CN106268931A - A kind of hydrocracking catalyst containing composite molecular screen and application thereof - Google Patents

Abstract

A kind of hydrocracking catalyst and application thereof, containing carrier and at least one selected from VIII and at least one is selected from the metal component of group vib, described carrier contains Beta molecular sieve, Y type molecular sieve and aluminium oxide, on the basis of carrier, the content of Beta type molecular sieve is 3 weight %～80 weight %, the content of Y type molecular sieve is 3 weight %～80 weight %, the content of aluminium oxide is 15 weight %～90 weight %, it is characterized in that, described carrier is by Beta type molecular sieve, Y type molecular sieve mixes with boehmite, molding, it is dried and roasting obtains, described boehmite includes PB1, characterize with X-ray diffraction, the κ of described PB1₁And κ₂It is respectively greater than 1 to less than or equal to 3, wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃It is respectively in the x-ray diffraction spectra of PB1 the peak height of three diffraction maximums at 2 θ angles being 24 °～30 °, 35 °～41 ° and 46 °～52 °.Compared with providing catalyst with prior art, the present invention provides catalyst to have more preferable hydrogenation aromatics-removing performance.

Description

A kind of hydrocracking catalyst containing composite molecular screen and application thereof

Technical field

The present invention relates to a kind of hydrocracking catalyst and application thereof.

Background technology

Beta molecular sieve has stronger isomerism ability owing to having three dimensional intersection pore passage structure, is hydrocracked and urges Agent generally use this component reduce raw material condensation point.

CN1315883 discloses a kind of hydrocracking catalyst containing modified Beta zeolite, with catalyst On the basis of percentage by weight, including: (a) Beta zeolite 5%～40%；(b) big pore volume refractory oxide 10%～70%；(c) little porous aluminum oxide 0%～30%；(d) group vib metal-oxide 10%～40%；(e)VIII Metal-oxide 1%～10%；Described Beta zeolite SiO₂/Al₂O₃Mol ratio is 20～150, > 2nm two Secondary aperture pore volume accounts for more than the 40% of total pore volume, specific surface 500～750m²/ g, infrared acidity 0.05～0.5mmol/g, Na₂< 0.2%, at 25 DEG C, when P/Po is 0.1, water adsorption amount is little for O weight content In 5 weight %, n-butyl alcohol adsorption experiment residual value is less than 0.4, ion exchange capacity < 0.07.Described hole Hold the refractory oxide mixture selected from aluminium oxide, sial or aluminium oxide with silicon oxide.

Using this catalyst to be hydrocracked, the measuring change of diesel oil solidifying point ratio in product is relatively low, can produce width and evaporate Divide low freezing point diesel fuel.Industry is hydrocracked charging and includes 350～540 DEG C of fractions such as VGO, and reaction temperature is general Between 350～440 DEG C, in charging, high boiling component contacts with catalyst in liquid form when reaction. Now solve resistance to mass tranfer, improve catalyst activity product key issue.

Need to improve catalyst pore passage structure, improve reaction molecular and touch hydrogenation active metals in catalyst Ability.Owing to molecular sieve and metal sulfide pore volume are less, particularly meet macromole required by PETROLEUM PROCESSING The middle macropore that hydrocarbon feed requires is less, and conventional method can be big by introducing in carrier of hydrocracking catalyst The method of pore volume heat-resistant inorganic oxide matrix realizes, such as, introduce alumina host.

ZL01123765.1 discloses a kind of catalyst for hydrogenation treatment of diesel oil, this catalyst contain a kind of carrier and Load molybdenum on this carrier and/or tungsten and nickel and/or cobalt, it is characterised in that described carrier is by aluminium oxide Forming with zeolite, aluminium oxide is 90:10～50:50 with the weight ratio of zeolite, and described aluminium oxide is by aperture The aluminium oxide that aluminium oxide and macroporous aluminium oxide are composited according to the weight ratio of 75:25～50:50, wherein, Little porous aluminum oxide is that diameter is less than the pore volume in 80 angstroms of holes and accounts for the aluminium oxide of total pore volume more than 95%, macropore Aluminium oxide is the aluminium oxide that the pore volume in diameter 60～600 angstroms of holes accounts for total pore volume more than 70%.

Summary of the invention

It is an object of the invention to provide a kind of performance obtain improve hydrocracking catalyst and this catalyst should With.

