CN107029779A - A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve - Google Patents
A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve Download PDFInfo
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Abstract
A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve, the catalyst contains the hydrogenation active metal component of carrier and load on this carrier, the carrier contains Y type molecular sieve and faintly acid sial and silica and aluminum oxide, the hydrogenation active metal component is selected from the molybdenum of vib and/or the nickel and/or cobalt of tungsten and group VIII, characterized in that, the pore size distribution of the catalyst is met：The pore volume that bore dia is less than 2nm holes accounts for the 2%~50% of catalyst total pore volume, and bore dia accounts for the 20%~85% of catalyst total pore volume for the pore volume in 2~100nm holes, and the pore volume that bore dia is more than 100nm holes accounts for the 3%~70% of catalyst total pore volume.Compared with the catalyst that prior art is provided, the catalyst that the present invention is provided has higher hydrogenation cracking activity.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and its application, it is more particularly related to a kind of
Multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve.
Background technology
Industry, which is hydrocracked charging, includes 350~540 DEG C of cuts such as VGO, heavy end molecular weight greatly, it is necessary to
Catalyst provides larger duct space, and loaded catalyst duct is mainly determined by carrier, and this is accomplished by increase
The aperture of carrier, improves the ability that reaction molecular touches hydrogenation active metals in catalyst.Due to molecular sieve
It is smaller with metal sulfide pore volume, particularly meet in macromolecule hydrocarbon feed needs required by PETROLEUM PROCESSING
Macropore is less, and conventional method can be aoxidized by introducing big pore volume heat resistant inorganic in carrier of hydrocracking catalyst
The method of thing matrix is realized, for example, introduce alumina host.
A kind of catalyst for hydrogenation treatment of diesel oil of ZL01123765.1, the catalyst contains a kind of carrier and is supported on
Molybdenum and/or tungsten and nickel and/or cobalt on the carrier, it is characterised in that the carrier is by aluminum oxide and zeolite group
Into the weight ratio of aluminum oxide and zeolite is 90:10~50:50, the aluminum oxide is by small porous aluminum oxide and macropore
Aluminum oxide is according to 75:25~50:50 weight than the aluminum oxide that is composited, wherein, small porous aluminum oxide is straight
Footpath accounts for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 angstroms of holes, and macroporous aluminium oxide is diameter
The pore volume in 60~600 angstroms of holes accounts for the aluminum oxide of total pore volume more than 70%.
The invention is applied to diesel modifying catalyst process, and to be hydrocracked charging boiling point higher by VGO, real
Generally reacted during the hydrocracking reaction of border with trickle bed pattern, 60nm ducts are not enough to improve liquid
What is dripped is scattered, and this causes mass transport process to turn into the critical process in hydrocracking process, it is necessary to further improve
The aperture of catalyst.
ZL97121663.0 discloses a kind of hydrocracking catalyst for being particularly suitable for use in producing intermediate oil,
Containing amorphous silicon oxide~alumina component and aperture alumina adhesive, amorphous silicon oxide~aluminum oxide
Content is 30~60 weight %, at least one group vib element and at least one VIII race element, hydrogenation metal oxygen
Compound total content is 20~35 weight %, and surplus is aperture alumina adhesive, it is characterised in that catalyst ratio
150~300 meters of surface2/ gram, 0.25~0.50 ml/g of pore volume, 4~15 nano-pores are distributed in 60%~90%,
Infrared mM/gram of acidity 0.30~0.50.
CN102030351A discloses a kind of macroporous aluminium oxide of bimodal pore distribution, and its pore volume is
0.6~3.0ml/g, specific surface area is 90~300m2/ g, wherein 35~100 angstroms of hole accounts for total pore volume
20%~55%, most probable pore size is located at 50~90 angstroms, and 200~800 angstroms of hole accounts for the 20%~55% of total pore volume,
Most probable pore size is located at 300~600 angstroms.The method that two step agings are employed in the aluminum oxide preparation process is carried out
Prepare, because the treatment conditions in ageing process are typically harsher, the work of aluminum oxide precursor thing surface can be reduced
Sprinkle hydroxyl so that metal-support interaction is changed, and the pore size distribution of catalyst can be also influenceed in addition, is made
Obtain the reactivity worth reduction of catalyst.
The 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
Using.The catalyst that the present invention is provided has specific multistage pore size distribution, for hydrocarbon oil hydrogenation cracking reaction
When, the catalyst has higher catalytic activity.
