CN106268917B - A kind of hydrocracking catalyst and its application - Google Patents
A kind of hydrocracking catalyst and its application Download PDFInfo
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Abstract
A kind of hydrocracking catalyst and its application, the hydrocracking catalyst contains carrier and at least one selected from VIII group and at least one metal component selected from group vib, the carrier contains Y type molecular sieve and aluminium oxide and Low acid sial, on the basis of carrier, the content of Y type molecular sieve is 3 weight of weight %~70 %, the content of aluminium oxide is 20 weight of weight %~90 %, Low acid sial content is 3 weight of weight %~60 %, it is characterized in that, the carrier is mixed by Y type molecular sieve with boehmite, molding, it dries and roasts to obtain, the boehmite includes PB1, with X-ray diffraction characterization, 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.Catalytic cracking tail oil is processed under the conditions of middle pressure using catalyst provided by the invention, tail oil balances arene content relative reduction up to 10%~30%.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and its applications.
Background technique
Industry be hydrocracked charging including VGO etc. 350-540 DEG C of fraction, reaction temperature generally between 350-440 DEG C, into
High boiling component is contacted with catalyst in liquid form in reaction in material.Catalyst cellular structure just has prior
Effect, this just needs to increase the aperture of 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 silica-alumina component that shapes and aperture alumina adhesive, the content of amorphous silica-alumina are 30-60 weight
%, 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-pore is 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 and/or cobalt on the carrier, 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, and 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 less than the pore volume in 80 angstroms of holes 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.
Summary of the invention
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 and Low acid sial, and on the basis of carrier, Y type molecular sieve contains
Amount is the 3 weight % of weight %~70, and the content of aluminium oxide is the 20 weight % of weight %~90, and Low acid sial content is 3 weights
Measure the weight of %~60 %, which is characterized in that the carrier mixes by Y type molecular sieve, Low acid sial with boehmite, at
Type, drying and roasting obtain, and the boehmite includes PB1, with X-ray diffraction characterization, 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 h3It is at 2 angles θ respectively in the x-ray diffraction spectra of PB1
The peak height of 24-30 °, 35-41 ° and 46-52 ° of three diffraction maximums.
The catalyst provided according to the present invention, under optimum condition, on the basis of carrier, the content of Y type molecular sieve is 5 weights
The weight % of %~65 is measured, the content of aluminium oxide is the 30 weight % of weight %~90, and the content of Low acid sial is 5 weight %~60
Weight %；With X-ray diffraction characterization, 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.
The catalyst provided according to the present invention, 0.01~0.1mmol/ of infrared B acidacidity value of the Low acid sial
G can pass through silicon-containing alumina, unformed silicon obtained by chemically reacting selected from silicon oxide-containing compound and alumina cpd body
Aluminium it is a kind of or several, such as using Sasol company of Germany produce Siral series aluminum silicon powder (Siral-5, Siral-10,
Siral-15, Siral-20, Siral-30, Siral-40 etc.) it is the silicon-containing alumina that precursor is prepared.With Low acid silicon
On the basis of aluminum amount, silicone content is calculated as the 20 weight % of weight %~60 with silica, and hole holds 0.5~1.0ml/g.；The Y
Type molecular sieve is super-stable Y molecular sieves, and the lattice constant of the Y type molecular sieve is 2.460~2.430, specific surface area is 550~
700 meters2/ gram, 0.30~0.45 ml/g of Kong Rongwei.The Y type molecular sieve can contain phosphorus, on the basis of the molecular sieve,
The content of phosphorus is 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, and 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；It 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 value for 10 weight of weight %~50 %, the PB2 is 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: that temperature is 50~350 DEG C, and the time is 1~24
Hour；The roasting condition includes: that temperature is 400~700 DEG C, and the time is 0.5~6 hour；Under optimum condition, described is dry
Dry condition includes: that temperature is 80~200 DEG C, and the time is 1~6 hour；The roasting condition includes: that 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 (contains selected from HY (hydrogen Y type molecular sieve), REY (alkene soil Y type molecular sieve), PY
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 be using arbitrary existing skill
Art preparation.For example, the disclosed method for preparing USY of ZL00123139.1, Zl200410071122.6 is disclosed to prepare PUSY's
Method is used as reference here.