The content that the present invention relates to includes:

A kind of hydrocracking catalyst, is selected from at least one selected from VIII with at least one containing carrier The metal component of group vib, described carrier contains Beta molecular sieve, Y type molecular sieve and aluminium oxide, with carrier On the basis of, the content of Beta type molecular sieve is 3 weight %～80 weight %, and the content of Y type molecular sieve is 3 Weight %～80 weight %, the content of aluminium oxide is 15 weight %～90 weight %, it is characterised in that described load Body is mixed with Y type molecular sieve, boehmite by Beta type molecular sieve, molding, be dried and roasting obtain Arriving, described boehmite includes PB1, characterizes with X-ray diffraction, the κ of described PB1₁And κ₂Value model Enclosing is 1 ＜ κ₁≤ 3,1 ＜ κ₂≤ 3, wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃It is respectively PB1's At the peak height of three diffraction maximums that 2 θ angles are 24～30 °, 35～41 ° and 46～52 ° in x-ray diffraction spectra.

The catalyst provided according to the present invention, under optimum condition, on the basis of carrier, Beta type molecular sieve Content is 5 weight %～65 weight %, and the content of Y type molecular sieve is 5 weight %～65 weight %, aluminium oxide Content be 30 weight %～90 weight %；Characterize with X-ray diffraction, the κ of described PB1₁And κ₂It is respectively 1.02～2.4；Further preferably, the κ of described PB1₁It is 1.2～2.3, κ₂It is 1.02～1.4；Described PB1's Specific surface area is 100～350 meters²/ gram, pore volume is 0.7～1.2 ml/g, it is preferable that the ratio of described PB1 Surface area is 150～280 meters²/ gram, pore volume is 0.85～1.12 ml/g.

The catalyst provided according to the present invention, described Beta molecular sieve is hydrogen type molecular sieve, and described Beta divides The silica alumina ratio of son sieve is 20～120, and specific surface area is 200～650 meters²/ gram, pore volume is 0.20～0.75 milliliter/ Gram；Described Y type molecular sieve is super-stable Y molecular sieves, and the lattice constant of described Y type molecular sieve is 2.460～2.430, specific surface area is 550～700 meters²/ gram, pore volume is 0.30～0.45 ml/g.

The catalyst provided according to the present invention, described Y type molecular sieve can contain phosphorus, with described molecular sieve be Benchmark, the content of phosphorus is 0.1 weight %～2.5 weight %, preferably 0.4 weight %～2.0 weight %.

In the catalyst that the present invention provides, the metal component of described VIII is selected from nickel and/or cobalt, described The metal component of group vib is selected from molybdenum/or tungsten, counts and on the basis of described catalyst by oxide, described nickel And/or the content of cobalt is 1 weight %～15 weight %, preferably 2 weight %～10 weight %, described molybdenum/or tungsten Content be 5 weight %～40 weight %, preferably 10 weight %～35 weight %.

The boehmite preparing catalyst of the present invention can be the mixture of PB1 and PB2, with butt Counting and on the basis of carrier, the content of PB1 is 10～90 weight %, and the content of PB2 is 5～60 weight %, With infrared spectrum characterization, the δ-value of PB2 is 1.5～4.5, wherein, δ=I₁/(I₂+I₃), I₁Thin for described plan Diaspore infrared hydroxyl spectrum in 3665～3680cm^-1The peak height of place's absworption peak, I₂It is 3720～3730cm^-1Place The peak height of absworption peak, I₃It is 3760～3780cm^-1The peak height of place's absworption peak；Under preferable case, in terms of butt And on the basis of carrier, the content of PB1 is 20 weight %～80 weight %, the content of PB2 is 10 weights Amount %～50 weight %, the δ-value of described PB2 is 1.8～3.8.Described PB2 is the modifier of PB1, modified Condition is that PB1 is dried 0.5～14 hour at 70～400 DEG C, it is preferable that modified condition is that PB1 exists 220～330 DEG C are dried 1～6 hour.

Preparing catalyst of the present invention, described drying condition includes: temperature is 50～350 DEG C, time Between be 1～24 hour；Described roasting condition includes: temperature is 400～700 DEG C, and the time is 0.5～6 little Time；Under optimum condition, described drying condition includes: temperature is 80～200 DEG C, and the time is 1～6 hour； Described roasting condition includes: temperature is 550～650 DEG C, and the time is 1～3 hour.

Present invention also offers the application in hydrocarbon ils is processed of the described catalyst.

