CN106391105A - Multi-level pore hydrocracking catalyst containing composite molecular sieve, and applications thereof - Google Patents

Abstract

The invention relates to a multi-level pore hydrocracking catalyst containing a composite molecular sieve, and applications thereof, wherein the catalyst contains a carrier and a hydrogenation activity metal component supported on the carrier, the carrier contains a Beta type molecular sieve, a Y type molecular sieve and alumina, the hydrogenation activity metal component is selected from molybdenum and/or tungsten in the group VIB and nickel and/or cobalt in the group VIII, and the pore distribution of the catalyst meets the following requirements that the volume of the pores having the pore diameter of less than 2 nm accounts for 2-50% of the total pore volume of the catalyst, the volume of the pores having the pore diameter of 2-100 nm accounts for 20-85% of the total pore volume of the catalyst, and the volume of the pores having the pore diameter of more than 100 nm accounts for 3-70% of the total pore volume of the catalyst. Compared to the catalyst in the prior art, the catalyst of the present invention has high hydrocracking activity.

Description

A kind of multi-stage porous hydrocracking catalyst containing composite molecular screen and its application

Technical field

The present invention relates to a kind of hydrocracking catalyst and its application, in particular, it is related to a kind of containing again Close multi-stage porous hydrocracking catalyst and its application of molecular sieve.

Background technology

Beta type molecular sieve has stronger isomerism ability due to having three dimensional intersection pore passage structure, is hydrocracked Generally raw material condensation point is reduced using this component in catalyst.

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,>The two of 2nm 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, Na₂O weight content<0.2%, at 25 DEG C, when P/Po is 0.1, water adsorption amount is little In 5 weight %, n-butanol adsorption experiment residual value is less than 0.4, ion exchange capacity<0.07.Described hole Hold the mixture that refractory oxide is selected from aluminum oxide, sial or aluminum oxide and silica.Entered using this catalyst Row is hydrocracked, and the measuring change of diesel oil solidifying point ratio in product is relatively low, can produce long distillate low freezing point diesel fuel.Industry Be hydrocracked charging include 350～540 DEG C of cuts such as VGO, reaction temperature typically between 350～440 DEG C, In charging, high boiling component is contacted with catalyst in liquid form in reaction.

Now solve resistance to mass tranfer, improve catalyst activity product key issue, need to improve catalyst duct Structure, improves the ability that reaction molecular touches hydrogenation active metals in catalyst.

Because molecular sieve and metal sulfide pore volume are less, particularly meet macromolecular hydrocarbon required by PETROLEUM PROCESSING The middle macropore of class feed needs is less, and conventional method can be by introducing macropore in carrier of hydrocracking catalyst The method holding heat-resistant inorganic oxide matrix to realize, for example, introduces 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 are it is characterised in that described carrier is by aluminum oxide With zeolite composition, the weight of aluminum oxide and zeolite ratio is for 90：10～50：50, described aluminum oxide is by aperture Aluminum oxide and macroporous aluminium oxide are according to 75：25～50：50 weight than the aluminum oxide being composited, wherein, The pore volume that little porous aluminum oxide is less than 80 angstroms of holes for diameter accounts for the aluminum oxide of total pore volume more than 95%, macropore Aluminum oxide is that the pore volume in 60～600 angstroms of holes of diameter accounts for the aluminum oxide of total pore volume more than 70%.

Content of the invention

The technical problem to be solved in the present invention is to provide a kind of hydrocracking catalyst and its in hydrocarbon ils processing Application.The catalyst that the present invention provides has specifically multistage pore size distribution, for hydrocarbon oil hydrogenation cracking reaction When, this catalyst has higher catalysis activity.

The present invention relates to a kind of multi-stage porous hydrocracking catalyst containing composite molecular screen, this catalyst contains load Body and load hydrogenation active metals component on this carrier, described carrier contains Beta type molecular sieve, Y type Molecular sieve and aluminum oxide, described hydrogenation active metals group is selected from molybdenum and/or tungsten and the VIII of vib The nickel of race and/or cobalt are it is characterised in that the pore size distribution of described catalyst meets：Bore dia is less than 2nm hole Pore volume account for the 2%～50% of catalyst total pore volume, bore dia is that the pore volume in 2～100nm hole accounts for catalysis The 20%～85% of agent total pore volume, the pore volume that bore dia is more than 100nm hole accounts for catalyst total pore volume 3%～70%.

