with an MFI structure, wherein the Y1 molecular sieve and the Y2 molecular sieve are Y-shaped molecular sieves, the proportion of pores with the aperture of more than 2nm and less than 100nm on the Y1 molecular sieve in the total pores is less than 30 percent, preferably 5 to 25 percent, and the proportion of pores with the aperture of more than 2nm and less than 100nm on the Y2 molecular sieve in the total pores is 30 to 70 percent, preferably 35 to 60 percent.
The ratio of the amount of B acid per weight of the Y1 molecular sieve to the amount of B acid per weight of the Y2 molecular sieve is 1.1:1 to 4:1, preferably 1.1:1 to 2.5:1.
The mesoporous volume of the Y1 molecular sieve is 0.03-0.12 cm 3 Preferably 0.06 to 0.11cm 3 And/g. The mesoporous volume of the Y2 molecular sieve is 0.12-0.50 cm 3 Preferably 0.15 to 0.40cm 3 /g。
The weight ratio of the Y1 molecular sieve to the Y2 molecular sieve is 1:9-9:1, preferably 1:1-1:4, and the content of the molecular sieve with an MFI structure accounts for 5-40%, preferably 5-30% of the composite molecular sieve.
The molecular sieve with MFI structure can be ZSM-5, ZRP-5 or their mixture, which can be commercial products or prepared by any existing method.
The hydrocracking catalyst of the invention can be prepared by the following method:
uniformly mixing a molecular sieve and a matrix, molding, and roasting to obtain a carrier;
preparing an impregnating solution of a compound containing an active metal component; and
the carrier is impregnated with the impregnating solution, and the hydrocracking catalyst is obtained after drying and roasting.
In the catalyst of the present invention, the carrier is made of composite molecular sieve and matrix, and various easy-to-handle shaped articles, such as microspheres, spheres, tablets or strips, etc., can be made according to different requirements. The molding can be carried out in a conventional manner, for example, by extrusion molding and calcination of the composite molecular sieve and the refractory inorganic oxide. When the carrier is extruded, a proper amount of extrusion aid and/or adhesive can be added into the carrier, and then the carrier is extruded. The kind and the amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, the common extrusion aid can be one or more selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethylene alcohol.
In the catalyst of the present invention, the active metal component comprises at least one metal component selected from group VIII and at least one metal component selected from group VIB. The metal component of group VIII may be iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and the metal component of group VIB may be chromium, molybdenum, tungsten, etc. The atomic ratio of the group VIII metal component to the group VIB metal component is 0.05 to 0.6, preferably 0.2 to 0.5. The active metal component is typically supported on a carrier in the form of a metal oxide.
The present invention is not particularly limited as long as it is sufficient to support the active metal component on the support, and a preferred method is an impregnation method comprising preparing an impregnation solution of the metal component-containing compound, and then impregnating the support with the solution. The impregnation method is a conventional method, and for example, may be an excess liquid impregnation method or a pore saturation method impregnation method. Wherein the specified level of catalyst can be prepared by adjusting and controlling the concentration, amount or amount of the impregnation solution containing the metal component, or the amount of the support, as will be readily understood and effected by those skilled in the art.
The compound containing a metal component selected from group VIB is selected from one or more of soluble compounds thereof, such as one or more of molybdenum oxide, molybdate and para-molybdate, preferably molybdenum oxide, ammonium molybdate and para-ammonium molybdate; one or more of tungstate, metatungstate and ethyl metatungstate, preferably ammonium metatungstate and ethyl ammonium metatungstate.
The compound containing the group VIII metal component is selected from one or more of their soluble compounds, such as one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and soluble complex of cobalt, preferably cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble complex of nickel, preferably nickel nitrate, basic nickel carbonate.
On the other hand, the invention also provides application of the hydrocracking catalyst in the production of light aromatic hydrocarbon by the polycyclic aromatic hydrocarbon hydrocracking reaction.