In the present invention, Beta zeolite is zeolite known to people, its Nomenclature Composition and Structure of Complexes at US3,308,069 Hes Re28341 is already described.The catalyst provided according to the present invention, wherein suitably Beta zeolite can be Commercially available commodity, it would however also be possible to employ prepared by any one prior art.Preferably zeolite is silicon oxide/oxidation Aluminum (mol ratio) at least 25, such as the Beta zeolite of 30～500, the Beta zeolite being more highly preferred to is oxidation Silicon/aluminium oxide (mol ratio) is 30～200, and EP164 is shown in the description for this Beta zeolite, 939, US4,923,690, US5,164,169, CN1108213A, CN1108214A, CN1086792A etc. are special Profit.On the basis of carrier, the content of Beta type molecular sieve is 3 weight %～80 weight %, preferably 5 weights Amount %～65 weight %.

In the present invention, described Y type molecular sieve is selected from HY (hydrogen Y type molecular sieve), REY (alkene soil Y Type molecular sieve), PY (phosphorus-contained gamma-type molecular sieve), USY (super-stable Y molecular sieves), PUSY (contain Phosphorus USY, including PHY, REUSY (the super steady Y of alkene soil)), USY, PUSY preferably wherein, Further preferably PUSY.Described molecular sieve can be commercially available commodity, it would however also be possible to employ arbitrary existing skill Prepared by art.Such as, the disclosed method preparing USY of ZL00123139.1, Zl200410071122.6 is public The method preparing PUSY opened, the most all as reference.

Described molding is carried out according to a conventional method, such as extruded moulding.Can add when extrusion molding and help in right amount Squeeze agent and/or adhesive, then extrusion molding.Described extrusion aid, the kind of peptizer and consumption are ability Well known to field technique personnel, it is not repeated herein.

The described method being dried with roasting is conventional method, such as, uses baking oven, guipure, converter heating side Method is dried, and drying condition includes temperature 50～350 DEG C, preferably 70～200 DEG C, time 1～24 hours, Preferably 2～6 hours；Using baking oven, guipure, converter heating means to carry out roasting, roasting condition includes temperature 350～800 DEG C, preferably 400～700 DEG C, time 0.5～6 hours, preferably 1～4 hour.

Inventors of the present invention have surprisingly found that, characterize with X-ray diffraction, use and include that one meets κ₁Value It is 1 to less than or equal to 3 with κ₂Value is 1 to the boehmite PB1 less than or equal to 3 and Beta molecule Sieve and Y type molecular sieve prepare carrier, this carrier, when preparing hydrocracking catalyst, catalyst has higher Aromatic hydrocarbons conversion performance.

Wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃It is respectively in the x-ray diffraction spectra of PB1 at 2 θ Angle is the peak height of three diffraction maximums of 24 °～30 °, 35 °～41 ° and 46 °～52 °.

According to the present invention, the κ of further preferred described PB1₁And κ₂Value be respectively 1.02～2.3, more excellent Select the κ of described PB1₁Value be 1.2～2.3, κ₂Value be 1.02～1.4.

On the premise of being sufficient for application claims, the source of PB1 is not particularly limited by the present invention, example As, can be commercially available commodity or use arbitrary existing method to prepare.Such as CN100999328B is open The boehmite prepared of the class boehmite method that uses aluminum sulfate and sodium metaaluminate neutralisation to prepare The requirement of the present invention can be met, herein by reference as quoting.

In the present invention, described PB1 is at κ₁And κ₂Value meet require on the premise of, specific surface preferably wherein Amass is 100～350 meters²/ gram, pore volume is 0.7～1.2 ml/g, and further preferred specific surface area is 150～280 Rice²/ gram, pore volume is the boehmite of 0.85～1.12 ml/g.

In the present invention, the pore volume of described boehmite, specific surface area etc., be by described boehmite in After 600 DEG C of roastings 4 hours, BET N2 adsorption characterize and obtain.

Inventor further study show that, is being done in 70～400 DEG C by the boehmite meeting aforementioned claim Dry 0.5～14 hour, it is preferable over 220～330 DEG C and is dried after 1～6 hour, obtain the modifier PB2 of PB1, Employing infrared absorption spectroscopy characterizes, and the δ-value of PB2 is 1.5～4.5, preferably 1.8～3.8.Use it and PB1 And Beta molecular sieve and Y type molecular sieve mixing, the carrier prepared of molding prepare hydrocracking catalyst Time, the performance of catalyst is further enhanced.Wherein, δ=I₁/(I₂+I₃), I₁For described plan thin water aluminum Stone infrared hydroxyl spectrum in 3665～3680cm^-1The peak height of place's absworption peak, I₂It is 3720～3730cm^-1Place absorbs The peak height at peak, I₃It is 3760～3780cm^-1The peak height of place's absworption peak.

