CN106268724B - A kind of hydrocracking catalyst and its application containing Y type molecular sieve - Google Patents

Abstract

A kind of hydrotreating catalyst and its application, the hydrotreating catalyst contain 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 aluminium oxide and two kinds of Y type molecular sieves, on the basis of carrier, the total content of Y type molecular sieve is 5 weight of weight %~70 %, the content of aluminium oxide is 30 weight of weight %~95 %, it is characterized in that, the carrier is mixed with boehmite by Y type molecular sieve, is molded, dried and roast 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 Y type molecular sieve

Technical field

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

Background technology

It includes the 350-540 DEG C of fraction such as VGO that industry, which is hydrocracked charging, reaction temperature generally between 350-440 DEG C, into High boiling component is contacted with catalyst in liquid form in reaction in material.Catalyst pore passage structure just has prior Effect, this just needs the aperture for increasing carrier, improves the ability that reaction molecular touches hydrogenation active metals in catalyst.Due to Molecular sieve and metal sulfide hole appearance are smaller, especially meet the middle macropore of macromolecule hydrocarbon feed needs required by PETROLEUM PROCESSING It is less, conventional method can by carrier of hydrocracking catalyst introduce macropore hold heat-resistant inorganic oxide matrix method come It realizes, such as introduces alumina host.

ZL97121663.0 disclose it is a kind of especially suitable for produce intermediate oil hydrocracking catalyst, containing whether there is or not The content of the silica-alumina component that shapes and aperture alumina adhesive, amorphous silica-alumina is 30-60 weights %, at least one group vib element and at least one VIII race's element are measured, hydrogenation metal oxide total content is 20-35 weight %, remaining Amount is aperture alumina adhesive, it is characterised in that 150-300 meters of catalyst specific surface²/ gram, 0.25-0.50 milliliters of hole appearance/ Gram, 4-15 nano-pores are distributed in 60-90%, 0.30-0.50 mMs/gram of infrared acidity.

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 75：25-50：50 The aluminium oxide that is combined of weight ratio, wherein small porous aluminum oxide is that diameter is less than the pore volume in 80 angstroms of holes and accounts for total pore volume 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.

CN87103714A discloses a kind of hydrocracking catalyst of midbarrel oil type, which, which includes catalysis, has The hydrogenation component and carrier of effect amount, this carrier, which contains, to be formed by the first modified Y zeolite component and refractory inorganic oxide matrix Homogeneous mixture, between 24.20-24.35 angstroms, above-mentioned catalyst changes the modified Y zeolite component elementary cell size range It is that this second using the second modified Y zeolite component for forming homogeneous mixture with the refractory inorganic oxide matrix into place The elementary cell size range of modified Y zeolite component also between 24.20-24.35 angstroms, but wherein this first and second be modified Y The elementary cell size of zeolite component is different, and the difference of elementary cell size is at least 0.1 angstrom.The catalyst has excellent Activity, selectivity and stability.

Invention content

The object of the present invention is to provide a kind of hydrocracking catalyst that performance has been modified and the catalyst applications.

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 aluminium oxide, Y type molecular sieve Y1 and Y type molecular sieve Y2, and on the basis of carrier, aluminium oxide contains Amount is 30 weight of weight %~95 %, and the total content of two kinds of Y type molecular sieves is 5 weight of weight %~70 %, which is characterized in that institute State carrier Y type molecular sieve Y1, Y type molecular sieve Y2 is mixed with boehmite, is molded, is dried and is roasted to obtain, the quasi- thin water Aluminium stone includes PB1, 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 h₃Spread out for three of 24-30 °, 35-41 ° and 46-52 ° at 2 angles θ respectively in the x-ray diffraction spectra of PB1 Penetrate the peak height at peak.

According to catalyst provided by the invention, under optimum condition, on the basis of carrier, the total content of Y type molecular sieve is 10 The content of the weight % of weight %~65, aluminium oxide are 35 weight of weight %~90 %；It is characterized with X-ray diffraction, the κ of the PB1₁With κ₂Respectively 1.02~2.4；Further preferably, the κ of the PB1₁For 1.2~2.3, κ₂It is 1.02~1.4；The ratio table of the PB1 Area is 100~350 meters²/ gram, 0.7~1.2 ml/g of Kong Rongwei, it is preferable that the specific surface area of the PB1 is 150~280 Rice²/ gram, 0.85~1.12 ml/g of Kong Rongwei.