Specifically, catalytic diesel is used as raw material, the hydrocracking catalyst is used, and the fixed bed sheet section series connection and the light diesel circulation process are adopted to carry out hydrocracking reaction to produce light aromatic hydrocarbon, mainly produce light aromatic hydrocarbon such as BTX (Benzene-tolene-Xylene, benzene-Toluene-Xylene mixture), such as C 6 -C 10 Light aromatic hydrocarbon and C 6 -C 8 Light aromatic hydrocarbon. The fixed bed sheet section series process comprises a hydrofining reaction zone and a hydrocracking reaction zone, catalytic diesel oil firstly enters the hydrofining reaction zone for reaction, then hydrofining effluent enters the hydrocracking reaction zone for reaction, and part of the obtained product is taken as a raw material by a light diesel oil circulation process and enters the hydrofining reaction zone and the hydrocracking reaction zone in the fixed bed sheet section series process again for reaction.
The catalytic diesel oil treated by the invention is a light cycle oil product of a catalytic cracking unit in the petroleum refining process, has higher aromatic hydrocarbon content and mainly contains dicyclic aromatic hydrocarbon. The dry point of the catalytic diesel is greater than 330 ℃, preferably greater than 350 ℃.
In the process provided by the present invention, the catalyst employed in the hydrofinishing reaction zone may be a variety of commercial catalysts or may be prepared in accordance with the prior art in the field.
The conditions of the hydrofining reaction zone and the hydrocracking reaction zone can be the same or different, and the independent conditions are as follows: the reaction temperature is 300-450 ℃, the reaction pressure is 4.0-10.0 MPa, the hydrogen-oil volume ratio is 200-1500, and the volume airspeed is 0.5-2.5; the light diesel oil circulation ratio of the light diesel oil circulation process is 0-0.5.
The nature of the acidic component in the catalyst not only affects the acid nature, but also affects the dispersion of metal dispersion, namely hydrogenation performance, so that the yield of light aromatic hydrocarbon such as BTX in the hydrocracking process of catalytic cracking diesel oil is further affected.
The ideal reaction for producing light aromatic hydrocarbons such as BTX and the like through hydrocracking and conversion of polycyclic aromatic hydrocarbons is that polycyclic aromatic hydrocarbons are selectively hydrogenated and saturated to tetrahydronaphthalene single-ring aromatic hydrocarbons, and then selective ring-opening reaction and alkylbenzene side chain breaking reaction are carried out on tetrahydronaphthalene single-ring aromatic hydrocarbons to generate micromolecule alkylbenzenes. It is found that the selective ring opening of tetrahydronaphthalene monocyclic aromatic hydrocarbon requires relatively larger pore size and moderate B acid quantity, and the relatively smaller pore size and higher B acid quantity are beneficial to the side chain breaking reaction of alkylbenzene, namely the ring opening reaction of tetrahydronaphthalene monocyclic aromatic hydrocarbon and the side chain breaking reaction of alkylbenzene have different requirements on the performance of the catalyst. In order to increase the yield and selectivity of the target product, it is necessary to strengthen the matching degree of the catalyst property and the reaction.
The invention can effectively regulate the matching of the pore structure and the acid center of the catalyst through the combination of molecular sieves with different properties, and the cooperation of the hydrogenation function and the cracking function ensures that the catalyst has high polycyclic aromatic hydrocarbon ring opening activity, high alkyl aromatic hydrocarbon side chain breaking performance and high monocyclic aromatic hydrocarbon retention, and can improve C in the polycyclic aromatic hydrocarbon hydrocracking reaction 6 -C 10 Light aromatic hydrocarbon and C 6 -C 8 Yield of light aromatic hydrocarbons.
The catalyst of the invention can be suitable for the efficient conversion process of the polycyclic aromatic hydrocarbon, and is especially suitable for the hydrocracking reaction of the catalytic diesel oil with higher dry point.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
Examples
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the present invention are analytically pure and all reagents used are commercially available, for example, from the carbofuran, national drug group.