The catalyst provided according to the present invention, described selected from VIII with selected from the containing of metal component of group vib Amount is for the usual content of hydrocracking catalyst, such as, by the basis of catalyst and in terms of oxide, described in urge Agent contains the group VIII metal component of 1 weight %～15 weight %, 5 weight %～the group vib of 40 weight % Metal component；Preferably comprise the group VIII metal component of 2 weight %～10 weight %, 10 weight %～35 weights The group vib metal component of amount %.One or more in Cr, Mo or W of described group vib metal, Preferably Mo and/or W, one or more in Fe, Co or Ni of described group VIII metal component, Preferably Co and/or Ni.Be enough to by described at least one selected from VIII and at least one is selected from group vib Metal component be carried on described alumina support on the premise of, concrete carrying method is limited the most especially System.Preferably method is infusion process.Including separately or concurrently preparing containing selected from VIII and the metal of group vib The dipping solution of component composition, described dipping according to impregnation liquid consumption difference can be excess immersion stain, The saturated dipping in hole, the mode difference realized according to dipping can be infusion method leaching, spray impregnating.Pass through Concentration, consumption or the regulation of carrier consumption and control to dipping solution, can prepare appointment content Described catalyst, this is that those skilled in the art are readily appreciated by, and does not repeats.

The method for preparing catalyst provided according to the present invention, described vib metals compound is selected from these One or more in the soluble compound of metal, for example, it may be silico-tungstic acid, silicotungstate, phosphorus molybdenum In acid, phosphomolybdate, molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate one Plant or several.

Described group VIII metallic compound is selected from the salt of these metals, including their inorganic acid salt or have Machine salt.Such as, described inorganic salt is selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphoric acid One or more in the partially decomposed product of salt, sulfate, chloride and these salts, it is preferable that One or more in nitrate, carbonate or subcarbonate.Described organic salt be Organic substance with Group VIII metal combines the salt or soluble complexes generated, and described Organic substance can be organic base, organic Carboxylic acid, amine, ketone, ethers, alkyls, preferably organic carboxylate.

The catalyst provided according to the present invention, it is also possible to containing organic additive, with described catalyst as base Standard, and in terms of carbon, the content of described organic additive is less than 10 weight %, the most not More than 6 weight %.

One or more in oxygen-containing and/or nitrogenous Organic substance of described organic additive.Described contain One or more in Organic Alcohol, the organic acid of oxygen compound, organic compounds containing nitrogen selected from organic amine, One or more in organic ammonium salt.Specifically, selected from oxygen containing Organic substance selected from ethylene glycol, glycerol, Polyethylene Glycol (molecular weight is 200～1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, One or several in aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid Kind, wherein preferred ethylene glycol, glycerol, Polyethylene Glycol and citric acid；Nitrogenous Organic substance is selected from second two Amine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, glycine, nitrilotriacetic acid(NTA), EDTA and One or more in ammonium salt, wherein preferred EDTA and nitrilotriacetic acid(NTA).Described organic additive is also Can include containing Organic Alcohol and organic acid simultaneously.

The preparation method provided according to the present invention, when the catalyst of the present invention contains organic additive further Time, also including the step introducing organic compound, described organic compound can be together with group VIII metal Introduce, it is also possible to introduce after group VIII metal introducing, and be dried, preferably by Organic substance and the Group VIII metal is configured to mixed solution and is simultaneously introduced by the way of dipping, is dried afterwards.Described dry The selection of dry temperature and time except not enough so that group VIII metal salt or complex decompose in addition to, also should allow Catalyst retains the Organic substance that major part is introduced, such as, retains the Organic substance of more than 50%, more preferably Ground, retains the Organic substance of more than 70%.Its method can be that in prior art, any one can realize above-mentioned mesh Method.Such as, heat drying, drying under reduced pressure and add the methods such as thermal drying under reduced pressure.When described When drying means is heat drying, preferred baking temperature is less than 250 DEG C, is further preferably less than 200 DEG C, more preferably not more than 180 DEG C.

According to the conventional method in this area, described hydrotreating catalyst before the use, generally can be at hydrogen In the presence of gas, at a temperature of 140～370 DEG C, carry out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this Presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component it loaded is converted into Metal sulfide component.