The invention still further relates to application in hydrocarbon ils processing for the aforesaid catalyst.

According to the present invention, the pore size distribution of preferably described catalyst meets：The pore volume that bore dia is less than 2nm accounts for The 4%～21% of catalyst total pore volume, bore dia is that the pore volume of 2～100nm accounts for catalyst total pore volume 20%～85%, the pore volume that bore dia is more than 100nm accounts for the 4%～60% of catalyst total pore volume.

In the present invention, Beta zeolite is zeolite known to people, its Nomenclature Composition and Structure of Complexes in US3,308,069 Hes It is already described in Re28341.The catalyst providing 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 silica/alumina (mol ratio) at least 25, such as 30～500 Beta zeolite, the Beta zeolite being more highly preferred to is silica / aluminum 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 specially Profit.

The silica alumina ratio of further preferably described Beta type molecular sieve is 20～120, and specific surface area is 200～650 Rice²/ gram, pore volume is 0.20～0.75 ml/g；Described aluminum oxide is γ～aluminum oxide.

According to the present invention, described Y type molecular sieve is preferably super-stable Y molecular sieves, described Y type molecular sieve Lattice constant be 2.460～2.430, specific surface area be 550～700 meters²/ gram, pore volume is 0.30～0.45 milli Rise/gram.

The catalyst being 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 0.1～2.5 weight %, preferably 0.4～2.0 weight %.

According to the present invention, described carrier contains Beta type molecular sieve and Y type molecular sieve and aluminum oxide, with On the basis of described carrier, the content of described Beta type molecular sieve is 3～80 weight %, preferably 3～70 weight %, More preferably 5～60 weight %, the content of aluminum oxide is 10～90 weight %, preferably 15～85 weight %, More preferably 15～60 weight %, Y type molecular sieve content is 3～80 weight %, preferably 5～60 weights Amount %.Wherein, when there is no other additive in carrier, Beta type molecular sieve, Y type molecular sieve and oxidation The change of aluminium content meets that each group is divided and is absolutely.

On the basis of catalyst, in described catalyst, the content of carrier is 45～85 weight %, in terms of oxide Described nickel and/or the content of cobalt be 1～15 weight %, the described molybdenum in terms of oxide and/or the content of tungsten are 5～40 weight %.In further preferably described catalyst, the content of carrier is 60～80 weight %, with oxide The content of the described nickel of meter and/or cobalt is 2～10 weight %, the described molybdenum in terms of oxide and/or the content of tungsten For 10～35 weight %.

Organic additive can be contained, described organic additive is selected from oxygen-containing and/or nitrogenous having in described catalyst One or more of machine thing, on the basis of catalyst, in described catalyst, the content of organic additive is 2～20 weight %.Further preferably described oxygen containing organic matter is selected from one of Organic Alcohol, organic acid or several Kind, nitrogenous organic matter is selected from one or more of organic amine, organic ammonium salt.More preferably described oxygen-containing Organic matter be selected from ethylene glycol, glycerine, molecular weight be 200～1500 polyethylene glycol, diethylene glycol, Butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- CDTA, citric acid, One or more of tartaric acid, malic acid, wherein preferred ethylene glycol, glycerine, polyethylene glycol and lemon Acid；Nitrogenous organic matter be selected from ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, One or more of NTA, EDTA and its ammonium salt.