In the following examples, preparation examples and comparative examples, the mesoporous volume of the molecular sieve was measured by a nitrogen adsorption and desorption method, and the mesoporous was a molecular sieve pore having a pore diameter of more than 2nm and less than 100 nm.
The specific measurement method is as follows: the measurement was carried out by using an AS-3, AS-6 static nitrogen adsorption instrument manufactured by Quantachrome instruments.
Test conditions: placing the sample in a sample processing system, and vacuumizing to 1.33X10 at 300 deg.C -2 Pa, preserving heat and pressure for 4h, and purifying a sample. Testing the purified sample at different temperatures of-196℃in liquid nitrogenThe adsorption capacity and desorption capacity of nitrogen under the specific pressure P/P0 condition to obtain N 2 Adsorption-desorption isotherms. And then calculating the total specific surface area, the micropore specific surface area and the mesopore specific surface area by using a two-parameter BET formula, taking the adsorption quantity with the specific pressure P/P0=0.98 or less as the total pore volume of the sample, calculating the pore size distribution of the mesopore part by using a BJH formula, and calculating the mesopore volume (2-100 nanometers) by using an integration method.
In the following examples, preparations and comparative examples, the measurement methods of the B acid amount are as follows:
FTS3000 type Fourier infrared spectrometer manufactured by BIO-RAD corporation of America was used.
Test conditions: pressing the sample into tablet, sealing in an in-situ cell of an infrared spectrometer, and vacuumizing to 10 at 350deg.C -3 Pa, maintaining for 1h, desorbing gas molecules on the surface of the sample, and cooling to room temperature. Pyridine vapor with the pressure of 2.67Pa is introduced into the in-situ tank, after being balanced for 30min, the temperature is increased to 200 ℃, and the vacuum is pumped again to 10 DEG C -3 Pa, maintaining for 30min, cooling to room temperature, and cooling to 1400-1700cm -1 Scanning in the wave number range, and recording an infrared spectrum chart of 200 ℃ pyridine adsorption. Then the sample in the infrared absorption pool is moved to a heat treatment area, the temperature is raised to 350 ℃, and the vacuum is pumped to 10 -3 Pa, holding for 30min, cooling to room temperature, and recording infrared spectrogram of pyridine adsorption at 350 ℃. And (5) automatically integrating by an instrument to obtain the amount of the acid B.
In the following examples, preparations and comparative examples, the kinds and contents of each metal element in the catalyst were measured by the X-ray fluorescence spectrum analysis method defined in RIPP 132-92 (the method of petrochemical analysis (RIPP Experimental method), yang Cuiding et al, scientific Press, month 9, 1 st edition 1990, pages 371-379). In the catalyst measurement, the catalyst sample was stored in an argon atmosphere.
In the following examples, preparations and comparative examples, the post-calcination composition of the catalyst refers to the composition of a sample after the catalyst was calcined at 550℃for 4 hours under an atmospheric atmosphere.
Preparation example 1 preparation of molecular sieve Y1-1
1) The method comprises the steps of carrying out a first ammonium exchange by using NaY zeolite as a raw material and using an ammonium sulfate solution, wherein the treatment conditions are as follows: according to NaY molecular sieves (dry basis): ammonium sulfate: water = 1:0.9:10, exchanged at 90 ℃ for 2h, then filtered and dried at 120 ℃ for 4h.
2) And (2) roasting the sample obtained in the step (1) in 100% steam atmosphere at 500 ℃ for 2 hours.
3) The molecular sieve obtained in step 2) is based on molecular sieve (dry basis): ammonium sulfate: water = 1:0.6:10, and after a second ammonium exchange at 90 ℃ for 1 hour, filtering.
4) The molecular sieve obtained in the step 3) is used as a molecular sieve (dry basis): ammonium sulfate: water = 1:0.6:10, carrying out the third ammonium exchange at 90 ℃ for 1h, and then filtering;
5) Washing the molecular sieve obtained in the step 4) by deionized water, and washing sulfate radical to be less than 0.8%;
6) Re-pulping and filtering the sample obtained in the step 5), and drying at 200 ℃ for 4 hours to obtain the molecular sieve Y1-1, wherein the physicochemical properties of the molecular sieve are shown in table 1.