The catalyst that the present invention provides can be used for hydrocracking or the hydro-upgrading of all kinds of hydrocarbon oil crude material.For adding The reaction condition of hydrogen cracking or hydro-upgrading is usual hydrocracking or hydro-upgrading reaction condition, the most instead Ying Wenwei degree 200～420 DEG C, more preferably 220～400 DEG C, pressure is 2～18 MPas, the most excellent Electing 2～15 MPas as, liquid hourly space velocity (LHSV) is 0.3～10 hour^-1, more preferably 0.3～5 hour^-1, hydrogen oil Volume ratio is 50～5000, more preferably 50～4000.

The device of the reaction of described hydrocracking or hydro-upgrading can make described raw oil add any being enough to Hydrogen processes and carries out, such as, described solid in reaction dress device catalytic with described catalyst under reaction condition Fixed bed reactor, moving-burden bed reactor or fluidized bed reactor are carried out.

Compared with providing catalyst with prior art, the present invention provides catalyst to have more preferable hydrogenation aromatics-removing Energy.Such as, 4%～10% is added at the aromatic hydrocarbons activity of conversion using rear catalyst of the present invention.

Accompanying drawing explanation

Accompanying drawing is in order to a further understanding of the present invention, and constitutes the part of description, with following tool Body embodiment is used for illustrating the present invention together, but is not intended that limitation of the present invention.In the accompanying drawings:

PB1-1 in Fig. 1 (XRD figure of boehmite) is the boehmite meeting application claims XRD spectra；PB2-2 is a kind of modifier of PB1-1；SB (the plan thin water aluminum that Sasol company produces Stone, trade name SB powder) it is the XRD spectra of a kind of boehmite that can not meet application claims.

The IR-OH spectrum of the modifier that PB2-2 is PB1-1 in Fig. 2 (the IR-OH figure of boehmite) Figure；PB2-3 is that PB1-1 is in the IR-OH spectrogram of 600 DEG C of product of roastings.

Detailed description of the invention

The present invention is described further for the following examples.

In experiment, XRD is carried out on the D5005 type X-ray diffractometer of Siemens, Cu Target, Ka radiates, solid probe, 40kV, 40mA, step-scan, stride 0.02 °, sweep limits 5 °～70 °.

IR-OH spectrogram is surveyed at U.S.'s BIO-RAD company FT3000 type Fourier transformation infrared spectrometer Fixed, the self-supporting sheet of 15mm, and vacuum is to 10^-3Pa, keeps 1h, scans after being cooled to room temperature 1000～4000cm^-1Wave-number range.

In heavy oil, saturated hydrocarbons and aromatic hydrocarbons composition use SH/T0659-1998 method to measure with content.

Boehmite, preparation method or source used in embodiment and comparative example:

PB1-1

It is the sodium metaaluminate of 195g/L by the aluminum sulfate that 500mL concentration is 93g/L and the concentration of clear (causticity coefficient is 1.6) is slowly added in the reactor of 2L band stirring, controls reaction temperature and is 40 DEG C, pH value 7.3.After reaction completely, it is that the sodium carbonate of 0.5mol/L is to pH value of solution that stirring adds concentration Value is 9.7.After constant temperature 50 DEG C reacts 1 hour, filter, deionized water wash three times, baking oven ventilates 120 DEG C of temperature are dried 3hr, obtain boehmite PB1-1.The h1 of PB1-1, h2, h3, k₁, k₂With And pore volume is listed in table 1.

PB1-2

The aluminum sulfate that 600mL concentration is 48g/L of clear and the ammonia of concentration 8% are slowly added simultaneously Entering in the reactor of 2L band stirring, reaction is filtered, and add ammonia controlling reaction temperature is 35 DEG C, pH value 6.0.After reaction completely, filtering, pulled an oar by filter cake, stirring adds ammonium hydrogen carbonate and to solution ph is 9.5.After constant temperature 35 DEG C reacts 12 hours, filter, deionized water wash three times, baking oven ventilates 120 DEG C Temperature is dried 3 hours, obtains boehmite PB1-2.The h1 of PB1-2, h2, h3, k₁, k₂And Its pore volume is listed in table 1.