The present invention relates to a kind of multi-stage porous hydrocracking catalyst containing Y type molecular sieve, the catalyst contains load
The hydrogenation active metal component of body and load on this carrier, the carrier contains Y type molecular sieve, faintly acid
Sial and silica and aluminum oxide, the hydrogenation active metal component be selected from vib molybdenum and/or tungsten with
And the nickel and/or cobalt of group VIII, it is characterised in that the pore size distribution of the catalyst is met：Bore dia is less than
The pore volume in 2nm holes accounts for the 2%~50% of catalyst total pore volume, and bore dia is the pore volume in 2~100nm holes
The 20%~85% of catalyst total pore volume is accounted for, the pore volume that bore dia is more than 100nm holes accounts for the total hole of catalyst
The 3%~70% of volume.
The invention further relates to application of the foregoing catalyst in hydrocarbon ils processing.
According to the present invention, the pore size distribution of preferably described catalyst is met：The pore volume that bore dia is less than 2nm is accounted for
The 4%~21% of catalyst total pore volume, bore dia accounts for catalyst total pore volume for 2~100nm pore volume
20%~85%, the pore volume that bore dia is more than 100nm accounts for the 4%~60% of catalyst total pore volume.
Wherein, described Y type molecular sieve be selected from HY (hydrogen Y type molecular sieve), REY (rare earth Y type molecular sieve),
PY (phosphorus-contained gamma-type molecular sieve), USY (super-stable Y molecular sieves), PUSY (phosphorous USY, including PHY,
REUSY (hyperastable Y-type RE)), USY, PUSY preferably wherein.The molecular sieve can be commercially available business
Product, it would however also be possible to employ prepared by arbitrary prior art.For example, ZL00123139.1 is disclosed to prepare USY
Method, the disclosed methods for preparing PUSY of Zl200410071122.6, here as reference.
It is preferred that the lattice constant of the Y type molecular sieve is 2.460~2.430, specific surface area is 550~700 meters2/ gram, pore volume is 0.30~0.45 ml/g；The aluminum oxide is gama-alumina.
According to the catalyst that provides of the present invention, the faintly acid sial can be commercially available commodity or using any
Prepared by a kind of prior art, its infrared B acidacidities 0.01~0.1mmol/g of value, and preferably specific surface area is
350~750 meters2/ gram, pore volume is 0.4~1.2 ml/g, and more preferably specific surface area is 400~650
Rice2/ gram, pore volume is 0.45~0.95 ml/g of faintly acid sial.The faintly acid sial, which can be selected from, to be contained
Silicon oxide compounds and alumina cpd body pass through silicon-containing alumina, amorphous silicon aluminium obtained by chemical reaction
It is a kind of or several, such as using the production of Germany Sasol companies 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
On the basis of faintly acid sial, wherein the content of silica is the weight % of 10 weight %~80, preferably 15 weights
Measure the weight % of %~55.
The precursor of the silica be selected from Ludox, loss on ignition for 0~60 weight % Silica hydrogel, White Carbon black,
Superfine silicon dioxide it is a kind of or several.
According to the present invention, the carrier contains Y type molecular sieve and faintly acid sial and silica and aluminum oxide,
On the basis of the carrier, the content of the Y type molecular sieve is 3~70 weight %, and the content of aluminum oxide is
10~85 weight %, faintly acid sial content is 5~60 weight %, and the content of silica is 4~30 weight %.
The content of further preferred Y type molecular sieve is 5~60 weight %, and the content of aluminum oxide is 15~60 weight %,
Faintly acid sial content is 5~60 weight %, and the content of silica is 5~25 weight %.Wherein, carrier is worked as
In when not containing other auxiliary agents, the change of Y type molecular sieve, faintly acid sial and alumina content and silica
Each component sum is met for absolutely.
On the basis of catalyst, the content of carrier is 45~85 weight % in the catalyst, in terms of oxide
The nickel and/or the content of cobalt be 1~15 weight %, the content of the molybdenum and/or tungsten in terms of oxide is
5~40 weight %.The content of carrier is 60~80 weight % in the further preferred catalyst, with oxide
The nickel of meter and/or the content of cobalt are 2~10 weight %, the content of the molybdenum and/or tungsten in terms of oxide
For 10~35 weight %.
Organic additive can be contained in the catalyst, described organic additive is selected from oxygen-containing and/or nitrogenous
One or more in organic matter, on the basis of catalyst, the content of organic additive is in the catalyst
2~20 weight %.The further preferred one kind or several of the oxygen containing organic matter in Organic Alcohol, organic acid
Kind, the one or more of nitrogenous organic matter in organic amine, organic ammonium salt.It is more preferably described oxygen-containing
Organic matter be selected from ethylene glycol, glycerine, molecular weight for 200~1500 polyethylene glycol, diethylene glycol,
Butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid,
One or more in tartaric acid, malic acid, wherein it is preferred that 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 in NTA, EDTA and its ammonium salt.