Preparation example 2 preparation of molecular sieves Y1-2
Molecular sieves Y1-2 were prepared in the same manner as in preparation example 1 except that the hydrothermal calcination temperature in step 2) was 550℃and the physicochemical properties thereof are shown in Table 1.
PREPARATION EXAMPLE 3 preparation of molecular sieves Y1-3
Molecular sieves Y1-3 were prepared in the same manner as in preparation example 1 except that the hydrothermal calcination temperature in step 2) was 650℃and the treatment time was 3 hours, and the physicochemical properties thereof were as shown in Table 1.
Preparation example 4 preparation of molecular sieve Y2-1
1) The method comprises the steps of carrying out a first ammonium exchange by using NaY zeolite as a raw material and using an ammonium sulfate solution, wherein the treatment conditions are as follows: according to NaY molecular sieves (dry basis): ammonium sulfate: water = 1:1:10, exchanged at 90 ℃ for 2h, then filtered and dried at 120 ℃ for 4h.
2) And (3) roasting the sample obtained in the step (1) at a hydrothermal roasting temperature of 500 ℃ for 2 hours.
3) Repeating the procedure of step 1) 3 times for the sample obtained in step 2).
4) And 3) carrying out hydrothermal roasting on the sample obtained in the step 3), wherein the roasting temperature is 550 ℃, and obtaining a sample Y2-1.
PREPARATION EXAMPLE 5 preparation of molecular sieves Y2-2
And (3) carrying out acid treatment on the Y2-1 sample, namely adding 100 g of Y2-1 into 1000 ml of 0.5N hydrochloric acid, uniformly stirring, heating to 90 ℃, stirring for 1 hour, filtering, washing, filtering again, and drying at 150 ℃ for 2 hours to obtain the Y2-2 sample.
Preparation example 6 preparation of molecular sieves Y2-3
The Y2-1 sample is subjected to acid treatment, specifically, 100 g of Y2-1 is added into 1000 ml of 0.25N hydrochloric acid, stirred uniformly, heated to 90 ℃ and stirred for 1 hour, filtered, washed, filtered again and dried for 2 hours at 150 ℃ to obtain the Y2-3 sample.
TABLE 1 molecular sieve numbering and physicochemical Properties
Molecular sieve Pores greater than 2nm and less than 100nm account for the total pore fraction/% B acid amount Mesoporous volume/(cm) 3 /g)
Y1-1 6 Datum 0.04
Y1-2 9 Benchmark of 92% 0.07
Y1-3 18 Benchmark × 85% 0.10
Y2-1 32 Benchmark 57% 0.13
Y2-2 40 Benchmark of 40% 0.25
Y2-3 32 Benchmark 24% 0.18
Example 1
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70%, 116.7 g of Y1-1 molecular sieve with a dry basis of 80%, 29.3 g of Y2-1 molecular sieve with a dry basis of 82%, and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81% (product of Changling catalyst, changling Co.) are weighed and uniformly mixed, extruded into a three-blade shape with a circumcircle diameter of 1.6 mm on a strip extruder, dried at 120 ℃ for 3 hours, and baked at 600 ℃ for 4 hours to obtain a catalyst carrier Z1.
Taking 100 g of carrier Z, and using 78 ml of carrier Z containing 59.8 g/L of NiO and MoO respectively 3 307.7 g/l, P 2 O 5 59.8 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain a catalyst C1.
The composition of the catalyst C1 after calcination is shown in Table 2, based on the catalyst.
Example 2
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70 percent, 36.7 g of Y1-1 molecular sieve with a dry basis of 80 percent, 108.6 g of Y2-1 molecular sieve with a dry basis of 82 percent and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81 percent (product of Changling catalyst, changling Co.) are weighed and uniformly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier Z2.
Taking 100 g of carrier Z, using 83 ml of NiO containing 56.2 g/L and MoO respectively 3 289.2 g/l, P 2 O 5 56.2 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain a catalyst C2.