In the present invention, the pore size distribution for making final catalyst meets requirement, and described carrier is preferably as follows by including The method preparation of step：(1) Beta type molecular sieve is mixed with boehmite, peptizing agent and water, obtain one Kind of mixture, the consumption of each component makes the amount of peptizing agent material and the powder weight ratio in described mixture be 0.28×10^-4～4.8 × 10^-4Mol/g, the weight of water is 2.0 × 10 with the ratio of the amount of peptizing agent material³～30 × 10³G/mol, described powder weight is described Beta type molecular sieve, boehmite and Y type molecular sieve weight Sum, the amount of described peptizing agent material refers to measure H proton molal quantity in described peptizing agent；Described lubrication Agent is one of sesbania powder, graphite or two kinds, and on the basis of powder weight, described lubricant is in powder Middle content is 1～9 weight %；(2) mixture kneading, shaping, drying the roasting obtaining step (1), obtains To carrier, wherein said boehmite includes PB1, with X-ray diffraction sign, the κ 1 of described PB1 Meet 1 ＜ κ 1≤3 and 1 ＜ κ 2≤3, the κ of further preferably described PB1 with κ 2₁For 1.2～2.3, κ₂For 1.02～1.4.Wherein, κ 1=h2/h1, κ 2=h3/h2, h1, h2 and h3 are respectively the X-ray diffraction spectra of PB1 In figure 2 θ angles be 24 °～30 °, the peak height of three diffraction maximums of 35 °～41 ° and 46 °～52 °.

Wherein, the specific surface area of preferably described PB1 is 100～350 meters²/ gram, pore volume be 0.7～1.2 milliliter/ Gram, the specific surface area of further preferred described PB1 is 150～280 meters²/ gram, pore volume is 0.85～1.12 Ml/g.In the described step (1) of preferred vector preparation method, the consumption of each component makes the glue in described mixture The amount of vehicle substance and powder weight ratio are 0.7 × 10^-4～4.0 × 10^-4Mol/g, the weight of water and peptizing agent The ratio of the amount of material is 2.0 × 10³～15 × 10³g/mol.

In the present invention, described catalyst multi-stage porous pore size distribution is adopted and is recorded with the following method：Using N2 adsorption method (BET method) records diameter in catalyst and is less than 2nm hole pore volume B1 and a diameter of 2～100nm hole pore volume B2, and record with diameter greater than 100nm hole pore volume H1 in catalyst using mercury injection method, three's sum is to urge Agent total pore volume V.With υ₁The pore volume representing the hole that bore dia is less than 2nm accounts for catalyst total pore volume Percentage, wherein υ₁=B1/V；With υ₂The pore volume representing bore dia 2～100nm hole accounts for the total hole body of catalyst Long-pending percentage, wherein υ₂=B2/V；With υ₃Represent bore dia and account for catalyst more than the pore volume in 100nm hole The percentage of total pore volume, wherein υ₃=H1/V.

The pore volume of described boehmite, specific surface area etc., are in 600 DEG C of roastings 4 by described boehmite After hour, characterized by BET N2 adsorption and obtain.

On the premise of being sufficient for application claims, the present invention is not particularly limited to the source of PB1, example As being commercially available commodity or using the preparation of arbitrary existing method.For example, CN100999328B is public The class opened adopts the plan thin water aluminium of the boehmite method preparation of aluminum sulfate and the preparation of sodium metaaluminate neutralisation Stone can meet the requirement of the present invention, herein by reference as quoting.

In the present invention, described shaping is preferably extruded moulding.

Inventor find, when carrier be molded, when preparing carrier especially with extrusion method, peptizing agent with The consumption of water produces impact to the pore size distribution of final molding carrier.When according to the inventive method each component of control It is 0.7 × 10 with powder weight ratio that consumption makes the amount of peptizing agent material in described mixture^-4～4.0 × 10^-4Mol/g, the weight of water is 2.0 × 10 with the ratio of the amount of peptizing agent material³～15 × 10³During g/mol, gained The pore size distribution relative distribution of the carrier arriving.To be used for adding by catalyst prepared by the carrier with this attribute During hydrogen cracking reaction, catalyst has more preferable weight activity (activity of Unit Weight catalyst).

In the present invention, the method for described drying and roasting is conventional method, for example, using baking oven, guipure, Converter heating means are dried, and drying condition includes 50～350 DEG C of temperature, preferably 70～200 DEG C, the time 1～24 hour, preferably 2～6 hours；Carry out roasting, roasting bar using baking oven, guipure, converter heating means Part includes 350～800 DEG C of temperature, preferably 400～700 DEG C, 0.5～6 hour time, preferably 1～4 hour.