In the present invention, to make the pore size distribution of final catalyst meet requirement, the carrier is preferably by including as follows
It is prepared by the method for step：(1) by Y type molecular sieve and boehmite, silica predecessor, peptizing agent and water
Mixing, obtains a kind of mixture, the consumption of each component makes the amount and powder of peptizing agent material in the mixture
Weight ratio is 0.28 × 10-4~4.8 × 10-4The ratio between mol/g, the weight of water and amount of peptizing agent material are 2.0
×103~30 × 103G/mol, the powder weight is the Y type molecular sieve, boehmite and faintly acid
Aluminum weight sum, the amount of the peptizing agent material refers to measuring H proton molal quantitys in the peptizing agent；
The lubricant is the one or two kinds of in sesbania powder, graphite, on the basis of powder weight, the lubrication
Agent content in powder is 1~9 weight %；(2) the mixture kneading that obtains step (1), shaping, dry simultaneously
Roasting, obtains carrier, wherein described boehmite includes PB1, is characterized with X-ray diffraction, the PB1
κ 1 and κ 2 meet 1 ＜ κ 1≤3 and 1 ＜ κ 2≤3, further preferred PB1 κ1For 1.2~2.3,
κ2For 1.02~1.4.Wherein, κ 1=h2/h1, κ 2=h3/h2, h1, h2 and h3 are respectively PB1 X-ray
In peak height of the 2 θ angles for 24 °~30 °, 35 °~41 ° and 46 °~52 ° of three diffraction maximums in diffraction spectrogram.
Wherein, further preferably the specific surface area of the PB1 is 100~350 meters2/ gram, pore volume is 0.7~1.2
Ml/g, further preferred PB1 specific surface area is 150~280 meters2/ gram, pore volume is 0.85~1.12
Ml/g.The consumption of each component makes the glue in the mixture in the step (1) of preferred vector preparation method
The amount of vehicle substance is 0.7 × 10 with powder weight ratio-4~4.0 × 10-4Mol/g, the weight and peptizing agent of water
The ratio between amount of material is 2.0 × 103~15 × 103g/mol.In the present invention, the catalyst multi-stage porous pore size distribution
Adopt and measure with the following method：Diameter in catalyst is measured using N2 adsorption method (BET method) and is less than 2nm holes hole
Volume B1 and a diameter of 2~100nm holes pore volume B2, and measure diameter in catalyst using mercury injection method and be more than
100nm holes pore volume H1, three's sum is catalyst total pore volume V.With υ1Bore dia is represented less than 2nm
The pore volume in hole account for the percentage of catalyst total pore volume, wherein υ1=B1/V；With υ2Represent bore dia
The pore volume in 2~100nm holes accounts for the percentage of catalyst total pore volume, wherein υ2=B2/V；With υ3Represent hole
Diameter accounts for the percentage of catalyst total pore volume, wherein υ more than the pore volume in 100nm holes3=H1/V.
Pore volume, specific surface area of the boehmite etc., are in 600 DEG C of roastings 4 by the boehmite
After hour, characterized and obtained by BET N2 adsorptions.
On the premise of application claims are sufficient for, PB1 source is not particularly limited the present invention, example
Such as, it can be commercially available commodity or be prepared using arbitrary existing method.For example, CN100999328B is public
The thin water aluminium of plan prepared by the boehmite method that the class opened is prepared using aluminum sulfate and sodium metaaluminate neutralisation
Stone can meet the requirement of the present invention, herein by reference as reference.
In the present invention, the shaping is preferably extruded moulding.
Inventor find, when carrier be molded, when preparing carrier especially with extrusion method, peptizing agent with
Pore size distribution of the consumption of water on final molding carrier produces influence.When according to the inventive method control each component
Consumption makes the amount of the peptizing agent material in the mixture and powder weight ratio be 0.7 × 10-4~4.0 ×
10-4The ratio between mol/g, the weight of water and amount of peptizing agent material are 2.0 × 103~15 × 103During g/mol, gained
The pore size distribution relative distribution of the carrier arrived.It is used to add in the catalyst that will be 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 the 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, time
1~24 hour, preferably 2~6 hours；It is calcined using baking oven, guipure, converter heating means, is calcined bar
Part includes 350~800 DEG C of temperature, preferably 400~700 DEG C, preferably 0.5~6 hour time, 1~4 hour.