The composition of the catalyst C2 after calcination is shown in Table 2, based on the catalyst.
Example 3
76.2 g of pseudo-boehmite with a dry basis of 70 percent (catalyst, longline division company) and 37.1 g of Y1-2 molecular sieve with a dry basis of 79 percent, 108.6 g of Y2-2 molecular sieve with a dry basis of 81 percent and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81 percent (product of longline catalyst division company) are weighed and uniformly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier Z3.
Taking 3 g of carrier Z, using 83 ml of NiO containing 56.2 g/L and MoO respectively 3 289.2 g/l, P 2 O 5 56.2 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain a catalyst C3.
The composition of the catalyst C3 after calcination is shown in Table 2, based on the catalyst.
Example 4
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70 percent, 34.9 g of Y1-3 molecular sieve with a dry basis of 84 percent, 108.6 g of Y2-3 molecular sieve with a dry basis of 81 percent and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81 percent (product of Changling catalyst, changling Co.) are weighed and uniformly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier Z4.
Taking carrier Z4 to 100 g, using 86 ml of NiO 54.3 g/L and MoO respectively 3 279.1 g/L, P 2 O 5 54.3 g/L mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain the catalyst C4.
The composition of the catalyst C4 after calcination is shown in Table 2, based on the catalyst.
Example 5
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70 percent, 34.9 g of Y1-3 molecular sieve with a dry basis of 84 percent, 108.6 g of Y2-3 molecular sieve with a dry basis of 81 percent and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81 percent (product of Changling catalyst, changling Co.) are weighed and uniformly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier Z5.
Taking 5 g of carrier Z and using 84 ml of carrier Z containing 55.6 g/L of NiO and MoO respectively 3 285.7 g/l, P 2 O 5 55.6 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain the catalyst C5.
The composition of the catalyst C5 after calcination is shown in Table 2, based on the catalyst.
Example 6
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70 percent, 25.4 g of Y1-3 molecular sieve with a dry basis of 84 percent, 82.3 g of Y2-3 molecular sieve with a dry basis of 81 percent and 72.4 g of ZRP-5 molecular sieve with a dry basis of 81 percent (product of Changling catalyst, changling Co.) are weighed and evenly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier Z6.
Taking 6 g of carrier Z and using 76 ml of carrier Z containing 61.4 g/L of NiO and MoO respectively 3 315.8 g/l, P 2 O 5 61.4 g/l basic nickel carbonate, molybdenum trioxide and phosphorusSoaking in the acid mixed solution for 3 hours, drying at 120 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the catalyst C6.
The composition of the catalyst C6 after calcination is shown in Table 2, based on the catalyst.
Example 7
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70 percent, 28.6 g of Y1-3 molecular sieve with a dry basis of 84 percent, 115.2 g of Y2-3 molecular sieve with a dry basis of 81 percent and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81 percent (product of Changling catalyst, changling Co.) are weighed and uniformly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier Z7.
Taking 7 g of carrier Z and using 84 ml of carrier Z containing 55.6 g/L of NiO and MoO respectively 3 285.7 g/l, P 2 O 5 55.6 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain a catalyst C7.
The composition of the catalyst C7 after calcination is shown in Table 2, based on the catalyst.
Comparative example 1
76.2 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70% and 174.6 g of Y1-3 molecular sieve with a dry basis of 84% are weighed and mixed uniformly, and extruded into a three-leaf strip with a circumscribed circle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier DZ1.
Taking 100 g of carrier DZ, and using 76 ml of carrier DZ containing 61.4 g/L of NiO and MoO respectively 3 315.8 g/l, P 2 O 5 61.4 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain the catalyst DC1.
The composition of the catalyst DC1 after calcination is shown in Table 2, based on the catalyst.
Comparative example 2
76.2 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70% and 181.1 g of Y2-2 molecular sieve with a dry basis of 81% are weighed and mixed uniformly, and extruded into a three-leaf strip with a circumscribed circle diameter of 1.6 mm on a strip extruder, and dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier DZ2.
