CN106268931B - A kind of hydrocracking catalyst and its application containing composite molecular screen - Google Patents

Abstract

A kind of hydrocracking catalyst and its application, containing carrier and it is at least one be selected from VIII group and at least one metal component selected from group vib, the carrier contains Beta molecular sieves, Y type molecular sieve and aluminium oxide, on the basis of carrier, the content of Beta type molecular sieves is 3 weight of weight %~80 %, the content of Y type molecular sieve is 3 weight of weight %~80 %, the content of aluminium oxide is 15 weight of weight %~90 %, it is characterized in that, the carrier is by Beta type molecular sieves, Y type molecular sieve is mixed with boehmite, molding, it dries and roasts to obtain, the boehmite includes PB1, it is characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively greater than 1 to less than be equal to 3, wherein κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃The peak height for three diffraction maximums for being 24 °~30 °, 35 °~41 ° and 46 °~52 ° at 2 angles θ respectively in the x-ray diffraction spectra of PB1.Compared with the prior art provides catalyst, the present invention, which provides catalyst, has better hydrogenation aromatics-removing performance.

Description

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

Technical field

The present invention relates to a kind of hydrocracking catalyst and its applications.

Background technology

Beta molecular sieves due to three dimensional intersection pore passage structure with stronger isomerism ability, in hydrocracking catalyst The generally use component reduces raw material condensation point.

CN1315883 discloses a kind of hydrocracking catalyst containing modified Beta zeolites, with the weight hundred of catalyst Divide on the basis of ratio, including：(a) Beta zeolites 5%~40%；(b) macropore holds refractory oxide 10%~70%；(c) aperture oxygen Change aluminium 0%~30%；(d) group vib metal oxide 10%~40%；(e) VIII metal oxides 1%~10%；It is described Beta zeolites SiO₂/Al₂O₃Molar ratio is 20~150,>The secondary pore pore volume of 2nm accounts for 40% of total pore volume or more, specific surface 500~750m²/ g, infrared 0.05~0.5mmol/g of acidity, Na₂O weight contents<0.2%, at 25 DEG C, when P/Po is 0.1, water Adsorbance is less than 5 weight %, and n-butanol adsorption experiment residual value is less than 0.4, ion exchange capacity<0.07.Described hole holds resistance to Molten oxide is selected from the mixture of aluminium oxide, sial or aluminium oxide and silica.

It is hydrocracked using the catalyst, the measuring change of diesel oil solidifying point in product is relatively low, and it is low solidifying can to produce long distillate Point diesel oil.It includes 350~540 DEG C of fractions such as VGO that industry, which is hydrocracked charging, reaction temperature generally between 350~440 DEG C, High boiling component is contacted with catalyst in liquid form in reaction in charging.Resistance to mass tranfer is solved at this time, improves catalysis Agent activated product critical issue.

It needs to improve catalyst pore passage structure, improves the ability that reaction molecular touches hydrogenation active metals in catalyst. Since molecular sieve and metal sulfide hole appearance are smaller, especially meet in macromolecule hydrocarbon feed needs required by PETROLEUM PROCESSING Macropore is less, the side that conventional method can hold heat-resistant inorganic oxide matrix by introducing macropore in carrier of hydrocracking catalyst Method is realized, such as introduces alumina host.

ZL01123765.1 discloses a kind of catalyst for hydrogenation treatment of diesel oil, which contains a kind of carrier and be supported on Molybdenum and/or tungsten and nickel on the carrier and/or cobalt, which is characterized in that the carrier is made of aluminium oxide and zeolite, aluminium oxide with The weight ratio of zeolite is 90：10~50：50, the aluminium oxide is by small porous aluminum oxide and macroporous aluminium oxide according to 75：25~50： The aluminium oxide that 50 weight ratio is combined, wherein small porous aluminum oxide is that diameter accounts for total pore volume less than the pore volume in 80 angstroms of holes 95% or more aluminium oxide, macroporous aluminium oxide are that the pore volume in 60~600 angstroms of holes of diameter accounts for the oxidation of 70% or more total pore volume Aluminium.

Invention content

The object of the present invention is to provide a kind of performances to obtain improved hydrocracking catalyst and the catalyst application.