According to the catalyst that provides of the present invention, the containing selected from VIII and the metal component selected from group vib
Measure as the usual content of hydrotreating catalyst, for example, on the basis of catalyst and in terms of oxide, it is described to urge
Agent contains 1~15 weight % group VIII metal component, 5~40 weight % group vib metal component；It is excellent
Select the group VIII metal component containing 2~10 weight %, 10~35 weight % group vib metal component.It is described
One or more of the group vib metal in Cr, Mo or W, preferably Mo and/or W, the VIII
One or more of the metal component in Fe, Co or Ni, preferably Co and/or Ni.
It is being enough at least one to load described selected from VIII and at least one metal component selected from group vib
On the premise of on the alumina support, specific carrying method is not particularly limited.It is preferred that method be
Infusion process.Contain the dipping of the metal component compound selected from VIII and group vib including separately or concurrently preparing
Solution, described dipping can be that excessive immersion stain, hole saturation impregnate according to maceration extract consumption difference, according to
The mode difference that dipping is realized can be infusion method leaching, spray impregnating.By the concentration to dipping solution,
The regulation and control of consumption or carrier consumption, can prepare the catalyst of specified content, and this is this
Art personnel are readily appreciated by, and do not repeat here.
The method for preparing catalyst provided according to the present invention, described vib metals compound is selected from these
One or more in the soluble compound of metal, for example, it may be silico-tungstic acid, silicotungstate, phosphorus molybdenum
One in acid, phosphomolybdate, molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate
Plant or several.
Described group VIII metallic compound be selected from these metals salt, including they inorganic acid salt or have
Machine salt.For example, the inorganic salts are selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphoric acid
One or more in salt, sulfate, the partially decomposed product of chloride and these salts, it is preferable that
One or more in nitrate, carbonate or subcarbonate.The organic salt is organic matter and VIII
Race metal combines the salt or soluble complexes of generation, the organic matter can be organic base, organic carboxyl acid,
Amine, ketone, ethers, alkyls, preferably organic carboxylate.
The catalyst provided according to the present invention, can also contain organic additive, when the catalyst of the present invention enters
When one step contains organic compound, in addition to the step of introduce organic compound, the organic compound can be with
It is concomitantly introduced into, can also be introduced after group VIII metal is introduced with group VIII metal, and is dried,
Introduced simultaneously by way of dipping it is preferred that organic matter and group VIII metal are configured into mixed solution, afterwards
It is dried.The selection of the drying temperature and time are except being insufficient to allow group VIII metal salt or complex compound point
Solution is outer, should also 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 any one in the prior art
The method for planting achievable above-mentioned purpose.For example, heat drying, is dried under reduced pressure and heats combination and be dried under reduced pressure
Etc. method.When the drying means is heat drying, drying temperature preferably is no more than 250 DEG C, enters one
Preferably more than 200 DEG C, more preferably not more than 180 DEG C of step.For example, in one preferred embodiment,
The drying temperature is 70 DEG C~180 DEG C.
According to the present invention, when preparing the catalyst containing organic compound, using the catalyst as base
The content of organic additive is 2~20 weight % in standard, the catalyst.
According to the conventional method in this area, the hydrotreating catalyst before the use, generally can be in hydrogen
In the presence of gas, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140~370 DEG C, it is this
Presulfurization can carry out also In-situ sulphiding in device outside device, and the active metal component that it is loaded is converted into
Metal sulfide component.
The catalyst that the present invention is provided can be used for hydrotreating or the hydro-upgrading of all kinds of hydrocarbon oil crude materials.For adding
Hydrogen processing or hydro-upgrading reaction condition be 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 be 2~18MPa, further it is excellent
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
Product is than being 50~5000, more preferably 50~4000, and the hydrogen to oil volume ratio refers to the volume flow of hydrogen
Speed and the ratio of the volume flow rate of hydrocarbon ils..
The device of the hydrotreating or the reaction of hydro-upgrading can be enough to add the feedstock oil any
With being carried out in the catalytic reaction dress device of the catalyst under hydrogen processing reaction condition, for example, described solid
Carried out in fixed bed reactor, moving-burden bed reactor or fluidized bed reactor.
Compared with prior art provides catalyst, present invention offer catalyst, which has, is preferably hydrocracked performance.
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 diffractometers of Siemens, Cu
Target, Ka radiation, solid probe, 40kV, 40mA, step-scan, 0.02 ° of stride, scanning range
5~70 °.