Taking 100 g of carrier DZ, and using 90 ml of carrier DZ containing 51.9 g/L of NiO and MoO respectively 3 266.7 g/l, P 2 O 5 51.9 g/L of mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain the catalyst DC2.
The composition of the catalyst DC2 after calcination is shown in Table 2, based on the catalyst.
Comparative example 3
76.2 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70% and 44.4 g of Y1-3 molecular sieve with a dry basis of 84% and 135.0 g of Y2-2 molecular sieve with a dry basis of 81% are weighed and mixed uniformly, and extruded into a three-leaf strip shape with a circumscribed circle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier DZ3.
Taking 5 g of carrier Z and using 86 ml of carrier Z containing 54.3 g/L of NiO and MoO respectively 3 279.1 g/L, P 2 O 5 54.3 g/L mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain the catalyst DC3.
The composition of the catalyst DC3 after calcination is shown in Table 2, based on the catalyst.
Comparative example 4
76.2 g of pseudo-boehmite (catalyst, kaolin, co.) with a dry basis of 70%, 34.8 g of Y1-2.75 g of Y1-3 molecular sieve with a dry basis of 79%, 34.8 g of ZRP-5 molecular sieve with a dry basis of 84% and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81% are weighed and uniformly mixed, extruded into a three-leaf strip shape with a circumcircle diameter of 1.6 mm on an extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier DZ4.
Taking 6 g of carrier Z and using 82 ml of NiO containing 57.0 g/L and MoO respectively 3 292.7 g/l, P 2 O 5 57.0 g/L mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain catalystAnd a chemical agent DC4.
The composition of the catalyst DC4 after calcination is shown in Table 2, based on the catalyst.
Comparative example 5
76.2 g of pseudo-boehmite (catalyst, changling Co.) with a dry basis of 70%, 85.58 g of Y2-2 molecular sieve with a dry basis of 81%, 36.1 g of Y2-3 molecular sieve with a dry basis of 81% and 36.2 g of ZRP-5 molecular sieve with a dry basis of 81% (product of Changling catalyst, changling Co.) are weighed and evenly mixed, extruded into a three-blade strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a catalyst carrier DZ5.
The carrier DZ was taken in an amount of 5 g and 88 ml of NiO was used in an amount of 53.1 g/l and MoO, respectively 3 272.7 g/L, P 2 O 5 53.1 g/L mixed solution of basic nickel carbonate, molybdenum trioxide and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and baked for 3 hours at 450 ℃ to obtain the catalyst DC5.
TABLE 2 composition of catalysts for examples and comparative examples
The performance of the hydrocracking catalysts provided by the present invention was tested by the following application examples.
Application example 1
At a density of 0.9561 g/cm 3 The performance of the catalyst C1 provided by the invention was evaluated on a 30 ml fixed bed apparatus with a catalytic cracking diesel oil as a raw material having a sulfur content of 9800ppm, a nitrogen content of 743ppm and a dry point of 345 ℃, wherein the upper part of the bed layer was filled with an industrial refined catalyst and the lower part was filled with the catalyst C1, and the loading amount of the catalyst C1 was 15 ml.
The catalyst C1 is presulfided before raw oil is fed, and the vulcanization conditions are as follows: vulcanizing at 110 ℃ for 2 hours and vulcanizing at 300 ℃ for 4 hours, wherein the vulcanized oil is kerosene containing 6 weight percent of carbon disulfide.
Reaction conditions: hydrofining reaction zone conditions: the reaction temperature is 360 ℃, the hydrogen partial pressure is 5.5MP, and the liquid hourly space velocity is 1.0h -1 Hydrogen-oil volume ratio 800, cracking agent reaction zoneConditions are as follows: the reaction temperature is 400 ℃, the hydrogen partial pressure is 5.5MPa, and the liquid hourly space velocity is 1.6h -1 Hydrogen oil volume ratio 800, light diesel oil circulation ratio 0.3.