The catalyst providing according to the present invention, described the containing of metal component selected from VIII with selected from group vib Measure as the usual content of hydrotreating catalyst, for example, on the basis of catalyst and in terms of oxide, described urge Agent contains the group VIII metal component of 1～15 weight %, the group vib metal component of 5～40 weight %；Excellent The group VIII metal component containing 2～10 weight % for the choosing, the group vib metal component of 10～35 weight %.Described Group vib metal is selected from one or more of Cr, Mo or W, preferably Mo and/or W, described VIII Metal component is selected from one or more of Fe, Co or Ni, preferably Co and/or Ni.

Enough to by described at least one selected from VIII with least one selected from group vib metal component load On the premise of on the described alumina support, concrete carrying method is not particularly limited.Preferably method is Infusion process.Including the dipping separately or concurrently prepared containing the metal component compound selected from VIII and group vib Solution, described dipping can be excessive immersion stain, hole saturation dipping according to maceration extract consumption difference, according to The mode difference that dipping is realized can be infusion method leaching, spray impregnating.By to the concentration of dipping solution, The regulation of consumption or carrier consumption and control, can prepare the described catalyst of specified content, and this is this Skilled person is readily appreciated by, and does not repeat here.

The method for preparing catalyst providing according to the present invention, described vib metals compound is selected from these One or more of soluble compound of metal, for example, it may be silico-tungstic acid, silicotungstate, phosphorus molybdenum Acid, phosphomolybdate, molybdate, paramolybdate, tungstates, metatungstate, in 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.For example, described inorganic salts are selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphoric acid One or more of partially decomposed product of salt, sulfate, chloride and these salts it is preferable that Selected from one or more of nitrate, carbonate or subcarbonate.Described organic salt is organic matter and VIII Race metal combines the salt generating or soluble complexes, described organic matter can be organic base, organic carboxyl acid, Amine, ketone, ethers, alkyls, preferably organic carboxylate.

The catalyst providing according to the present invention, can also contain organic additive.When the catalyst of the present invention contains When having organic compound, also include the step introducing organic compound, described organic compound can be with VIII Race's metal is concomitantly introduced into it is also possible to introduce after introducing group VIII metal, and is dried, and preferably will Organic matter and group VIII metal are configured to mixed solution and are simultaneously introduced by way of dipping, are done afterwards Dry.The selection of described baking temperature and time in addition to being insufficient to allow group VIII metal salt or complex compound and decomposing, Also should allow to retain most of introduced organic matter in the catalyst, for example, retain more than 50% organic matter, It is highly preferred that retaining more than 70% organic matter.Its method can be that in prior art, any one can achieve The method of above-mentioned purpose.For example, heat drying, drying under reduced pressure and heating combine the methods such as drying under reduced pressure. When described drying means is heat drying, preferred baking temperature is less than 250 DEG C, further preferably not More than 200 DEG C, more preferably not more than 180 DEG C.For example, in one preferred embodiment, described dry Dry temperature is 70 DEG C～180 DEG C.

According to the present invention, when preparing the described catalyst containing organic compound, with described catalyst as base Standard, in described catalyst, the content of organic additive is 2～20 weight %.

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

The catalyst that the present invention provides can be used for hydrotreating or the hydro-upgrading of all kinds of hydrocarbon oil crude materials.For adding Hydrogen is processed or the reaction condition of hydro-upgrading is usual hydrotreating or hydro-upgrading reaction condition, for example instead 200～420 DEG C of Ying Wenwei degree, more preferably 220～400 DEG C, pressure is 2～18MPa, excellent further Elect 2～15MPa as, liquid hourly space velocity (LHSV) is 0.3～10 hour^-1, more preferably 0.3～5 hour^-1, hydrogen oil body Long-pending ratio is 50～5000, is more preferably 50～4000, and described hydrogen to oil volume ratio refers to the volume flow of hydrogen The ratio of the volume flow rate of speed and hydrocarbon ils..

The device of the reaction of described hydrotreating or hydro-upgrading can be any enough to make described feedstock oil add Hydrogen processes and carries out, for example, described solid in reaction dress device catalytic with described catalyst under reaction condition Carry out in fixed bed reactor, moving-burden bed reactor or fluidized bed reactor.

Compared with providing catalyst with prior art, the present invention provides catalyst to have preferably and is hydrocracked performance.

Specific embodiment

The present invention is described further for the following examples.

The invention will be further described by 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, 0.02 ° of stride, 5～70 ° of sweep limits.