Content of the present invention includes：

A kind of hydrocracking catalyst contains carrier and at least one selected from VIII group and at least one selected from group vib Metal component, the carrier contains Beta molecular sieves, Y type molecular sieve and aluminium oxide, on the basis of carrier, Beta type molecular sieves Content is the 3 weight % of weight %~80, and the content of Y type molecular sieve is the 3 weight % of weight %~80, and the content of aluminium oxide is 15 weights Measure the weight of %~90 %, which is characterized in that the carrier mixes by Beta types molecular sieve with Y type molecular sieve, boehmite, at Type, drying and roasting obtain, and the boehmite includes PB1, are characterized with X-ray diffraction, the κ of the PB1₁And κ₂Value range For 1 < κ₁≤ 3,1 < κ₂≤ 3, wherein κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃Respectively 2 in the x-ray diffraction spectra of PB1 The peak height for three diffraction maximums that the angles θ are 24~30 °, 35~41 ° and 46~52 °.

According to catalyst provided by the invention, under optimum condition, on the basis of carrier, the content of Beta type molecular sieves is 5 The weight % of weight %~65, the content of Y type molecular sieve are the 5 weight % of weight %~65, the content of aluminium oxide be 30 weight %~ 90 weight %；It is characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively 1.02~2.4；Further preferably, the κ of the PB1₁For 1.2~2.3, κ₂It is 1.02~1.4；The specific surface area of the PB1 is 100~350 meters²/ gram, 0.7~1.2 milliliter of Kong Rongwei/ Gram, it is preferable that the specific surface area of the PB1 is 150~280 meters²/ gram, 0.85~1.12 ml/g of Kong Rongwei.

According to catalyst provided by the invention, the Beta molecular sieves are hydrogen type molecular sieve, the silicon of the Beta molecular sieves Aluminium ratio is 20~120, and specific surface area is 200~650 meters²/ gram, 0.20~0.75 ml/g of Kong Rongwei；The Y type molecular sieve Lattice constant for super-stable Y molecular sieves, the Y type molecular sieve is 2.460~2.430, and specific surface area is 550~700 meters²/ Gram, 0.30~0.45 ml/g of Kong Rongwei.

According to catalyst provided by the invention, the Y type molecular sieve can contain phosphorus, on the basis of the molecular sieve, phosphorus Content be the 0.1 weight % of weight %~2.5, preferably 0.4 weight of weight %~2.0 %.

In catalyst provided by the invention, the metal component of the VIII group is selected from nickel and/or cobalt, the gold of the group vib Category group is selected from molybdenum/or tungsten, is counted by oxide and on the basis of the catalyst, the content of the nickel and/or cobalt is 1 weight % The content of~15 weight %, preferably 2 weight of weight %~10 %, the molybdenum/or tungsten is the 5 weight % of weight %~40, preferably For 10 weight of weight %~35 %.

The boehmite for preparing catalyst of the present invention can be the mixture of PB1 and PB2, in terms of butt and to carry On the basis of body, the content that the content of PB1 is 10~90 weight %, PB2 is 5~60 weight %, with infrared spectrum characterization, the δ of PB2 Value is 1.5~4.5, wherein δ=I₁/(I₂+I₃), I₁For 3665~3680cm in the infrared hydroxyl spectrum of the boehmite^-1 Locate the peak height of absorption peak, I₂For 3720~3730cm^-1Locate the peak height of absorption peak, I₃For 3760~3780cm^-1Locate the peak of absorption peak It is high；Under preferable case, is counted by butt and on the basis of carrier, the content of PB1 is the content of 20 weight of weight %~80 %, PB2 δ values for 10 weight of weight %~50 %, the PB2 are 1.8~3.8.The PB2 is the modifier of PB1, and modified condition is PB1 is 0.5~14 hour dry at 70~400 DEG C, it is preferable that modified condition is PB1 1~6 hour dry at 220~330 DEG C.

Catalyst of the present invention is prepared, the drying condition includes：Temperature is 50~350 DEG C, and the time is 1~24 Hour；The roasting condition includes：Temperature is 400~700 DEG C, and the time is 0.5~6 hour；Under optimum condition, described is dry Dry condition includes：Temperature is 80~200 DEG C, and the time is 1~6 hour；The roasting condition includes：Temperature is 550~650 DEG C, the time is 1~3 hour.

The present invention also provides application of the catalyst in hydrocarbon ils processing.