The test results are shown in Table 3.
Application example 2
The performance of catalyst C5 was tested under the same conditions as in application example 1, and the test results are shown in Table 3.
Application example 3
The performance of catalyst C6 was tested under the same conditions as in application example 1, and the test results are shown in Table 3.
Comparative application example 1
The performance of catalyst DC1 was tested according to the same conditions and raw materials as in application example 1, and the test results are shown in Table 3.
Comparative application example 2
The performance of catalyst DC2 was tested according to the same conditions and raw materials as in application example 1, and the test results are shown in Table 3.
Comparative application example 3
The performance of catalyst DC3 was tested according to the same conditions and raw materials as in application example 1, and the test results are shown in Table 3.
Comparative application example 4
The performance of catalyst DC4 was tested according to the same conditions and raw materials as in application example 1, and the test results are shown in Table 3.
Comparative application example 5
The performance of catalyst DC5 was tested according to the same conditions and raw materials as in application example 1, and the test results are shown in Table 3.
TABLE 3 catalyst reactivity
Application example 4
At a density of 0.9664 g/cm 3 The catalytic cracking diesel oil having a sulfur content of 9200ppm, a nitrogen content of 912ppm and a dry point of 365℃was used as a raw material, and the performance of the catalyst C1 was tested under the same reaction conditions as in application example 1, with the test results shown in Table 4.
Application example 5
At a density of 0.9664 g/cm 3 The catalytic cracking diesel oil having a sulfur content of 9200ppm, a nitrogen content of 912ppm and a dry point of 365℃was used as a raw material, and the performance of the catalyst C5 was tested under the same reaction conditions as in application example 1, with the test results shown in Table 4.
Comparative application example 6
The performance of catalyst DC1 was tested according to the same conditions and raw materials as in application example 4, and the test results are shown in Table 4.
Comparative application example 7
The performance of catalyst DC2 was tested according to the same conditions and raw materials as in application example 4, and the test results are shown in Table 4.
Comparative application example 8
The performance of catalyst DC3 was tested according to the same conditions and raw materials as in application example 4, and the test results are shown in Table 4.
Comparative application example 9
The performance of catalyst DC4 was tested according to the same conditions and raw materials as in application example 4, and the test results are shown in Table 4.
Comparative application example 10
The performance of catalyst DC5 was tested according to the same conditions and raw materials as in application example 4, and the test results are shown in Table 4.
TABLE 4 catalyst reactivity (higher raw oil dry point)
The test results in tables 3 and 4 show that the hydrocracking catalyst of the present invention can increase C when used in the process of producing light aromatic hydrocarbon by catalytic diesel hydrocracking, as compared with the existing catalyst 6 -C 10 And C 6 -C 8 The hydrocracking catalyst has more obvious effect when the yield of the light aromatic hydrocarbon is equal, especially when the catalytic diesel with higher dry point is used as the raw material.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.

Claims (19)

1. A hydrocracking catalyst for producing light aromatic hydrocarbon by polycyclic aromatic hydrocarbon hydrocracking reaction is characterized in that the hydrocracking catalyst comprises a carrier and an active metal component loaded on the carrier, the carrier comprises a matrix and a composite molecular sieve,
the composite molecular sieve comprises a Y1 molecular sieve, a Y2 molecular sieve and a molecular sieve with an MFI structure, wherein the proportion of pores with the pore diameter of more than 2nm and less than 100nm on the Y1 molecular sieve in the total pores is less than 30%, the proportion of pores with the pore diameter of more than 2nm and less than 100nm on the Y2 molecular sieve in the total pores is 30-70%, the ratio of the B acid amount of the Y1 molecular sieve per unit weight to the B acid amount of the Y2 molecular sieve per unit weight is 1.1:1-4:1, and the content of the molecular sieve with the MFI structure in the composite molecular sieve is 5-40 wt%;
the mesoporous volume of the Y1 molecular sieve is 0.03-0.12 cm 3 /g；
The mesoporous volume of the Y2 molecular sieve is 0.12-0.50 cm 3 /g；
In the composite molecular sieve, the weight ratio of the Y1 molecular sieve to the Y2 molecular sieve is 1:9-9:1;
the active metal component comprises at least one metal component selected from VIII groups and at least one metal component selected from VIB groups, and the atomic ratio of the VIII group metal to the VIB group metal is 0.05-0.6.