PB1-3

The aluminum sulfate that 600mL concentration is 93g/L of clear and the ammonia of concentration 8% are slowly added simultaneously Entering in the reactor of 2L band stirring, controlling reaction temperature is 50 DEG C, pH value 4.6.After reaction completely, mistake Filter, pulls an oar filter cake, and it is 8.4 that stirring adds sodium carbonate to solution ph.Constant temperature 35 DEG C reacts 0.5 hour After, filtering, deionized water wash three times, 120 DEG C of temperature of ventilating in baking oven are dried 3 hours, obtain intending thin Diaspore PB1-3.The h1 of PB1-3, h2, h3, k₁, k₂And its pore volume is listed in table 1.

SB

The boehmite that Sasol company produces, trade name SB powder.The h1 of SB, h2, h3, k₁, k₂And its pore volume is listed in table 1.

Table 1 boehmite XRD characterizes data

Wherein, SB can not meet application claims.

Boehmite modifier used in embodiment and comparative example and preparation method thereof:

PB2-1

300 grams of PB1-1 are placed in Muffle furnace, are heated to 250 DEG C and constant temperature 3 hours at such a temperature, Obtain PB2-1.The h1 of PB2-1, h2, h3, k1, k2 and its pore volume are listed in table 1, the I1 of PB2-1, I2, I3 and δ-value are listed in table 2.

PB2-2

300 grams of PB1-1 are placed in Muffle furnace, are heated to 300 DEG C and constant temperature 3 hours at such a temperature, Obtain PB2-2.The h1 of PB2-2, h2, h3, k1, k2 and its pore volume are listed in table 1, the I1 of PB2-2, I2, I3 and δ-value are listed in table 2.

PB2-3

300 grams of PB1-1 are placed in Muffle furnace, are heated to 600 DEG C and constant temperature 3 hours at such a temperature, Obtain PB2-3.The I1 of PB2-3, I2, I3 and δ-value are listed in table 2.

PB2-4

300 grams of PB1-2 are placed in Muffle furnace, are heated to 230 DEG C and constant temperature 5 hours at such a temperature, Obtain PB2-4.The I1 of PB2-4, I2, I3 and δ-value are listed in table 2.

PB2-5

300 grams of PB1-3 are placed in Muffle furnace, are heated to 330 DEG C and constant temperature 2 hours at such a temperature, Obtain PB2-5.The I1 of PB2-5, I2, I3 and δ-value are listed in table 2.

Table 2 boehmite PB Infrared Characterization data

Comparative example 1

By 533 grams of boehmite SB, (butt 0.75, butt assay method is for insert a certain amount of former powder Crucible with cover is put in Muffle furnace, is warming up to 700 DEG C of constant temperature after 1 hour, calculates the residue ratio with former powder Value, lower with) with 62.5 mole sieve Beta (middle Effect of Catalysis In Petrochemistry Ji Jianchang branch company produces, silica alumina ratio 24, Pore volume 0.39ml/g, butt 0.8), with 61.7g gram of phosphorous super stable molecular sieve PUSY (middle Effect of Catalysis In Petrochemistry agent Branch company's Chang Ling catalyst plant produces, trade name USY-5, phosphorus pentoxide content 1.2%, lattice constant 24.44, pore volume 0.40ml/g, butt 0.81), the mixing of 16 grams of sesbania powder, being extruded into circumscribed circle diameter is 1.6 The trilobal bar of millimeter, dries 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 hours, obtains carrier, catalysis Agent carrier composition is shown in Table 3.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, oxidation W content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, oxidation Nickel content is 51 weight %) 8.7 grams, 10.5g citric acid 70mL aqueous impregnation, 180 DEG C are dried 10 hours, Obtain catalyst R-1.On the basis of catalyst total amount, in R1, the mass fraction of metal component is (for calculating Value, lower same) it is listed in table 3.

Embodiment 1

By 533 grams of boehmite powder PB1-1 (butt 0.75) with 62.5 mole sieve Beta, 61.7g Gram USY-5, the mixing of 16 grams of sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C Dry 3 hours, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier composition is shown in Table 3.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, oxidation W content is 82 weight %) 51 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, oxidation Nickel content is 51 weight %) 8.7 grams, 10.5g citric acid 80mL aqueous impregnation, 180 DEG C are dried 10 hours, Obtain catalyst C-1.On the basis of catalyst total amount, in C-1, the mass fraction of metal component is listed in table 3.

Embodiment 2

By 267 grams of boehmite powder PB1-1 with the PB2-2 of 214 grams of contents on dry basis 0.92,62.5 grams points Son sieve Beta, 61.8g gram of USY-5, the mixing of 16 grams of sesbania powder, being extruded into circumscribed circle diameter is 1.6 millimeters Trilobal bar, 120 DEG C of drying, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier composition is shown in Table 3.