Infrared B acidacidity 0.01~0.1mmol/g of value of the Low acid sial can be selected from silicon oxide-containing compound
With alumina cpd body by a kind of or several of silicon-containing alumina, amorphous silicon aluminium obtained by chemically reacting, such as use
Siral series aluminum silicon powder (Siral-5, Siral-10, Siral-15, Siral-20, the Siral- of German Sasol company production
30, Siral-40 etc.) silicon-containing alumina being prepared for precursor.On the basis of Low acid sial quality, silicone content with
Silica is calculated as the 20 weight % of weight %~60, and hole holds 0.5~1.0ml/g.
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, mesh belt, converter heating means
Dry, drying condition includes 50~350 DEG C of temperature, preferably 70~200 DEG C, the time 1~24 hour, preferably 2~6 hours；Using baking
Case, mesh belt, 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 meeting κ using including a kind of with X-ray diffraction characterization1Value is 1 to small
In equal to 3 and κ2Value is that the 1 to less than boehmite PB1 equal to 3 and Beta molecular sieve and Y type molecular sieve prepare carrier,
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 one kind disclosed in CN100999328B is using aluminum sulfate and partially
The boehmite of the boehmite method preparation of sodium aluminate neutralisation preparation can meet requirement of the 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 to roast the boehmite in 600 DEG C
After burning 4 hours, characterize to obtain by BET N2 adsorption.
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
Sign, the δ value of PB2 are 1.5~4.5, preferably 1.8~3.8.It is mixed with PB1 and Beta molecular sieve 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 of Fe, Co or Ni or several
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 dipping, can be infusion method leaching according to the mode difference that dipping is realized, spray soaks
Stain etc..By the regulation and control of concentration to 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, including 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 the salt or soluble complexes that organic matter generates in conjunction 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
Element meter, the content of the organic additive are no more than 10 weight %, are 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 be selected from one or more of Organic Alcohol, organic acid, organic compounds containing nitrogen be selected from one of organic amine, organic ammonium salt or
It is several.Specifically, ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200~1500), two are selected from selected from oxygen containing organic matter
Ethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, 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 of 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 pure and mild having containing organic simultaneously
Machine acid.
It is also wrapped according to preparation method provided by the invention when catalyst of the 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 are preferably configured to mixed solution and passed 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 in the catalyst most of introduced organic matter, for example, retain 50% with
On organic matter, it is highly preferred that retain 70% or more organic matter.Its method can be in the prior art any one can realize
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
Can also be In-situ sulphiding in device, the active metal component that it is loaded is converted into 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 can be enough to add the feedstock oil at hydrogen any
It is carried out under reason reaction condition with catalytic react in dress device of the catalyst, 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 10%~30%.
Detailed description of the invention
Attached drawing constitutes part of specification to a further understanding of the present invention, with following specific implementation
Mode is used to illustrate together the present invention, 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 company production, trade name SB powder) is that one kind cannot
Meet the present invention claims boehmite XRD spectra.
The IR-OH spectrogram for the modifier that PB2-2 is PB1-1 in Fig. 2 (IR-OH of boehmite schemes)；PB2-3 is PB1-
1 in the IR-OH spectrogram of 600 DEG C of product of roasting.
Specific embodiment
The present invention is described further for the following examples.
In experiment, XRD is carried out on the D5005 type X-ray diffractometer of Siemens, Cu target, Ka radiation, solid
Detector, 40kV, 40mA, step-scan, 0.02 ° of stride, 5 °~70 ° of scanning range.
IR-OH spectrogram is measured in U.S.'s BIO-RAD company FT3000 type Fourier transformation infrared spectrometer, 15mm's
Self-supporting piece, and vacuum is to 10-3Pa keeps 1h, scans 1000~4000cm after being cooled to room temperature-1Wave-number range.