In the present invention, Beta zeolites are zeolites well known to people, and the Nomenclature Composition and Structure of Complexes is in US3,308,069 and Re28341 In be already described.It can also be adopted according to catalyst provided by the invention wherein suitable Beta zeolites can be commercially available commodity With any one prior art preparation.Preferred zeolite is that silica/alumina (molar ratio) is at least 25, such as 30~500 Beta zeolites, more preferably Beta zeolites are that silica/alumina (molar ratio) is 30~200, for this Beta zeolites Description see EP164,939, US4,923,690, US5,164,169, CN1108213A, CN1108214A, CN1086792A etc. Patent.On the basis of carrier, the content of Beta type molecular sieves is the 3 weight % of weight %~80, preferably 5 weights of weight %~65 Measure %.

In the present invention, the Y type molecular sieve is selected from HY (hydrogen Y type molecular sieve), REY (alkene soil Y type molecular sieve), PY and (contains Phosphorus Y type molecular sieve), USY (super-stable Y molecular sieves), PUSY (phosphorous USY, including PHY, REUSY (the super steady Y of alkene soil)), preferably its In USY, PUSY, further preferred PUSY.The molecular sieve can be commercially available commodity, can also use arbitrary existing skill It is prepared by art.For example, the disclosed methods for preparing USY of ZL00123139.1, Zl200410071122.6 is disclosed to prepare PUSY's Method, here as with reference to reference.

The molding carries out according to a conventional method, such as extruded moulding.Can be added in extrusion molding appropriate extrusion aid and/ Or adhesive, then extrusion molding.The extrusion aid, the type of peptizing agent and dosage are known to those skilled in the art, This is not repeated.

The method of the drying and roasting is conventional method, for example, being done using baking oven, guipure, converter heating means Dry, drying condition includes 50~350 DEG C of temperature, preferably 70~200 DEG C, 1~24 hour time, preferably 2~6 hours；Using baking Case, guipure, converter heating means are roasted, and roasting condition includes 350~800 DEG C of temperature, preferably 400~700 DEG C, time 0.5~6 hour, preferably 1~4 hour.

Inventors of the present invention have surprisingly found that being characterized with X-ray diffraction, meeting κ using including a kind of₁Value is 1 to small In equal to 3 and κ₂Value is that the 1 to less than boehmite PB1 equal to 3 prepares carrier with Beta molecular sieves and Y type molecular sieve, When preparing hydrocracking catalyst by the carrier, catalyst has higher aromatic hydrocarbons conversion performance.

Wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃Respectively in the x-ray diffraction spectra of PB1 2 angles θ be 24 °~ The peak height of 30 °, 35 °~41 ° and 46 °~52 ° of three diffraction maximums.

According to the present invention, the κ of the further preferred PB1₁And κ₂Value be respectively 1.02~2.3, it is more preferably described The κ of PB1₁Value be 1.2~2.3, κ₂Value be 1.02~1.4.

Be sufficient for the present invention claims under the premise of, the source of PB1 is not particularly limited in the present invention, for example, can be with It is commercially available commodity or is prepared using arbitrary existing method.Such as it is a kind of using aluminum sulfate and inclined disclosed in CN100999328B Boehmite prepared by boehmite method prepared by sodium aluminate neutralisation can meet the requirement of the present invention, here as join Examine reference.

In the present invention, the PB1 is in κ₁And κ₂Value meet the requirements under the premise of, preferably wherein specific surface area be 100~ 350 meters²/ gram, 0.7~1.2 ml/g of Kong Rongwei, further preferred specific surface area is 150~280 meters²/ gram, Kong Rongwei 0.85 ~1.12 mls/g of boehmite.

In the present invention, Kong Rong, specific surface area of the boehmite etc. are by the boehmite in 600 DEG C of roastings After burning 4 hours, characterize to obtain by BET N2 adsorptions.

Inventor further study show that, the boehmite that will meet aforementioned claim in 70~400 DEG C dry 0.5~ 14 hours, after being preferable over 220~330 DEG C of dryings 1~6 hour, the modifier PB2 of PB1 is obtained, using infrared absorption spectrum table The δ values of sign, PB2 are 1.5~4.5, preferably 1.8~3.8.It is mixed with PB1 and Beta molecular sieves and Y type molecular sieve using it When carrier prepared by conjunction, molding prepares hydrocracking catalyst, the performance of catalyst is further enhanced.Wherein, δ=I₁/ (I₂+I₃), I₁For 3665~3680cm in the infrared hydroxyl spectrum of the boehmite^-1Locate the peak height of absorption peak, I₂For 3720~ 3730cm^-1Locate the peak height of absorption peak, I₃For 3760~3780cm^-1Locate the peak height of absorption peak.