Boehmite, preparation method or source used in embodiment and comparative example：
PB1-1
The sodium metaaluminate that the aluminum sulfate and concentration for being 93g/L by the 500mL concentration of clear are 195g/L
(causticity coefficient is 1.6), while being slowly added in reactors of the 2L with stirring, controlling reaction temperature is 40 DEG C,
PH value 7.3.After reaction completely, it is 9.7 that stirring, which adds sodium carbonate to the solution ph that concentration is 0.5mol/L,.
After the reaction 1 hour of 50 DEG C of constant temperature, filtering, deionized water is washed three times, and 120 DEG C of temperature of being divulged information in baking oven are done
Dry 3hr, obtains boehmite PB1-1.PB1-1 h1, h2, h3, k1, k2And its pore volume is listed in
Table 1.
PB1-2
It is that 48g/L aluminum sulfate and the ammoniacal liquor of concentration 8% slowly add simultaneously by the 600mL concentration of clear
Enter in reactors of the 2L with stirring, reaction filtering, it is 35 DEG C, pH value to add ammoniacal liquor controlling reaction temperature
6.0.After reaction completely, filter cake is beaten by filtering, and it is 9.5 that stirring, which adds ammonium hydrogen carbonate to solution ph,.
After the reaction 12 hours of 35 DEG C of constant temperature, filtering, deionized water is washed three times, and 120 DEG C of temperature of being divulged information in baking oven are done
Dry 3hr, obtains boehmite PB1-2.PB1-2 h1, h2, h3, k1, k2And its pore volume is listed in
Table 1.
PB1-3
It is that 93g/L aluminum sulfate and the ammoniacal liquor of concentration 8% slowly add simultaneously by the 600mL concentration of clear
Enter in reactors of the 2L with stirring, controlling reaction temperature is 50 DEG C, pH value 4.6.After reaction completely, mistake
Filter, filter cake is beaten, and it is 8.4 that stirring, which 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 being divulged information in baking oven dry 3hr, obtain intending thin water aluminium
Stone PB1-3.PB1-3 h1, h2, h3, k1, k2And its pore volume is listed in table 1.
SB：The boehmite of Sasol companies production, trade name SB powder.SB h1, h2, h3,
k1, k2And its pore volume is listed in table 1.
The boehmite XPS of table 1 is characterized
Wherein, SB can not meet application claims.
Comparative example 1
By 366.7 grams of boehmite SB, (butt 0.75, butt assay method is to put a certain amount of former powder
Enter crucible with cover to be put into Muffle furnace, be warming up to after 700 DEG C of constant temperature 1hr, calculate ratio of the residue with former powder
Value, similarly hereinafter) (sinopec catalyst branch company Chang Ling catalyst plant is produced, business with 66 grams of super stable molecular sieve LAY
Brand LAY lattice constants 24.58, pore volume 0.39ml/g, butt 0.75, similarly hereinafter), 132 grams of faintly acids
Sial (German Condea companies production, trade name Sira-40, pore volume 0.88ml/g, than surface 468m2/ g,
Silica weight content 40%, infrared B acidacidities value 0.04mmol/g, butt 0.76), sesbania powder 11
Gram, 300g Ludox (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, dioxide-containing silica 25%,
Silica dioxide granule diameter 9-11nm), 36.1ml purity for 65% concentrated nitric acid (molar concentration is 14.4mol/L,
Similarly hereinafter), 299ml deionized waters are well mixed, and are extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C
Drying 3 hours, 600 DEG C of roasting temperatures 3 hours obtain carrier, and catalyst carrier composition is shown in Table 2.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 63ml aqueous solution dipping, 180 DEG C are dried 10 hours, are urged
Agent R-1.On the basis of catalyst total amount, the mass fraction (being calculated value, similarly hereinafter) of metal component in R-1
It is listed in table 2.
Comparative example 2
By 367 grams of boehmite PB1-1 (butt 0.75) and 66 grams of super stable molecular sieve LAY, sesbania powders
11.14 grams, 132 grams of faintly acid sial (German Condea companies production, trade name Sira-40, pore volume 0.88ml/g,
Than surface 468m2/ g, silica weight content 40%, infrared B acidacidities value 0.04mmol/g, butt 0.76),
300g Ludox (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, dioxide-containing silica 25%, two
Silicon oxide particle diameter 9-11nm), 41.7ml purity for 65% concentrated nitric acid, 361ml deionized waters mixing
Uniformly, it is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 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 2.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 72ml aqueous solution dipping, 180 DEG C are dried 10 hours, are urged
Agent R-2.On the basis of catalyst total amount, the mass fraction (being calculated value, similarly hereinafter) of each metal component is listed in
Table 2.