Saturated hydrocarbons and aromatic hydrocarbons composition are measured with content using SH/T0659-1998 method in heavy oil.
Boehmite used in embodiment and comparative example, preparation method or source:
PB1-1
By the 500mL concentration of clear be 93g/L aluminum sulfate and concentration be 195g/L sodium metaaluminate (causticity coefficient
1.6) to be slowly added in reaction kettle of the 2L with stirring simultaneously, control reaction temperature is 40 DEG C, pH value 7.3.After fully reacting, stir
Mixing and sodium carbonate to the solution ph that concentration is 0.5mol/L is added is 9.7.After 50 DEG C of constant temperature are reacted 1 hour, filtering, deionized water
Three times, the dry 3hr of 120 DEG C of temperature of ventilation, obtain boehmite PB1-1 in baking oven for washing.The h1 of PB1-1, h2, h3, k1, k2
And its hole appearance is listed in table 1.
PB1-2
The ammonium hydroxide of aluminum sulfate and concentration 8% that the 600mL concentration of clear is 48g/L is slowly added to 2L band simultaneously to stir
In the reaction kettle mixed, reaction filtering, adding ammonium hydroxide control reaction temperature is 35 DEG C, pH value 6.0.After fully reacting, filter, it will
Filter cake mashing, it is 9.5 that ammonium hydrogen carbonate to solution ph, which is added, in stirring.After 35 DEG C of constant temperature are reacted 12 hours, filtering, deionization washing
It washs three times, 120 DEG C of temperature of divulging information in baking oven are 3 hours dry, obtain boehmite PB1-2.The h1 of PB1-2, h2, h3, k1, k2
And its hole appearance is listed in table 1.
PB1-3
The ammonium hydroxide of aluminum sulfate and concentration 8% that the 600mL concentration of clear is 93g/L is slowly added to 2L band simultaneously to stir
In the reaction kettle mixed, control reaction temperature is 50 DEG C, pH value 4.6.After fully reacting, filter cake is beaten by filtering, and carbon is added in stirring
Sour sodium to solution ph is 8.4.35 DEG C of constant temperature after reaction 0.5 hour, filtering, deionized water is washed three times, divulges information 120 in baking oven
DEG C temperature is 3 hours dry, obtains boehmite PB1-3.The h1 of PB1-3, h2, h3, k1, k2And its hole appearance is listed in table 1.
SB
The boehmite of Sasol company production, trade name SB powder.The h1 of SB, h2, h3, k1, k2And its hole holds column
In table 1.
1 boehmite XRD characterization data of table
Wherein, SB be not able to satisfy the present invention claims.
Boehmite modifier and preparation method thereof used in embodiment and comparative example:
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 measuring 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, calculate residue with original powder ratio, similarly hereinafter) with 333.3 grams it is super steady
(production of middle Effect of Catalysis In Petrochemistry agent branch company Chang Ling catalyst plant, lattice constant 24.58, hole hold 0.39ml/g, butt to molecular sieve LAY
0.75), 96g Low acid sial (production of Sasol Germany, trade name Siral-40, dioxide-containing silica 40%, butt 0.78, hole
Hold 0.9ml/g, infrared B acid value 0.04mmol/g, L acid value 0.27mmol/g), 16 grams of sesbania powder mixing, be extruded into circumscribed circle diameter
For 1.6 millimeters of trilobal item, 120 DEG C dry 3 hours, 600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carrier composition
It 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. of Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 68ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst R-1.On the basis of catalyst total amount, in R1
The mass fraction (for calculated value, similarly hereinafter) of metal component is listed in table 3.
Example 1
By 233.3 grams of boehmite powder PB1-1 (butt 0.75) with 333.3 grams of super stable molecular sieves LAY, 96gSiral-
40,16 grams of sesbania powder mixing 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 temperature
Lower roasting 3 hours, obtains carrier, and 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. of Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 77ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst C-1.On the basis of catalyst total amount, C-1
The mass fraction of middle metal component is listed in table 3.