According to catalyst provided by the invention, the content selected from VIII group and the metal component selected from group vib is to add The usual content of hydrogen Cracking catalyst, for example, on the basis of catalyst and in terms of oxide, the catalyst contain 1 weight %~ The group VIII metal component of 15 weight %, the group vib metal component of 5 weight of weight %~40 %；Preferably comprise 2 weight %~10 The group VIII metal component of weight %, the group vib metal component of 10 weight of weight %~35 %.The group vib metal be selected from Cr, One or more of Mo or W, preferably Mo and/or W, the group VIII metal group are selected from one kind or several in Fe, Co or Ni Kind, preferably Co and/or Ni.Be enough will it is described it is at least one be selected from VIII group and at least one metal component selected from group vib Under the premise of being carried on the alumina support, specific carrying method is not particularly limited.Preferred method is infusion process. Contain the dipping solution of the metal component compound selected from VIII group and group vib, the dipping root including separately or concurrently preparing Can be excessive liquid dipping, hole saturation dipping according to maceration extract dosage difference, the mode difference realized according to dipping can be impregnated Method leaching, spray impregnating.By the adjusting and control to the concentration of dipping solution, dosage or carrier dosage, finger can be prepared Determine the catalyst of content, this is that those skilled in the art are readily appreciated by, and is not repeated here.

According to method for preparing catalyst provided by the invention, the vib metals compound is selected from these metals One or more of soluble compound, for example, it may be silico-tungstic acid, silicotungstate, phosphomolybdic acid, phosphomolybdate, molybdate, One or more of paramolybdate, tungstates, metatungstate, ethyl metatungstate.

The group VIII metallic compound is selected from the salt of these metals, includes their inorganic acid salt or organic salt. For example, the inorganic salts be selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulfate, chloride and One or more of partially decomposed product of these salts, it is preferable that in nitrate, carbonate or subcarbonate It is one or more of.The organic salt is that organic matter is combined the salt generated or soluble complexes with group VIII metal, described to have Machine object can be organic base, organic carboxyl acid, amine, ketone, ethers, alkyls, preferably organic carboxylate.

According to catalyst provided by the invention, organic additive can also be contained, on the basis of the catalyst, and with carbon The content of element meter, the organic additive is no more than 10 weight %, is further preferably no more than 6 weight %.

The organic additive is selected from oxygen-containing and/or nitrogenous one or more of organic matter.The oxygen-containing chemical combination Object is selected from Organic Alcohol, one or more of organic acid, one kind in organic amine, organic ammonium salt of organic compounds containing nitrogen or It is several.Specifically, it is selected from oxygen containing organic matter and is selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200~1500), two Ethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid, One or more of malic acid, wherein it is preferred that ethylene glycol, glycerine, polyethylene glycol and citric acid；Nitrogenous organic matter is selected from One kind in ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, nitrilotriacetic acid, EDTA and its ammonium salt Or it is several, wherein it is preferred that EDTA and nitrilotriacetic acid.The organic additive can also include containing Organic Alcohol and having simultaneously Machine acid.

It is also wrapped according to preparation method provided by the invention when the catalyst of the present invention further contains organic additive The step of introducing organic compound is included, the organic compound can be concomitantly introduced into group VIII metal, can also introduced It introduces, and is dried after group VIII metal, organic matter and group VIII metal, which are preferably configured to mixed solution, passes through The mode of dipping introduces simultaneously, is dried later.The selection of the drying temperature and time are golden in addition to being insufficient to allow VIII group Belong to salt or complex compound and decompose outer, should also allow to retain most of introduced organic matter in the catalyst, for example, retain 50% with On organic matter, it is highly preferred that retain 70% or more organic matter.Its method can be that any one can be realized in the prior art The method of above-mentioned purpose.For example, heat drying, it is dried under reduced pressure and heats in conjunction with the methods of being dried under reduced pressure.When the drying side When method is heat drying, preferred drying temperature is no more than 250 DEG C, is further preferably no more than 200 DEG C, more preferably not more than 180℃。

According to the conventional method in this field, the hydrotreating catalyst before the use, can usually exist in hydrogen Under, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140~370 DEG C, this presulfurization can carry out outside device Also can be In-situ sulphiding in device, convert the active metal component that it is loaded to metal sulfide component.