According to catalyst provided by the invention, the Y type molecular sieve is super-stable Y molecular sieves, selected from y-type zeolite, containing dilute Native y-type zeolite, ultrastable and containing extremely steady y-type zeolite of rare earth, phosphorus-contained gamma-type molecular sieve, the structure cell of the Y type molecular sieve is normal Number is 2.465~2.420, and specific surface area is 500~850 meters²/ gram, 0.25~0.55 ml/g of Kong Rongwei；The Y types molecule Sieve can contain phosphorus, and on the basis of the molecular sieve, the content of phosphorus is the 0.1 weight % of weight %~2.5, preferably 0.4 weight Measure the weight of %~2.0 %.

According to catalyst provided by the invention, the absolute value of the Y type molecular sieve Y1 and Y2 framework si-al ratio differences is 0.2 ~10.8, preferably 0.5~2.74, the framework si-al ratio are SiO in framework of molecular sieve₂And Al₂O₃Molar ratio；Further It is preferred that the Y type molecular sieve Y1 framework si-al ratios are 5~20, Y type molecular sieve Y2 framework si-al ratios are 4.8~10, Y1 and Y2 weights Amount is than being 1:0.05~20.

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, 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 the 1 to less than boehmite PB1 equal to 3 and Y type molecular sieve, and USY or PUSY preferably wherein divide Sub- sieve prepares carrier, and 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 mixed with PB1 and Y type molecular sieve using it, be molded preparation When carrier prepares hydrocracking catalyst, the performance of catalyst is further enhanced.Wherein, δ=I₁/(I₂+I₃), I₁For institute State 3665~3680cm in the infrared hydroxyl spectrum of boehmite^-1Locate the peak height of absorption peak, I₂For 3720~3730cm^-1Place absorbs The peak height at 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 by it is described it is at least one selected from VIII group and it is at least one be carried on selected from the metal component of group vib described in Under the premise of on alumina support, specific carrying method is not particularly limited.Preferred method is infusion process.Including respectively or It is prepared simultaneously containing the dipping solution selected from VIII group and the metal component compound of group vib, the dipping is used according to maceration extract Amount difference can be excessive liquid dipping, hole saturation impregnates, and can be infusion method leaching, spray leaching according to the mode difference realized is impregnated Stain etc..By the adjusting and control to the concentration of dipping solution, dosage or carrier dosage, the described of specified content can be prepared Catalyst, 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, catalytic cracking tail oil is processed under the conditions of pressure in 6.4MPa using catalyst provided by the invention, tail oil balances arene content Relative reduction is up to 7%~23%.

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.

PB2-2 is a kind of IR-OH spectrograms of the modifier of PB1-1 in Fig. 2 (IR-OH of boehmite schemes)；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.

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 233.3 grams of boehmite SB, (butt 0.75, butt assay method are that a certain amount of original powder is placed in earthenware with cover Crucible is put into Muffle furnace, after being warming up to 700 DEG C of constant temperature 1hr, calculates ratio of the residue with original powder, similarly hereinafter) and 200 grams super steady point (sinopec catalyst branch Chang Ling catalyst plant produces son sieve LAY, lattice constant 24.58, and hole holds 0.39ml/g, butt 0.75), (sinopec catalyst branch Chang Ling catalyst plant produces phosphorous super stable molecular sieve PUSY, trade name USY-5, five oxygen Change two phosphorus contents 1.2%, lattice constant 24.44, hole holds 0.40ml/g, butt 0.81) 216g, 16 grams of mixing of sesbania powder, be extruded into Circumscribed circle diameter is 1.6 millimeters of trilobal item, and 120 DEG C dry 3 hours, and 600 DEG C of roasting temperatures 3 hours obtain carrier, are catalyzed Agent 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 %) 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 68ml 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

By 233.3 grams of boehmite powder PB1-1 (butt 0.75) with 200 grams of super stable molecular sieve LAY, 216gUSY-5, fields 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 77ml 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 133 grams of boehmite powder PB1-1 with the PB2-2 of 81.5 grams of contents on dry basis 0.92,200g super stable molecular sieves 16 grams of LAY, 216gUSY-5, sesbania powder mixing, are extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry, and 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 84ml 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 197g grams of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 28g contents on dry basis 0.89,185gLAY, 16 grams of 216gUSY-5, sesbania powder mixing, are extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of drying, 600 DEG C of temperature The lower roasting of degree 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 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 75gPB2-3, 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 263g grams of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 56g contents on dry basis 0.89,62gLAY, 247gUSY-5, the mixing of 16 grams of sesbania powder, be extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of drying, 480 DEG C of temperature The lower roasting of degree 8 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 %) 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-5 The mass fraction of component is listed in table 3.

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

Embodiment 6

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

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

In this example, the evaluation method of catalyst is：By catalyst breakage at the particle of 2-3 millimeters of diameter, at 30 milliliters In fixed bed reactors be packed into 20 milliliters of catalyst, react before first under a hydrogen atmosphere with containing 2 heavy % carbon disulfide kerosene according to Following procedure is vulcanized, and reaction raw materials reaction is then switched.