Example 2
By 133 grams of boehmite powder PB1-1 with the PB2-2 of 81.5 grams of contents on dry basis 0.92,333.3g super stable molecular sieve
LAY, 96gSiral-40,16 grams of sesbania powder mixing, are extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry,
600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carrier composition is shown in Table 3.
After being cooled to room temperature, 100g carrier (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. of Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 84ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst C-2.On the basis of catalyst total amount, C-2
The mass fraction of middle metal component is listed in table 3.
Embodiment 3
197g grams of boehmite powder PB1-3 (butt 0.76) is contained with the PB2-1 of 28g contents on dry basis 0.89,308.6g
(production of middle Effect of Catalysis In Petrochemistry agent branch company Chang Ling catalyst plant, trade name USY-5, phosphorus pentoxide contain phosphorus super stable molecular sieve PUSY
Amount 1.2%, lattice constant 24.44, hole hold 0.40ml/g, butt 0.81), 96gSiral-40,16 grams of sesbania powder mixing, be extruded into
Circumscribed circle diameter is 1.6 millimeters of trilobal item, 120 DEG C of drying, 600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carries
Body composition is shown in Table 3.
After being cooled to room temperature, 100g carrier (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. of Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 90ml aqueous solution dipping, 140 DEG C are dried 3 hours, obtain catalyst C-3.On the basis of catalyst total amount, in C-3
The mass fraction of metal component is listed in table 3.
Embodiment 4
With embodiment 2, except that replacing PB-2-2 with 75gPB2-3, catalyst R-2 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 263.2g grams of boehmite powder PB1-3 (butt 0.76) with the PB2-1 of 56g contents on dry basis 0.89,62g is phosphorous
Super stable molecular sieve PUSY (production of middle Effect of Catalysis In Petrochemistry agent branch company Chang Ling catalyst plant, trade name USY-5, phosphorus pentoxide content
1.2%, lattice constant 24.44, hole hold 0.40ml/g, butt 0.81), 256gSiral-40,16 grams of sesbania powder mixing, be extruded into
Circumscribed circle diameter is 1.6 millimeters of trilobal item, 120 DEG C of drying, 480 DEG C roasting temperature 8 hours, obtain carrier, catalyst carries
Body composition is shown in Table 3.
After being cooled to room temperature, 100g carrier (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. of Jiangsu, nickel oxide content are 51 weight %), 25g
Citric acid 90ml aqueous solution dipping, 110 DEG C are dried 20 hours, obtain catalyst C-5.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
Example 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 2-3 millimeters of diameter of particle, 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.
Vulcanization program: being warming up to 150 DEG C, introduces sulfurized oil, constant temperature 1hr Wen Bo to be adsorbed is 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 stable 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 lower, so that tail oil aromatic hydrocarbons is used close to so-called thermodynamical equilibrium region
Tail oil arene content relative reduction 10%~30% after this method.
Claims (19)
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 Y type molecular sieve, aluminium oxide and Low acid sial, on the basis of carrier, the content of Y type molecular sieve
For the 3 weight % of weight %~70, the content of aluminium oxide is the 20 weight % of weight %~90, and Low acid sial content is 3 weight %
~60%, which is characterized in that the carrier is mixed with boehmite by Y type molecular sieve, Low acid sial, formed, dried simultaneously
Roasting obtains, and the boehmite includes PB1, with X-ray diffraction characterization, the κ of the PB11And κ2It respectively greater than 1 to less than waits
In 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 °,
The peak height of 35 °~41 ° and 46 °~52 ° of three diffraction maximums.
2. catalyst according to claim 1, which is characterized in that on the basis of carrier, the content of Y type molecular sieve is 5 weights
The weight % of %~65 is measured, the content of aluminium oxide is the 30 weight % of weight %~90, and the content of Low acid sial is 5 weight %~60
Weight %；With X-ray diffraction characterization, the κ of the PB11And κ2Respectively 1.02~2.4.