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

PB1-1

By the sodium metaaluminate for 195g/L for the aluminum sulfate and concentration for 93g/L for the 500mL concentration of clear (causticity coefficient is 1.6) is slowly added in the reactor with stirring for the 2L, and controlling reaction temperature is 40 DEG C, PH value 7.3.After reaction completely, it is 9.7 that stirring adds the sodium carbonate that concentration is 0.5mol/L to solution ph. After 50 DEG C of reactions of constant temperature 1 hour, filter, deionized water is washed three times, in baking oven, 120 DEG C of temperature of ventilation are done Dry 3hr, obtains boehmite PB1-1.The h1 of PB1-1, h2, h3, k₁, k₂And its pore volume is listed in Table 1.

PB1-2

By the 600mL concentration of clear be the aluminum sulfate of 48g/L and concentration 8% ammoniacal liquor simultaneously slowly plus Enter in the reactor with stirring for the 2L, reaction is filtered, add ammoniacal liquor controlling reaction temperature and be 35 DEG C, pH value 6.0.After reaction completely, filter, filter cake is pulled an oar, it is 9.5 that stirring adds ammonium hydrogen carbonate to solution ph. After 35 DEG C of reactions of constant temperature 12 hours, filter, deionized water is washed three times, in baking oven, 120 DEG C of temperature of ventilation are done Dry 3hr, obtains boehmite PB1-2.The h1 of PB1-2, h2, h3, k₁, k₂And its pore volume is listed in Table 1.

PB1-3

By the 600mL concentration of clear be the aluminum sulfate of 93g/L and concentration 8% ammoniacal liquor simultaneously slowly plus Enter in the reactor with stirring for the 2L, controlling reaction temperature is 50 DEG C, pH value 4.6.After reaction completely, mistake Filter, filter cake is pulled an oar, and it is 8.4 that stirring adds sodium carbonate to solution ph.35 DEG C of constant temperature reacts 0.5 hour Afterwards, filter, deionized water is washed three times, 120 DEG C of temperature of divulging information in baking oven are dried 3hr, obtain intending thin water aluminium Stone 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.H1, h2, the h3 of SB, k₁, k₂And its pore volume is listed in table 1.

Table 1 boehmite XPS characterizes

Wherein, SB can not meet application claims.

Comparative example 1

By 533.3 grams of boehmite SB, (butt 0.75, butt assay method is to put a certain amount of former powder Enter crucible with cover to put in Muffle furnace, after being warming up to 700 DEG C of constant temperature 1hr, calculate the ratio with former powder for the residue Value, similarly hereinafter) (sinopec catalyst Jian Chang branch company produces, silica alumina ratio 27, pore volume with 61 gram molecule sieve Beta 0.395mL/g, butt 0.82), 65.8 grams of LAY molecular sieve (sinopec catalyst branch company Chang Ling catalyst Factory produces, trade name LAY, lattice constant 24.58, pore volume 0.39ml/g, butt 0.75), sesbania powder 11 Gram, 19.3ml purity be 65% red fuming nitric acid (RFNA) (molar concentration be 14.4mol/L, similarly hereinafter), 319ml deionization Water mixes, and is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, dries 3 hours for 120 DEG C, 600 DEG C Roasting temperature 3 hours, obtains carrier, and catalyst carrier composition is shown in Table 2.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 63ml aqueous impregnation, 180 DEG C are dried 10 hours, are urged Agent R-1.On the basis of catalyst total amount, the mass fraction (for calculated value, similarly hereinafter) of metal component in R-1 It is listed in table 2.

Comparative example 2

By 533.3 grams of boehmite PB1-1 (butt 0.75) and 61 gram molecule sieve Beta (sinopec catalyst Jian Chang branch company produces, silica alumina ratio 27, pore volume 0.395mL/g, butt 0.82), 11.14 grams of sesbania powder, 66 grams of LAY molecular sieves, 22ml purity be 65% red fuming nitric acid (RFNA), 385.5ml deionized water mix, It is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, dry 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 Hour, obtain carrier, catalyst carrier composition is shown in Table 2.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 72ml aqueous impregnation, 180 DEG C are dried 10 hours, are urged Agent R-2.On the basis of catalyst total amount, the mass fraction of each metal component (for calculated value, similarly hereinafter) is listed in Table 2.