After being cooled to room temperature, take 100g carrier with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide Content is 82 weight %) 51 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide Content is 51 weight %) 8.7 grams, 10.5g citric acid 85mL aqueous impregnation, 180 DEG C are dried 10 hours, Obtain catalyst C-2.On the basis of catalyst total amount, in C-2, the mass fraction of metal component is listed in table 3.

Embodiment 3

By 460g gram of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 56g contents on dry basis 0.89, 62.5g molecular sieve Beta, 62gUSY-5, the mixing of 16 grams of sesbania powder, being extruded into circumscribed circle diameter is 1.6 millimeters Trilobal bar, 120 DEG C of drying, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier forms It is shown in Table 3.

After being cooled to room temperature, take 100g carrier with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide Content is 82 weight %) 51 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide Content is 51 weight %) 8.7 grams, 10.5g citric acid 90ml aqueous impregnation, 140 DEG C are dried 3 hours, Obtain catalyst C-3.On the basis of catalyst total amount, in C-3, the mass fraction of metal component is listed in table 3.

Embodiment 4

With embodiment 2, except that replace PB2-2 with 200gPB2-3, obtain catalyst C-4.To urge On the basis of agent total amount, in C-4, the mass fraction of metal component is listed in table 3.

Embodiment 5

By 197g gram of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 56g contents on dry basis 0.89, 344g molecular sieve Beta, 31gUSY-5, the mixing of 16 grams of sesbania powder, being extruded into circumscribed circle diameter is 1.6 millimeters Trilobal bar, 120 DEG C of drying, 480 DEG C of roasting temperatures 8 hours, obtain carrier, catalyst carrier forms It is shown in Table 3.

After being cooled to room temperature, take 100g carrier with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide Content is 82 weight %) 30 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide Content is 51 weight %) 18 grams, 25g citric acid 90ml aqueous impregnation, 110 DEG C are dried 20 hours, To catalyst C-5.On the basis of catalyst total amount, in C-4, the mass fraction of metal component is listed in table 3.

Embodiment 6

With embodiment 5, except that molecular sieve Beta consumption is 31g, USY-5 consumption is 344g, To catalyst C-6.On the basis of catalyst total amount, in C-6, the mass fraction of metal component is listed in table 3.

In table 3 catalyst, carrier and metal quality mark characterize data

Embodiment 7

This example demonstrates that the present invention provides the performance of catalyst.

In the present embodiment, the evaluation methodology of catalyst is: catalyst breakage becomes diameter 0.3～0.45 millimeter Granule, loads catalyst 0.15 gram in 2 milliliters of fixed bed reactors and reacts.Reaction temperature 330 DEG C, Reaction pressure 4.0 MPas, hydrogen-oil ratio (mol ratio) is 25, and liquid hourly space velocity (LHSV) is 30 hours^-1, with containing tetrahydrochysene The normal octane solution of naphthalene 5.61 weight % carries out micro anti-evaluation, and catalyst vulcanizes before entering reaction oil, sulfuration Condition is: under conditions of Hydrogen Vapor Pressure 4.0MPa, is warming up to 60 DEG C, is passed through containing 6%CS₂Normal hexane Solution, is warming up to 360 DEG C, constant temperature 3 hours.

Aromatic hydrocarbons activity of conversion with following formula definition catalyst:

Aromatics conversion rate=(5.61%-w)/5.61% × 100%, wherein, w is the weight of naphthane in product Percentage composition.

The results are shown in Table shown in 4:

Aromatics conversion rate under table 4 different catalysts effect

The aromatic hydrocarbons activity of conversion using rear catalyst of the present invention adds 4%～10%.

Claims (20)

1. a hydrocracking catalyst, containing carrier, selected from VIII and at least one is selected from group vib with at least one Metal component, described carrier contains Beta molecular sieve, Y type molecular sieve and aluminium oxide, with carrier as base Standard, the content of Beta type molecular sieve is 3 weight %～80 weight %, and the content of Y type molecular sieve is 3 weights Amount %～80 weight %, the content of aluminium oxide is 15 weight %～90 weight %, it is characterised in that described load Body is mixed with Y type molecular sieve, boehmite by Beta type molecular sieve, molding, be dried and roasting obtain Arriving, described boehmite includes PB1, characterizes with X-ray diffraction, the κ of described PB1₁And κ₂The biggest In 1 to less than or equal to 3, wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃It is respectively the X-ray of PB1 At the peak height of three diffraction maximums that 2 θ angles are 24～30 °, 35～41 ° and 46～52 ° in diffraction spectrogram.