Comparative example 3
By 367 grams of boehmite SB powder and 66 grams of super stable molecular sieve LAY, 16 grams of sesbania powder, 132
(German Condea companies production, trade name Sira-40, pore volume 0.88ml/g compare surface for gram faintly acid sial
468m2/ g, silica weight content 40%, infrared B acidacidities value 0.04mmol/g, butt 0.76), 300g
Ludox (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, dioxide-containing silica 25%, titanium dioxide
Silicon grain diameter 9-11nm), 29.3ml purity for 65% concentrated nitric acid, 299ml deionized waters be well mixed,
It is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C dry 3 hours, 600 DEG C of roasting temperatures 3
Hour, carrier is obtained, catalyst carrier composition is shown in Table 2.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 78ml aqueous solution dipping, 180 DEG C are dried 10 hours, are urged
Agent R-3.On the basis of catalyst total amount, the mass fraction (being calculated value, similarly hereinafter) of each metal component is listed in
Table 2.
The carrier of table 2 and catalyst characterization
Powder weight refers to Y type molecular sieve, faintly acid sial and boehmite weight sum；Peptizing agent thing
The amount of matter is metering H proton molal quantitys in peptizing agent used.
Embodiment 1
By 371.6 grams of boehmite PB1-2 (butt 0.74) and 65.8 grams of super stable molecular sieve LAY, sesbanias
16 grams, 131.6 grams faintly acid sial of powder (German Condea companies production, trade name Sira-40, pore volume
0.88ml/g, than surface 468m2/ g, silica weight content 40%, infrared B acidacidities value 0.04mmol/g,
Butt 0.76), 300g Ludox (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, silica
Content 25%, silica dioxide granule diameter 9-11nm), 20.5ml purity for 65% concentrated nitric acid, 409.7ml
Deionized water is well mixed, and is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry 3 hours,
600 DEG C of roasting temperatures 3 hours, obtain carrier, and catalyst carrier composition is shown in Table 2.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 78ml aqueous solution dipping, 180 DEG C are dried 10 hours, are urged
Agent C-1.On the basis of catalyst total amount, the mass fraction (being calculated value, similarly hereinafter) of each metal component is listed in
Table 2.
Embodiment 2
By 361.8 grams of boehmite PB1-3 (butt 0.76) and 65.8 grams of super stable molecular sieve LAY, sesbanias
16 grams, 131.6 grams faintly acid sial of powder (German Condea companies production, trade name Sira-40, pore volume
0.88ml/g, than surface 468m2/ g, silica weight content 40%, infrared B acidacidities value 0.04mmol/g,
Butt 0.76), 300g Ludox (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, silica
Content 25%, silica dioxide granule diameter 9-11nm), 6.7ml purity for 65% concentrated nitric acid, 598.4ml
Deionized water is well mixed, and is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry 3 hours,
600 DEG C of roasting temperatures 3 hours, obtain carrier, and catalyst carrier composition is shown in Table 2.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 110ml aqueous solution dipping, 180 DEG C are dried 10 hours, are obtained
Catalyst C-2.On the basis of catalyst total amount, the mass fraction (being calculated value, similarly hereinafter) of each metal component
It is listed in table 2.
Embodiment 3
By 164.5 grams of boehmite PB1-3 (butt 0.76) and 308.6 grams of super stable molecular sieve PUSY (in
The Chang Ling catalyst plant production of Effect of Catalysis In Petrochemistry agent branch company, trade name USY-5, the weight of phosphorus pentoxide content 1.2
Measure %, lattice constant 24.44, pore volume 0.40ml/g, butt 0.81), 16 grams, 65.8 grams weak acid of sesbania powder
Property sial (production of German Condea companies, trade name Sira-40, pore volume 0.88ml/g, than surface 468m2/ g,
Silica weight content 40%, infrared B acidacidities value 0.04mmol/g, butt 0.76), 300g Ludox
(Beijing effective company of flying dragon horse economy and trade, trade name JN-25, dioxide-containing silica 25%, silica dioxide granule
Diameter 9-11nm), 27ml purity for 65% concentrated nitric acid, 366.5ml deionized waters be well mixed, be extruded into
Circumscribed circle diameter is 1.6 millimeters of trilobal bar, and 120 DEG C dry 3 hours, and 600 DEG C of roasting temperatures 3 are small
When, carrier is obtained, catalyst carrier composition is shown in Table 2.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 100ml aqueous solution dipping, 180 DEG C are dried 10 hours, are obtained
Catalyst C-3.On the basis of catalyst total amount, the mass fraction (being calculated value, similarly hereinafter) of each metal component
It is listed in table 2.