Comparative example 3

533.3 grams of boehmite SB powder and 61 gram molecules are sieved Beta (sinopec catalyst Jian Chang branch company Produce, silica alumina ratio 27, pore volume 0.395mL/g, butt 0.82), 16 grams, 78.9 grams LAY of sesbania powder divide The red fuming nitric acid (RFNA) that son sieves, 15.7ml purity is 65%, 319ml deionized water mix, and are extruded into circumscribed circle straight Footpath is 1.6 millimeters of trilobal bar, dries 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 hours, obtains load Body, catalyst carrier composition is shown in Table 2.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 78ml aqueous impregnation, 180 DEG C are dried 10 hours, are urged Agent R-3.On the basis of catalyst total amount, the mass fraction of each metal component (for calculated value, similarly hereinafter) is listed in Table 2.

Embodiment 1

By 540.5 grams of boehmite PB1-2 (butt 0.74) and 61 gram molecule sieve Beta (sinopec catalyst Jian Chang branch company produces, silica alumina ratio 27, pore volume 0.395mL/g, butt 0.82), 16 grams of sesbania powder, 66 Gram LAY molecular sieve, 11ml purity be 65% red fuming nitric acid (RFNA), 439ml deionized water mix, be extruded into Circumscribed circle diameter is 1.6 millimeters of trilobal bar, dries 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 are little When, obtain carrier, catalyst carrier composition is shown in Table 2.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 78ml aqueous impregnation, 180 DEG C are dried 10 hours, are urged Agent C-1.On the basis of catalyst total amount, the mass fraction of each metal component (for calculated value, similarly hereinafter) is listed in Table 2.

Embodiment 2

By 526.3 grams of boehmite PB1-3 (butt 0.76) and 61 gram molecule sieve Beta (sinopec catalyst Jian Chang branch company produces, silica alumina ratio 27, pore volume 0.395mL/g, butt 0.82), 16 grams of sesbania powder, 66 Gram LAY molecular sieve, 3.3ml purity be 65% red fuming nitric acid (RFNA), 637ml deionized water mix, be extruded into Circumscribed circle diameter is 1.6 millimeters of trilobal bar, dries 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 are little When, obtain carrier, catalyst carrier composition is shown in Table 2.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 110ml aqueous impregnation, 180 DEG C are dried 10 hours, obtain Catalyst C-2.On the basis of catalyst total amount, the mass fraction of each metal component (for calculated value, similarly hereinafter) It is listed in table 2.

Embodiment 3

By 329 grams of boehmite PB1-3 (butt 0.76) and 268 gram molecule sieve Beta (sinopec catalyst Jian Chang branch company produces, silica alumina ratio 87, pore volume 0.43mL/g, butt 0.84), 16 grams of sesbania powder, 31 (sinopec catalyst branch company Chang Ling catalyst plant produces, trade name USY-5, five oxygen for gram USY molecular sieve Change two phosphorus contents 1.2%, lattice constant 24.44, pore volume 0.40ml/g, butt 0.81), 15.3ml purity be 65% red fuming nitric acid (RFNA), 417ml deionized water mix, and are extruded into the trilobal that circumscribed circle diameter is 1.6 millimeters Bar, dries 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 hours, obtains carrier, catalyst carrier group prejudice Table 2.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 100ml aqueous impregnation, 180 DEG C are dried 10 hours, obtain Catalyst C-3.On the basis of catalyst total amount, the mass fraction of each metal component (for calculated value, similarly hereinafter) It is listed in table 2.

Embodiment 4

Carry out the preparation of carrier using embodiment 3 identical method, except for the difference that during extrusion, purity is 65% Nitric acid dosage is 4.3ml, and water consumption is 644ml.

After being cooled to room temperature, take 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide workses, tungsten oxide Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content For 51 weight %) 8.7 grams, 10.5g citric acid 110ml aqueous impregnation, 180 DEG C are dried 10 hours, obtain Catalyst C-4.On the basis of catalyst total amount, in C-4 metal component mass fraction (for calculated value, under With) it is listed in table 2.

Catalyst pores distribution characterization result is listed in table 3.