2. The hydrocracking catalyst according to claim 1, wherein the pores with a pore size of more than 2nm and less than 100nm on the Y1 molecular sieve account for 5 to 25% of the total pores.
3. The hydrocracking catalyst according to claim 1, wherein the pores with a pore size of more than 2nm and less than 100nm on the Y2 molecular sieve account for 35 to 60% of the total pores.
4. The hydrocracking catalyst of claim 1 wherein the ratio of the amount of B acid per weight of the Y1 molecular sieve to the amount of B acid per weight of the Y2 molecular sieve is from 1.1:1 to 2.5:1.
5. The hydrocracking catalyst of claim 1 wherein the Y1 molecular sieve has a mesoporous volume of from 0.06 cm to 0.11cm 3 /g。
6. The hydrocracking catalyst of claim 1 wherein the Y2 molecular sieve has a mesoporous volume of from 0.15 cm to 0.40cm 3 /g。
7. The hydrocracking catalyst of claim 1 wherein the molecular sieve having an MFI structure is ZSM-5, ZRP-5 or a mixture thereof.
8. The hydrocracking catalyst according to claim 1, wherein the content of the molecular sieve having MFI structure is 5wt% to 30wt%, based on the composite molecular sieve.
9. The hydrocracking catalyst of claim 1 wherein the weight ratio of the Y1 molecular sieve to the Y2 molecular sieve in the composite molecular sieve is from 1:1 to 1:4.
10. The hydrocracking catalyst of any one of claims 1 to 9, wherein the hydrocracking catalyst comprises, in weight percent, from 5% to 30% of the active metal component, from 45% to 70% of the composite molecular sieve, and from 10% to 25% of the matrix.
11. The hydrocracking catalyst of claim 10 wherein the active metal component comprises at least one metal component selected from group VIII and at least one metal component selected from group VIB and the atomic ratio of group VIII metal to group VIB metal is from 0.2 to 0.5.
12. The hydrocracking catalyst of claim 10 wherein the substrate is an inorganic oxide.
13. The hydrocracking catalyst of claim 12 wherein the substrate is alumina.
14. The method for producing a hydrocracking catalyst as claimed in any one of claims 1 to 13, comprising:
uniformly mixing the molecular sieve and the matrix, molding, and roasting to obtain the carrier;
and impregnating the carrier with a solution containing the active metal component, and drying and roasting to obtain the hydrocracking catalyst.
15. Use of a hydrocracking catalyst according to any one of claims 1 to 13 in the hydrocracking reaction of polycyclic aromatic hydrocarbons to produce light aromatic hydrocarbons.
16. The use according to claim 15, characterized in that the hydrocracking reaction is carried out using a catalytic diesel as starting material, using a fixed bed sheet section series and a light diesel recycle process.
17. The use according to claim 16, wherein the fitted sheet stage series process comprises a hydrofinishing reaction zone and a hydrocracking reaction zone, the catalytic diesel first entering the hydrofinishing reaction zone and then entering the hydrocracking reaction zone, the reaction conditions of the hydrofinishing reaction zone and the hydrocracking reaction zone each independently comprising: the reaction temperature is 300-450 ℃, the reaction pressure is 4.0-10.0 MPa, the hydrogen-oil volume ratio is 200-1500, and the volume airspeed is 0.5-2.5; the light diesel oil circulation ratio of the light diesel oil circulation process is 0-0.5.
18. The use according to claim 16, wherein the catalytic diesel has a dry point of greater than 330 ℃.
19. The use according to claim 18, wherein the catalytic diesel has a dry point of greater than 350 ℃.
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