Embodiment 4
The preparation of carrier is carried out using the identical method of embodiment 3, the difference is that purity is 65% during extrusion
Nitric acid dosage is 7.5ml, and water consumption is 566ml.
It is cooled to after room temperature, takes 100 grams of carriers (Zigong, Sichuan cemented carbide workses, tungsten oxide containing ammonium metatungstate
Content is 82 weight %) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content
For 51 weight %) 8.7 grams, 10.5g citric acid 110ml aqueous solution dipping, 180 DEG C are dried 10 hours, are obtained
Catalyst C-4.On the basis of catalyst total amount, in C-4 metal component mass fraction (be calculated value, under
Table 2 is listed in together).
Catalyst pores distribution characterization result is listed in table 3.
The distribution of the catalyst pores of table 3 is characterized
Embodiment 5
This example illustrates that the present invention provides the performance of catalyst.
Raw materials used oil is the husky light vacuum gas oil (VGO) that subtracts two, and its physico-chemical property is shown in Table 4.
The raw material oil nature of table 4
In this example, the evaluation method of catalyst is：By catalyst breakage into 2~3 millimeters of diameter particle,
Load 20 milliliters of catalyst 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 switches reaction raw materials reaction.
Vulcanization program：150 DEG C are warming up to, sulfurized oil is introduced, constant temperature 1hr Wen Bo to be adsorbed pass through two reactions
Device, is warming up to 230 DEG C, stable 2hr is warming up to 360 DEG C, stable 6hr with 60 DEG C/hr with 60 DEG C/hr.
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 sampling analysis after 20 hours.Raw material and response sample are subtracted
Separated is pressed, calculates and is more than 350 DEG C of cut percentage compositions.With the conversion ratio evaluation of Unit Weight catalyst
The activity of catalyst, computational methods are as follows：
Wherein, m1To be more than 350 DEG C of cut amounts, m in raw material2To be more than 350 DEG C of cut amounts in generation oil,
mcFor loaded catalyst.
The catalyst performance evaluation of table 5
Using reference catalyst R-1 conversion ratio as 100%, the relative activity of other catalyst is calculated.Evaluate
Catalyst and its results are shown in Table 5.
As a result show, the relative activity of the catalyst provided relative to reference catalyst, the present invention is generally improved
More than 10%.
Claims (20)
1. a kind of multi-stage porous hydrocracking catalyst containing Y type molecular sieve, containing carrier and load on this carrier
Hydrogenation active metal component, the carrier contains Y type molecular sieve and faintly acid sial and silica and oxidation
Aluminium, the hydrogenation active metal component is selected from the molybdenum of vib and/or the nickel and/or cobalt of tungsten and group VIII,
Characterized in that, the pore size distribution of the catalyst is met：It is total that bore dia accounts for catalyst less than the pore volume in 2nm holes
The 2%~50% of pore volume, bore dia accounts for the 20%~85% of catalyst total pore volume for the pore volume in 2~100nm holes,
The pore volume that bore dia is more than 100nm holes accounts for the 3%~70% of catalyst total pore volume.
2. catalyst according to claim 1, it is characterised in that the pore size distribution of the catalyst is met：
The pore volume that bore dia is less than 2nm holes accounts for the 4%~21% of catalyst total pore volume, and bore dia is 2~100nm holes
Pore volume account for the 20%~85% of catalyst total pore volume, the pore volume that bore dia is more than 100nm holes accounts for catalyst
The 4%~60% of total pore volume.
3. catalyst according to claim 1, it is characterised in that the Y type molecular sieve be selected from HY,
REY、PY、USY、PUSY；The aluminum oxide is gama-alumina.
4. catalyst according to claim 3, it is characterised in that the Y type molecular sieve be selected from USY,
PUSY。
5. the catalyst according to claim 1 or 3, it is characterised in that the structure cell of the Y type molecular sieve
Constant is 2.460~2.430, and specific surface area is 550~700 meters2/ gram, pore volume is 0.30~0.45 ml/g.
6. catalyst according to claim 1, it is characterised in that on the basis of the carrier, the Y
The content of type molecular sieve is 3~70 weight %, and the content of aluminum oxide is 10~85 weight %, faintly acid sial content
For 5~60 weight %, the content of silica is 4~30 weight %.