Table 2 carrier and catalyst characterization

Powder weight refers to Beta type molecular sieve, Y type molecular sieve and boehmite weight sum；Peptizing agent The amount of material is to measure H proton molal quantity in peptizing agent used.

The distribution of table 3 catalyst pores characterizes

Embodiment 5

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

Raw materials used oil is the sand vacuum gas oil (VGO) that gently subtracts two, and its physico-chemical property is shown in Table 4.

In this example, the evaluation method of catalyst is：Catalyst breakage is become the particle of 2～3 millimeters of diameter, 20 milliliters of catalyst is loaded in 30 milliliters of fixed bed reactors.First under a hydrogen atmosphere with containing 2 weights before reaction The kerosene of amount % carbon disulfide is vulcanized according to following program, then the reaction of switching reaction raw materials.

Sulfuration program：It is warming up to 150 DEG C, introduces sulfurized oil, constant temperature 1hr Wen Bo to be adsorbed passes through two reactors, It is warming up to 230 DEG C with 60 DEG C/hr, stablizes 2hr, be warming up to 360 DEG C with 60 DEG C/hr, stablize 6hr.

Cracking reaction：Reaction temperature is 355 DEG C, and reaction pressure is 6.4MPa, and liquid hourly space velocity (LHSV) (LHSV) is 1 Hour^-1, hydrogen to oil volume ratio is 800, stablizes sample analysis after 20 hours.Raw material and response sample are subtracted Pressure separated, calculates and is more than 350 DEG C of cut percentage compositions.

Table 4 raw material oil nature

Evaluate the activity of catalyst with the conversion ratio of Unit Weight catalyst, computational methods are as follows：

Wherein, m₁For being more than 350 DEG C of cut amounts, m in raw material₂It is more than 350 DEG C of cut amounts for generating in oil, m_cFor loaded catalyst.

Table 5 catalyst activity evaluation

With the conversion ratio of reference catalyst R-1 for 100%, calculate the relative activity of other catalyst, evaluation Catalyst and its results are shown in Table 5.Result shows, with respect to reference catalyst, what the present invention provided urges The relative activity of agent generally improves more than 10%.

Claims (19)

1. a kind of multi-stage porous hydrocracking catalyst containing composite molecular screen, containing carrier with load on this carrier Hydrogenation active metals component, described carrier contains Beta type molecular sieve, Y type molecular sieve and aluminum oxide, described Hydrogenation active metals group is selected from the molybdenum of vib and/or the nickel of tungsten and group VIII and/or cobalt, its feature It is, the pore size distribution of described catalyst meets：The pore volume that bore dia is less than 2nm hole accounts for catalyst total pore volume 2%～50%, bore dia is that the pore volume in 2～100nm hole accounts for 20%～85%, Kong Zhi of catalyst total pore volume The pore volume that footpath is more than 100nm hole accounts for the 3%～70% of catalyst total pore volume.

2. catalyst according to claim 1 is it is characterised in that the pore size distribution of described catalyst meets： The pore volume that bore dia is less than 2nm hole accounts for the 4%～21% of catalyst total pore volume, and bore dia is 2～100nm hole Pore volume account for the 20%～85% of catalyst total pore volume, bore dia be more than 100nm hole pore volume account for catalyst The 4%～60% of total pore volume.

3. catalyst according to claim 1 is it is characterised in that Beta described in described Beta type molecular sieve The silica alumina ratio of type molecular sieve is 20～120, and specific surface area is 200～650 meters^2/Gram, pore volume is 0.20～0.75 milliliter / gram；Described aluminum oxide is gama-alumina.

4. catalyst according to claim 1 is it is characterised in that the lattice constant of described Y type molecular sieve For 2.460～2.430, specific surface area is 550～700 meters²/ gram, pore volume is 0.30～0.45 ml/g.

5. the catalyst according to any one of claim 1,3 or 4 is it is characterised in that described Y type molecule Sieve contains phosphorus, and on the basis of described molecular sieve, the content of phosphorus is 0.1～2.5 weight %.

6. catalyst according to claim 1 is it is characterised in that on the basis of described carrier, described Beta The content of type molecular sieve is 3～80 weight %, and the content of aluminum oxide is 10～90 weight %, Y type molecular sieve content For 3～80 weight %.