Vulcanize program：150 DEG C are warming up to, introduces sulfurized oil, constant temperature 1hr Wen Bo to be adsorbed are by two reactors, with 60 DEG C/hr is warming up to 230 DEG C, stablize 2hr, is warming up to 360 DEG C with 60 DEG C/hr, stablizes 6hr.Reaction oil is replaced, reaction temperature is adjusted To 355 DEG C, at least stablize 20hr.Reaction hydrogen partial pressure is 6.4 megapascal, liquid hourly space velocity (LHSV) (LHSV) 1 hour^-1, hydrogen-oil ratio (volume) 800, the catalyst of evaluation and its results are shown in Table 5.

4 raw material oil nature of table

Products obtained therefrom is evaporated under reduced pressure by 350 DEG C after reaction, products obtained therefrom carries out mass spectrum PONA analysis, as a result It is shown in Table 5：

5 catalyst removal tail oil aromatic hydrocarbons performance characterization of table

Since evaluating catalyst reaction pressure is relatively low so that tail oil aromatic hydrocarbons is used close to so-called thermodynamical equilibrium region Tail oil arene content relative reduction 7%~23% after this method.

Claims (19)

1. a kind of hydrotreating 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 aluminium oxide, Y type molecular sieve Y1 and Y type molecular sieve Y2, on the basis of carrier, Y type molecular sieve it is total Content is the 5 weight % of weight % ~ 70, and the content of aluminium oxide is 30 weight of weight % ~ 95 %, which is characterized in that the carrier is by Y types point Son sieve Y1, Y type molecular sieve Y2 are mixed with boehmite, are molded, drying and roast to obtain, and 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、h₂With h₃Respectively in the x-ray diffraction spectra of PB1 2 angles θ be 24^o~30^o、35^o~41^oWith 46^o~52^oThree diffraction maximums peak height.

2. catalyst according to claim 1, which is characterized in that on the basis of carrier, the total content of Y type molecular sieve is 10 The content of the weight % of weight % ~ 65, aluminium oxide are 35 weight of weight % ~ 90 %；It is characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively It is 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 Y type molecular sieve is selected from y-type zeolite, contains Y-type rare earth Zeolite, ultrastable and containing extremely steady y-type zeolite of rare earth, phosphorus-contained gamma-type molecular sieve, which is characterized in that the Y type molecular sieve Lattice constant is 2.465 ~ 2.420nm, and specific surface area is 500 ~ 850 meters²/ gram, 0.25 ~ 0.55 ml/g of Kong Rongwei.

7. catalyst according to claim 1, which is characterized in that the Y type molecular sieve Y1 and Y type molecular sieve Y2 framework silicons Aluminium is 0.2 ~ 10.8 than the absolute value of difference, and the framework si-al ratio is SiO in framework of molecular sieve₂And Al₂O₃Molar ratio.

8. catalyst according to claim 7, which is characterized in that the Y type molecular sieve Y1 and Y type molecular sieve Y2 framework silicons Aluminium is 0.5 ~ 2.74 than the absolute value of difference, and the Y type molecular sieve Y1 framework si-al ratios are 5 ~ 20, the Y type molecular sieve Y2 bones Frame silica alumina ratio is 4.8 ~ 10, and the Y type molecular sieve Y1 is 1 with Y type molecular sieve Y2 weight ratios:0.05~20.

9. according to the catalyst described in claim 1,6 or 7, which is characterized in that the Y type molecular sieve contains phosphorus, with described point On the basis of son sieve, the content of phosphorus is 0.1 weight of weight % ~ 2.5 %.

10. catalyst according to claim 9, which is characterized in that on the basis of the molecular sieve, the content of the phosphorus is 0.4 weight of weight % ~ 2.0 %.

11. 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 %.

12. catalyst according to claim 11, 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 %.

13. 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 are 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.

14. catalyst according to claim 13, which is characterized in that counted by butt and on the basis of carrier, the content of PB1 The δ values that content for 20 weight of weight % ~ 80 %, PB2 is 10 weight of weight % ~ 50 %, the PB2 are 1.8-3.8.

15. 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 hours；The roasting condition includes：Temperature is 400-700 DEG C, and the time is 0.5-6 hours.

16. catalyst according to claim 15, which is characterized in that the drying condition includes：Temperature is 80-200 DEG C, the time is 1-6 hours；The roasting condition includes：Temperature is 550-650 DEG C, and the time is 1-3 hours.

17. catalyst according to claim 13, which is characterized in that the PB2 is PB1 in 70-400 DEG C of dry 0.5-14 The modifier of hour.

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

19. according to application of the claim 1-18 any one of them catalyst in hydrocarbon ils processing.