Catalyst the most according to claim 1, it is characterised in that on the basis of carrier, Beta type molecular sieve Content is 5 weight %～65 weight %, and the content of Y type molecular sieve is 5 weight %～65 weight %, aluminium oxide Content be 30 weight %～90 weight %；Characterize with X-ray diffraction, the κ of described PB1₁And κ₂It is respectively 1.02～2.4.

Catalyst the most according to claim 2, it is characterised in that characterize with X-ray diffraction, the κ of described PB1₁ It is 1.2～2.3, κ₂It is 1.02～1.4.

Catalyst the most according to claim 1, it is characterised in that the specific surface area of described PB1 is 100～350 Rice²/ gram, pore volume is 0.7～1.2 ml/g.

Catalyst the most according to claim 4, it is characterised in that the specific surface area of described PB1 is 150～280 Rice²/ gram, pore volume is 0.85～1.12 ml/g.

Catalyst the most according to claim 1, it is characterised in that described Beta molecular sieve is that Hydrogen Beta divides Son sieve.

Catalyst the most according to claim 6, it is characterised in that the silica alumina ratio of described Beta molecular sieve is 20～120, specific surface area is 200～650 meters²/ gram, pore volume is 0.20～0.75 ml/g.

Catalyst the most according to claim 1, it is characterised in that described Y type molecular sieve is superstable gamma-type molecule Sieve.

Catalyst the most according to claim 8, it is characterised in that the lattice constant of described Y type molecular sieve is 2.460～2.430, specific surface area is 550～700 meters²/ gram, pore volume is 0.30～0.45 ml/g.

10. according to the catalyst described in any one of claim 1,8 or 9, it is characterised in that described Y type molecular sieve Containing phosphorus, on the basis of described molecular sieve, the content of phosphorus is 0.1 weight %～2.5 weight %.

11. catalyst according to claim 10, it is characterised in that on the basis of described molecular sieve, described phosphorus Content be 0.4 weight %～2.0 weight %.

12. catalyst according to claim 1, it is characterised in that the metal component of described VIII selected from nickel and / or cobalt, the metal component of described group vib is selected from molybdenum/or tungsten, counts with oxide and with described catalyst as base Standard, the content of described nickel and/or cobalt is 1 weight %～15 weight %, and the content of described molybdenum/or tungsten is 5 weights Amount %～40 weight %.

13. catalyst according to claim 12, it is characterised in that in terms of oxide and with described catalyst be Benchmark, the content of described nickel and/or cobalt is 2 weight %～10 weight %, and the content of described molybdenum/or tungsten is 10 Weight %～35 weight %.

14. catalyst according to claim 1, it is characterised in that described boehmite is PB1 and PB2 Mixture, count and on the basis of carrier by butt, the content of PB1 is 10 weight %～90 weight %, The content of PB2 is 5 weight %～60 weight %, and with infrared spectrum characterization, the δ-value of PB2 is 1.5～4.5, Wherein, δ=I1/ (I2+I3), I1 be described boehmite infrared hydroxyl spectrum in 3665～3680cm^-1 The peak height of place's absworption peak, I2 is 3720～3730cm^-1The peak height of place's absworption peak, I3 is 3760～3780cm^-1 The peak height of place's absworption peak.

15. catalyst according to claim 14, it is characterised in that count and on the basis of carrier by butt, The content of PB1 is 20 weight %～80 weight %, and the content of PB2 is 10 weight %～50 weight %, described The δ-value of PB2 is 1.8～3.8.

16. catalyst according to claim 14, it is characterised in that described PB2 is that PB1 is in 70～400 DEG C It is dried the modifier of 0.5～14 hour.

17. catalyst according to claim 16, it is characterised in that described PB2 is that PB1 is in 220～330 DEG C It is dried the modifier of 1～6 hour.

18. catalyst according to claim 1, it is characterised in that described drying condition includes: temperature is 50～350 DEG C, the time is 1～24 hour；Described roasting condition includes: temperature is 400～700 DEG C, time Between be 0.5～6 hour.

19. catalyst according to claim 18, it is characterised in that described drying condition includes: temperature is 80～200 DEG C, the time is 1～6 hour；Described roasting condition includes: temperature is 550～650 DEG C, the time It it is 1～3 hour.

20. according to the catalyst described in any one of claim 1～19 hydrocarbon ils process in application.