3. catalyst according to claim 2, which is characterized in that with X-ray diffraction characterization, the κ of the PB11For 1.2-2.3,
κ2For 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,
0.7~1.2 ml/g of Kong Rongwei.
5. catalyst according to claim 4, which is characterized in that the specific surface area of the PB1 is 150~280 meters2/ gram,
0.85~1.12 ml/g of Kong Rongwei.
6. catalyst according to claim 1, which is characterized in that the Y type molecular sieve is super-stable Y molecular sieves.
7. catalyst according to claim 6, which is characterized in that the lattice constant of the Y type molecular sieve is 2.460-
2.430, specific surface area is 550~700m20.30~0.45mL/g of/g, Kong Rongwei.
8. according to claim 1,6 or 7 described in any item 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 %.
9. catalyst according to claim 8, 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 %.
10. catalyst according to claim 1, which is characterized in that the infrared B acidacidity value 0.01 of the Low acid sial
~0.1mmol/g is selected from one of silicon-containing alumina, amorphous silicon aluminium or several, on the basis of Low acid sial, silicon
Content is calculated as the 20 weight % of weight %~60 with silica, and hole holds 0.5~1.0ml/g.
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/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 %, and the content of the molybdenum/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/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 5 weights of weight %~60
% is measured, with infrared spectrum characterization, the δ value of PB2 is 1.5~4.5, wherein δ=I1/ (I2+I3), I1 are the boehmite
Infrared hydroxyl spectrum in 3665~3680cm-1Locate the peak height of absorption peak, I2 is 3720~3730cm-1Locate the peak height of absorption peak, I3
For 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 value that content for 20 weight of weight %~80 %, PB2 is 10 weight of weight %~50 %, the PB2 is 1.8-3.8.
15. catalyst according to claim 1, which is characterized in that the drying condition includes: that temperature is 50-350
DEG C, the time is 1-24 hours；The roasting condition includes: that 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: that temperature is 80-200
DEG C, the time is 1-6 hours；The roasting condition includes: that 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. application of -18 described in any item catalyst in hydrocarbon ils processing according to claim 1.
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| US11524281B2 (en) | 2017-10-31 | 2022-12-13 | China Petroleum & Chemical Corporation | Phosphorus-containing molecular sieve, its preparation and application thereof |
| CN110116021A (en) * | 2018-02-07 | 2019-08-13 | 中国石油天然气股份有限公司 | The double elements method of modifying and its modified molecular screen of molecular sieve in a kind of FCC catalyst |
| CN108816273B (en) * | 2018-06-04 | 2021-04-09 | 中国中化股份有限公司 | Preparation method of hydrocracking catalyst with high light oil selectivity |
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| CN108722473B (en) * | 2018-06-04 | 2020-10-02 | 中国中化股份有限公司 | Preparation method of hydrocracking catalyst |
| CN111085248B (en) * | 2018-10-23 | 2022-08-09 | 中国石油化工股份有限公司 | Catalyst containing acidic material, preparation method and application thereof |
| CN111097504B (en) * | 2018-10-26 | 2022-08-09 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing composite molecular sieve and preparation method and application thereof |
| CN111097508B (en) * | 2018-10-26 | 2023-02-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing composite Beta molecular sieve and preparation method and application thereof |
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| CN111097505B (en) * | 2018-10-26 | 2023-02-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing Beta molecular sieve, and preparation method and application thereof |
| CN111097506B (en) * | 2018-10-26 | 2023-02-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing composite molecular sieve and silicon-aluminum, and preparation method and application thereof |
| JP7178271B2 (en) * | 2019-01-15 | 2022-11-25 | Ｅｎｅｏｓ株式会社 | Artificial graphite material, method for producing artificial graphite material, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN112742441B (en) * | 2019-10-30 | 2023-07-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN112742440B (en) * | 2019-10-30 | 2023-08-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
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