7. catalyst according to claim 5, it is characterised in that on the basis of the carrier, the Y
The content of type molecular sieve is 5~60 weight %, and the content of aluminum oxide is 15~60 weight %, faintly acid sial content
For 5~60 weight %.
8. the catalyst according to claim 1,5 or 6 any one, it is characterised in that the silica
Precursor selected from Ludox, loss on ignition be 0~60 weight % Silica hydrogel, in White Carbon black, superfine silicon dioxide
One or several kinds, on the basis of carrier, silica content be 5~25 weight %.
9. catalyst according to claim 1, it is characterised in that on the basis of catalyst, the catalysis
The content of carrier is 45~85 weight % in agent, and the nickel counted using oxide and/or the content of cobalt is 1~15 weights
% is measured, the molybdenum counted using oxide and/or the content of tungsten is 5~40 weight %.
10. catalyst according to claim 8, it is characterised in that on the basis of catalyst, the catalysis
The content of carrier is 60~80 weight % in agent, and the nickel counted using oxide and/or the content of cobalt is 2~10 weights
% is measured, the molybdenum counted using oxide and/or the content of tungsten is 10~35 weight %.
11. catalyst according to claim 1, it is characterised in that contain organic additive in the catalyst,
One or more of the described organic additive in oxygen-containing and/or nitrogenous organic matter, on the basis of catalyst,
The content of organic additive is 2~20 weight % in the catalyst.
12. catalyst according to claim 10, it is characterised in that the oxygen containing organic matter, which is selected from, to be had
One or more in machine alcohol, organic acid, one kind in organic amine, organic ammonium salt of nitrogenous organic matter or
It is several.
13. catalyst according to claim 11, it is characterised in that the oxygen containing organic matter is selected from second
Glycol, glycerine, relative molecular mass for 200~1500 polyethylene glycol, diethylene glycol, butanediol, acetic acid,
In maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid, malic acid
One or more, wherein it is preferred that 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
And its one or more in ammonium salt.
14. catalyst according to claim 1, it is characterised in that the preparation method of the carrier is included such as
Lower step：(1) by Y type molecular sieve and faintly acid sial, boehmite, silica predecessor, peptizing agent,
Lubricant and water mixing, obtain a kind of mixture, the consumption of each component makes peptizing agent material in the mixture
Amount is 0.28 × 10 with powder weight ratio-4~4.8 × 10-4The ratio between mol/g, the weight of water and amount of peptizing agent material
For 2.0 × 103~30 × 103G/mol, the powder weight is the Y type molecular sieve, boehmite and weak acid
Property aluminum weight sum, the amount of the peptizing agent material refers to measuring H proton molal quantitys in the peptizing agent；
The lubricant is the one or two kinds of in sesbania powder, graphite, on the basis of powder weight, the lubricant
Content is 1~9 weight % in powder；(2) the mixture kneading that obtains step (1), shaping, dry and be calcined,
Obtain carrier.
15. catalyst according to claim 13, it is characterised in that the boehmite includes PB1,
Characterized with X-ray diffraction, the κ 1 and κ 2 of the PB1 meet 1 ＜ κ 1≤3 and 1 ＜ κ 2≤3, wherein, κ 1=h2/h1,
κ 2=h3/h2, h1, h2 and h3 be respectively PB1 x-ray diffraction spectra in 2 θ angles be 24 °~30 °, 35 °~41 °
With the peak height of 46 °~52 ° of three diffraction maximums.
16. catalyst according to claim 14, it is characterised in that characterized with X-ray diffraction, the PB1
κ 1 be that 1.2~2.3, κ 2 is 1.02~1.4.
17. catalyst according to claim 14, it is characterised in that the specific surface area of the PB1 is
100~350 meters2/ gram, pore volume is 0.7~1.2 ml/g.
18. catalyst according to claim 16, it is characterised in that the specific surface area of the PB1 is
150~280 meters2/ gram, pore volume is 0.85~1.12 ml/g.
19. catalyst according to claim 13, it is characterised in that the use of each component in the step (1)
Amount makes the amount of the peptizing agent material in the mixture and powder weight ratio be 0.7 × 10-4~4.0 × 10-4Mol/g,
The ratio between the weight of water and the amount of peptizing agent material are 2.0 × 103~15 × 103g/mol。
20. application of the catalyst in hydrocarbon ils processing according to any one of claim 1~18.
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| CN114433186B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing macropores, and stepwise preparation method and application thereof |
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