Catalyst provided by the invention can be used for hydrocracking or the hydro-upgrading of all kinds of hydrocarbon oil crude materials.For hydrocracking Or the reaction condition of hydro-upgrading is usual hydrocracking or hydro-upgrading reaction condition, such as reaction Wen Weidu 200~420 DEG C, further preferably 220~400 DEG C, pressure be 2~18 megapascal, further preferably 2~15 megapascal, liquid hourly space velocity (LHSV) 0.3 ~10 hours^-1, further preferably 0.3~5 hour^-1, hydrogen to oil volume ratio is 50~5000, further preferably 50~4000.

The device of the hydrocracking or the reaction of hydro-upgrading any can be enough that the feedstock oil is made to add at hydrogen It is carried out with catalytic react in dress device of the catalyst under reason reaction condition, for example, in the fixed bed reactors, it is mobile It is carried out in bed reactor or fluidized bed reactor.

Compared with the prior art provides catalyst, the present invention, which provides catalyst, has better hydrogenation aromatics-removing performance.Example Such as, 4%~10% is increased in the aromatic hydrocarbons activity of conversion of catalyst after applying the present invention.

Description of the drawings

Attached drawing is to a further understanding of the present invention, and a part for constitution instruction, with following specific implementation Mode is used to illustrate the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

PB1-1 in Fig. 1 (XRD diagram of boehmite) be meet the present invention claims boehmite XRD spectra； PB2-2 is a kind of modifier of PB1-1；SB (boehmite of Sasol companies production, trade name SB powder) is that one kind cannot Meet the present invention claims boehmite XRD spectra.

The IR-OH spectrograms for the modifier that PB2-2 in Fig. 2 (IR-OH of boehmite schemes) is PB1-1；PB2-3 is PB1-1 is in the IR-OH spectrograms of 600 DEG C of product of roasting.

Specific implementation mode

The present invention is described further for the following examples.

In experiment, XRD is carried out on the D5005 type X-ray diffractometers of Siemens, Cu targets, Ka radiation, solid Detector, 40kV, 40mA, step-scan, 0.02 ° of stride, 5 °~70 ° of scanning range.

IR-OH spectrograms are measured in U.S.'s BIO-RAD companies FT3000 type Fourier transformation infrared spectrometers, 15mm's Self-supporting piece, and vacuum is to 10^-3Pa keeps 1h, and 1000~4000cm is scanned after being cooled to room temperature^-1Wave-number range.

Saturated hydrocarbons and aromatic hydrocarbons composition are measured with content using SH/T0659-1998 methods in heavy oil.

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

PB1-1

By sodium metaaluminate (the causticity coefficient of the aluminum sulfate of a concentration of 93g/L of the 500mL of clear and a concentration of 195g/L For 1.6) and meanwhile be slowly added to 2L with stirring reaction kettle in, controlling reaction temperature be 40 DEG C, pH value 7.3.After the reaction was complete, stir It is 9.7 to mix and sodium carbonate to the solution ph of a concentration of 0.5mol/L is added.After the reaction 1 hour of 50 DEG C of constant temperature, filtering, deionized water Three times, 120 DEG C of temperature of ventilation dry 3hr in baking oven, obtain boehmite PB1-1 for washing.The h1 of PB1-1, h2, h3, k₁, k₂ And its hole appearance is listed in table 1.

PB1-2

The aluminum sulfate of a concentration of 48g/L of the 600mL of clear and the ammonium hydroxide of concentration 8% are slowly added to 2L bands simultaneously to stir In the reaction kettle mixed, reaction filtering, it is 35 DEG C to add ammonium hydroxide controlling reaction temperature, pH value 6.0.After the reaction was complete, filter, it will Filter cake is beaten, and it is 9.5 that ammonium hydrogen carbonate to solution ph, which is added, in stirring.After the reaction 12 hours of 35 DEG C of constant temperature, filtering, deionization washing It washs three times, 120 DEG C of temperature of divulging information in baking oven are dried 3 hours, and boehmite PB1-2 is obtained.The h1 of PB1-2, h2, h3, k₁, k₂ And its hole appearance is listed in table 1.