7. catalyst according to claim 6 is it is characterised in that on the basis of described carrier, described Beta The content of type molecular sieve is 3～70 weight %, and the content of aluminum oxide is 15～85 weight %, Y type molecular sieve content For 5～60 weight %.

8. catalyst according to claim 1 is it is characterised in that on the basis of catalyst, described catalysis In agent, the content of carrier is 45～85 weight %, and the described nickel counted with oxide and/or the content of cobalt are for 1～15 weight Amount %, the described molybdenum counted with oxide and/or the content of tungsten are for 5～40 weight %.

9. catalyst according to claim 8 is it is characterised in that on the basis of catalyst, described catalysis In agent, the content of carrier is 60～80 weight %, and the described nickel counted with oxide and/or the content of cobalt are for 2～10 weights Amount %, the described molybdenum counted with oxide and/or the content of tungsten are for 10～35 weight %.

10. catalyst according to claim 1 it is characterised in that in described catalyst contain organic additive, Described organic additive is selected from one or more of oxygen-containing and/or nitrogenous organic matter, on the basis of catalyst, In described catalyst, the content of organic additive is 2～20 weight %.

11. catalyst according to claim 10 it is characterised in that described oxygen containing organic matter be selected from have One or more of machine alcohol, organic acid, nitrogenous organic matter be selected from one of organic amine, organic ammonium salt or Several.

12. catalyst according to claim 11 are it is characterised in that described oxygen containing organic matter is selected from second Glycol, glycerine, relative molecular mass be 200～1500 polyethylene glycol, diethylene glycol, butanediol, acetic acid, In maleic acid, oxalic acid, aminotriacetic acid, 1,2- CDTA, citric acid, tartaric acid, malic acid One or more, wherein preferably ethylene glycol, glycerine, polyethylene glycol and citric acid；Nitrogenous organic matter choosing From ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, EDTA One or more of and its ammonium salt.

13. catalyst according to claim 1 it is characterised in that the preparation method of described carrier include as Lower step：(1) Beta type molecular sieve and Y type molecular sieve, boehmite, peptizing agent, lubricant and water are mixed Close, obtain a kind of mixture, the consumption of each component makes the amount of peptizing agent material and powder weight in described mixture Ratio is 0.28 × 10^-4～4.8 × 10^-4Mol/g, the weight of water is 2.0 × 10 with the ratio of the amount of peptizing agent material³～30 ×10³G/mol, described powder weight is described Beta type molecular sieve, boehmite and Y type molecular sieve weight Sum, the amount of described peptizing agent material refers to measure H proton molal quantity in described peptizing agent；Described lubricant For one of sesbania powder, graphite or two kinds, on the basis of powder weight, described lubricant contains in powder Measure as 1～9 weight %；(2) mixture kneading, shaping, drying the roasting obtaining step (1), obtains carrier.

14. catalyst according to claim 13 it is characterised in that described boehmite includes PB1, Characterized with X-ray diffraction, the κ 1 and κ 2 of described PB1 meet 1 ＜ κ 1≤3 and 1 ＜ κ 2≤3, wherein, κ 1=h2/h1, κ 2=h3/h2, h1, h2 and h3 are respectively in the x-ray diffraction spectra of PB1 and are 24 °～30 °, 35 °～41 ° at 2 θ angles Peak height with 46 °～52 ° of three diffraction maximums.

15. catalyst according to claim 14 are it is characterised in that characterized with X-ray diffraction, described PB1 κ 1 be 1.2～2.3, κ 2 be 1.02～1.4.

16. catalyst according to claim 14 are it is characterised in that the specific surface area of described PB1 is 100～350 meters²/ gram, pore volume is 0.7～1.2 ml/g.

17. catalyst according to claim 16 are it is characterised in that the specific surface area of described PB1 is 150～280 meters²/ gram, pore volume is 0.85～1.12 ml/g.

18. catalyst according to claim 13 it is characterised in that in described step (1) each component use It is 0.7 × 10 with powder weight ratio that amount makes the amount of peptizing agent material in described mixture^-4～4.0 × 10^-4Mol/g, The weight of water is 2.0 × 10 with the ratio of the amount of peptizing agent material³～15 × 10³g/mol.

Application in hydrocarbon ils processing for 19. catalyst according to any one of claim 1～18.