PB1-3

The aluminum sulfate of a concentration of 93g/L of the 600mL of clear and the ammonium hydroxide of concentration 8% are slowly added to 2L bands simultaneously to stir In the reaction kettle mixed, controlling reaction temperature is 50 DEG C, pH value 4.6.After the reaction was complete, filter cake is beaten by filtering, and carbon is added in stirring Sour sodium to solution ph is 8.4.After the reaction 0.5 hour of 35 DEG C of constant temperature, filtering, deionized water is washed three times, divulges information 120 in baking oven DEG C temperature is dried 3 hours, and boehmite PB1-3 is obtained.The h1 of PB1-3, h2, h3, k₁, k₂And its hole appearance is listed in table 1.

SB

The boehmite of Sasol companies production, trade name SB powder.The h1 of SB, h2, h3, k₁, k₂And its hole holds row In table 1.

1 boehmite XRD characterization data of table

Wherein, SB cannot meet the present invention 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, 250 DEG C and at such a temperature constant temperature 3 hours is heated to, obtains PB2-1. The h1 of PB2-1, h2, h3, k1, k2 and its hole, which hold, is listed in table 1, and I1, I2, I3 and the δ value of PB2-1 is listed in table 2.

PB2-2

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

PB2-3

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

PB2-4

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

PB2-5

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

2 boehmite PB IR Characterization data of table

Comparative example 1

By 533 grams of boehmite SB, (butt 0.75, butt assay method are that a certain amount of original powder is placed in crucible with cover It is put into Muffle furnace, is warming up to 700 DEG C of constant temperature after 1 hour, calculates ratio of the residue with original powder, similarly hereinafter) and 62.5 gram molecules It sieves Beta (sinopec catalyst Jian Chang branch companies produce, silica alumina ratio 24, and hole holds 0.39ml/g, butt 0.8), contain with 61.7g grams (sinopec catalyst branch Chang Ling catalyst plant produces phosphorus super stable molecular sieve PUSY, and trade name USY-5, phosphorus pentoxide contains Amount 1.2%, lattice constant 24.44, hole hold 0.40ml/g, butt 0.81), the mixing of 16 grams of sesbania powder, being extruded into circumscribed circle diameter is 1.6 millimeters of trilobal item, 120 DEG C dry 3 hours, and 600 DEG C of roasting temperatures 3 hours obtain carrier, catalyst carrier group prejudice Table 3.

After being cooled to room temperature, taking 100 grams of carriers to use, (Zigong, Sichuan cemented carbide works, tungsten oxide content are containing ammonium metatungstate 82 weight %) 50 grams, 8.7 grams of basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content are 51 weight %), 10.5g citric acid 70mL aqueous solutions impregnate, and 180 DEG C are dried 10 hours, and catalyst R-1 is obtained.On the basis of catalyst total amount, in R1 The mass fraction of metal component (for calculated value, similarly hereinafter) is listed in table 3.

Embodiment 1

533 grams of boehmite powder PB1-1 (butt 0.75) are sieved into Beta, 61.7g grams of USY-5, fields with 62.5 gram molecules The 16 grams of mixing of cyanines powder, are extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry 3 hours, 600 DEG C of roasting temperatures 3 hours, carrier is obtained, catalyst carrier composition is shown in Table 3.

After being cooled to room temperature, taking 100 grams of carriers to use, (Zigong, Sichuan cemented carbide works, tungsten oxide content are containing ammonium metatungstate 82 weight %) 51 grams, 8.7 grams of basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content are 51 weight %), 10.5g citric acid 80mL aqueous solutions impregnate, and 180 DEG C are dried 10 hours, and catalyst C-1 is obtained.On the basis of catalyst total amount, C-1 The mass fraction of middle metal component is listed in table 3.

Embodiment 2

By 267 grams of boehmite powder PB1-1 with 214 grams of contents on dry basis 0.92 PB2-2,62.5 gram molecules sieve Beta, 16 grams of 61.8g grams of USY-5, sesbania powder mixing, are extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, 120 DEG C dry, 600 DEG C Roasting temperature 3 hours, obtains carrier, and catalyst carrier composition is shown in Table 3.

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

Embodiment 3

By 460g grams of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 56g contents on dry basis 0.89,62.5g molecules 16 grams of Beta, 62gUSY-5, sesbania powder mixing are sieved, the trilobal item that circumscribed circle diameter is 1.6 millimeters is extruded into, 120 DEG C dry, 600 DEG C of roasting temperatures 3 hours, obtain carrier, and catalyst carrier composition is shown in Table 3.

After being cooled to room temperature, 100g carriers (Zigong, Sichuan cemented carbide works, tungsten oxide content 82 containing ammonium metatungstate is taken Weight %) 51 grams, 8.7 grams of basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content are 51 weight %), 10.5g citric acid 90ml aqueous solutions impregnate, and 140 DEG C are dried 3 hours, and catalyst C-3 is obtained.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 replacing PB2-2 with 200gPB2-3, catalyst C-4 is obtained.It is with catalyst total amount Benchmark, the mass fraction of metal component is listed in table 3 in C-4.

Embodiment 5

By 197g grams of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 56g contents on dry basis 0.89,344g molecules 16 grams of Beta, 31gUSY-5, sesbania powder mixing are sieved, the trilobal item that circumscribed circle diameter is 1.6 millimeters is extruded into, 120 DEG C dry, 480 DEG C of roasting temperatures 8 hours, obtain carrier, and catalyst carrier composition is shown in Table 3.

After being cooled to room temperature, 100g carriers (Zigong, Sichuan cemented carbide works, tungsten oxide content 82 containing ammonium metatungstate is taken Weight %) 30 grams, 18 grams of basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content are 51 weight %), 25g Citric acid 90ml aqueous solutions impregnate, and 110 DEG C are dried 20 hours, and catalyst C-5 is obtained.On the basis of catalyst total amount, metal in C-4 The mass fraction of component is listed in table 3.

Embodiment 6

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

Carrier and metal quality score characterize data in 3 catalyst of table

Embodiment 7

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

In the present embodiment, the evaluation method of catalyst is：By catalyst breakage at the particle of 0.3~0.45 millimeter of diameter, 0.15 gram of catalyst is packed into 2 milliliters of fixed bed reactors to be reacted.330 DEG C of reaction temperature, 4.0 megapascal of reaction pressure, Hydrogen-oil ratio (molar ratio) is 25, and liquid hourly space velocity (LHSV) is 30 hours^-1, carried out with the normal octane solution of the 5.61 weight % containing naphthane micro- anti- Evaluation, into being vulcanized before reaction oil, conditions of vulcanization is catalyst：Under conditions of Hydrogen Vapor Pressure 4.0MPa, 60 DEG C are warming up to, It is passed through and contains 6%CS₂Hexane solution, be warming up to 360 DEG C, constant temperature 3 hours.

Following formula defines the aromatic hydrocarbons activity of conversion of catalyst：

Aromatics conversion rate=(5.61%-w)/5.61% × 100%, wherein w is that the weight percent of naphthane in product contains Amount.

It the results are shown in Table shown in 4：

Aromatics conversion rate under the effect of 4 different catalysts of table

The aromatic hydrocarbons activity of conversion of catalyst increases 4%~10% after applying the present invention.

Claims (20)

1. a kind of hydrocracking catalyst, containing carrier and at least one it is selected from VIII group and at least one gold selected from group vib Belong to component, the carrier contains Beta molecular sieves, Y type molecular sieve and aluminium oxide, and on the basis of carrier, Beta type molecular sieves contain Amount is the 3 weight % of weight % ~ 80, and the content of Y type molecular sieve is the 3 weight % of weight % ~ 80, and the content of aluminium oxide is 15 weights of weight % ~ 90 Measure %, which is characterized in that the carrier is mixed with Y type molecular sieve, boehmite by Beta types molecular sieve, is molded, dried and roast Burning obtains, and the boehmite includes PB1, is characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively greater than 1 to less than it is equal to 3, wherein κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃Respectively in the x-ray diffraction spectra of PB1 2 angles θ be 24 ~ 30^o、35~41^oWith 46~52^oThree diffraction maximums peak height.

2. catalyst according to claim 1, which is characterized in that on the basis of carrier, the content of Beta type molecular sieves is 5 The content of the weight % of weight % ~ 65, Y type molecular sieve are the 5 weight % of weight % ~ 65, and the content of aluminium oxide is 30 weight of weight % ~ 90 %； It is characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively 1.02 ~ 2.4.

3. catalyst according to claim 2, which is characterized in that characterized with X-ray diffraction, the κ of the PB1₁It is 1.2 ~ 2.3, κ₂It is 1.02 ~ 1.4.

4. catalyst according to claim 1, which is characterized in that the specific surface area of the PB1 is 100 ~ 350 meters²/ gram, hole Hold is 0.7 ~ 1.2 ml/g.

5. catalyst according to claim 4, which is characterized in that the specific surface area of the PB1 is 150 ~ 280 meters²/ gram, hole Hold is 0.85 ~ 1.12 ml/g.

6. catalyst according to claim 1, which is characterized in that the Beta molecular sieves are Hydrogen Beta molecular sieves.

7. catalyst according to claim 6, which is characterized in that the silica alumina ratio of the Beta molecular sieves is 20 ~ 120, than Surface area is 200 ~ 650 meters²/ gram, 0.20 ~ 0.75 ml/g of Kong Rongwei.

8. catalyst according to claim 1, which is characterized in that the Y type molecular sieve is super-stable Y molecular sieves.

9. catalyst according to claim 8, which is characterized in that the lattice constant of the Y type molecular sieve be 2.460 ~ 2.430, specific surface area is 550 ~ 700 meters²/ gram, 0.30 ~ 0.45 ml/g of Kong Rongwei.

10. according to claim 1,8 or 9 any one of them catalyst, which is characterized in that the Y type molecular sieve contains phosphorus, with On the basis of the molecular sieve, the content of phosphorus is 0.1 weight of weight % ~ 2.5 %.

11. catalyst according to claim 10, which is characterized in that on the basis of the molecular sieve, the content of the phosphorus For 0.4 weight of weight % ~ 2.0 %.

12. catalyst according to claim 1, which is characterized in that the metal component of the VIII group be selected from nickel and/or Cobalt, the metal component of the group vib are selected from molybdenum and/or tungsten, are counted by oxide and on the basis of the catalyst, the nickel and/ Or the content of cobalt is 1 weight of weight % ~ 15 %, the content of the molybdenum and/or tungsten is 5 weight of weight % ~ 40 %.

13. catalyst according to claim 12, which is characterized in that it is counted by oxide and on the basis of the catalyst, The content of the nickel and/or cobalt is the 2 weight weight of % ~ 10 %, and the content of the molybdenum and/or tungsten is 10 weight of weight % ~ 35 %.

14. catalyst according to claim 1, which is characterized in that the boehmite is the mixture of PB1 and PB2, It is counted by butt and on the basis of carrier, the content that the content of PB1 is 10 weight of weight % ~ 90 %, PB2 is the 5 weight % of weight % ~ 60, With infrared spectrum characterization, the δ values of PB2 are 1.5 ~ 4.5, wherein δ=I1/（I2+I3）, I1 is the infrared hydroxyl of the boehmite 3665 ~ 3680cm in base spectrum^-1Locate the peak height of absorption peak, I2 is 3720 ~ 3730cm^-1Locate absorption peak peak height, I3 be 3760 ~ 3780cm^-1Locate the peak height of absorption peak.

15. catalyst according to claim 14, which is characterized in that counted by butt and on the basis of carrier, the content of PB1 Content for 20 weight of weight % ~ 80 %, PB2 is that the δ values of 10 weight of weight % ~ 50 %, the PB2 are 1.8 ~ 3.8.

16. catalyst according to claim 14, which is characterized in that the PB2 is PB1 in 70 ~ 400 DEG C dry 0.5 ~ 14 The modifier of hour.

17. catalyst according to claim 16, which is characterized in that the PB2 is PB1 small in 220 ~ 330 DEG C of dryings 1 ~ 6 When modifier.

18. catalyst according to claim 1, which is characterized in that the drying condition includes：Temperature is 50 ~ 350 DEG C, the time is 1 ~ 24 hour；The roasting condition includes：Temperature is 400 ~ 700 DEG C, and the time is 0.5 ~ 6 hour.

19. catalyst according to claim 18, which is characterized in that the drying condition includes：Temperature is 80 ~ 200 DEG C, the time is 1 ~ 6 hour；The roasting condition includes：Temperature is 550 ~ 650 DEG C, and the time is 1 ~ 3 hour.

20. according to application of claim 1 ~ 19 any one of them catalyst in hydrocarbon ils processing.