CN107029779B - 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 aluminium oxide, the hydrogenation active metal component is selected from the molybdenum of group VIB and/or the nickel and/or cobalt of tungsten and group VIII, it is characterized in that, the pore size distribution of the catalyst meets: the pore volume that bore dia is less than the hole 2nm accounts for the 2%~50% of catalyst total pore volume, bore dia is that the pore volume in the hole 2~100nm accounts for the 20%~85% of catalyst total pore volume, the pore volume that bore dia is greater than the hole 100nm accounts for the 3%~70% of catalyst total pore volume.Compared with the catalyst that the prior art provides, catalyst provided by the invention has higher hydrogenation cracking activity.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and its applications, it is more particularly related to a kind of type containing Y point
The multi-stage porous hydrocracking catalyst of son sieve and its application.
Background technique
Industry is hydrocracked charging 350~540 DEG C of fractions such as including VGO, and heavy end molecular weight is big, and catalyst is needed to mention
For larger duct space, loaded catalyst duct is mainly determined by carrier, this just needs to increase the aperture of carrier, improves reaction
The ability of hydrogenation active metals in molecule contacts to catalyst.It is especially full since molecular sieve and metal sulfide hole appearance are smaller
The middle macropore of macromolecule hydrocarbon feed needs required by sufficient PETROLEUM PROCESSING is less, and conventional method can be by hydrocracking catalyst
Macropore is introduced in carrier and holds the method for heat-resistant inorganic oxide matrix to realize, such as introduces alumina host.
A kind of catalyst for hydrogenation treatment of diesel oil of ZL01123765.1, the catalyst contain a kind of carrier and are supported on the carrier
On molybdenum and/or tungsten and nickel and/or cobalt, which is characterized in that the carrier is made of aluminium oxide and zeolite, aluminium oxide and zeolite
Weight ratio is 90:10~50:50, and the aluminium oxide is the weight by small porous aluminum oxide and macroporous aluminium oxide according to 75:25~50:50
Amount is than the aluminium oxide that is combined, wherein small porous aluminum oxide be diameter less than the pore volume in 80 angstroms of holes account for total pore volume 95% with
On aluminium oxide, macroporous aluminium oxide is that the pore volume in 60~600 angstroms of holes of diameter accounts for the aluminium oxide of 70% or more total pore volume.
The invention be suitable for diesel modifying catalyst process, and VGO be hydrocracked charging boiling point it is higher, be actually hydrocracked
It is usually reacted in reaction process with trickle bed mode, the duct 60nm is not enough to improve the dispersion of drop, this makes mass transfer mistake
Critical process in Cheng Chengwei hydrocracking process requires further improvement the aperture of catalyst.
ZL97121663.0 disclose it is a kind of especially suitable for produce intermediate oil hydrocracking catalyst, containing whether there is or not
Silica~the alumina component that shapes and aperture alumina adhesive, amorphous silicon oxide~aluminium oxide content are 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 %,
Surplus is aperture alumina adhesive, it is characterised in that 150~300 meters of catalyst specific surface2/ gram, 0.25~0.50 milli of Kong Rong
Rise/gram, 4~15 nano-pores are distributed in 60%~90%, infrared 0.30~0.50 mM/gram of acidity.
CN102030351A discloses a kind of macroporous aluminium oxide of bimodal pore distribution, and pore volume is 0.6~3.0ml/g,
Specific surface area is 90~300m2/ g, wherein 35~100 angstroms of hole accounts for the 20%~55% of total pore volume, most probable pore size is located at
50~90 angstroms, 200~800 angstroms of hole accounts for the 20%~55% of total pore volume, and most probable pore size is located at 300~600 angstroms.The oxidation
Prepared by the method that two step agings are used during aluminum is standby, since the treatment conditions in ageing process are generally more severe
It carves, in addition can reduce aluminum oxide precursor object surface active hydroxyl groups also will affect and urge so that metal-support interaction changes
The pore size distribution of agent, so that the reactivity worth of catalyst reduces.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hydrocracking catalyst and its applications in hydrocarbon ils processing.
Catalyst provided by the invention has specific multistage pore size distribution, and when being used for hydrocarbon oil hydrogenation cracking reaction, which has
Higher catalytic activity.
The present invention relates to a kind of multi-stage porous hydrocracking catalyst containing Y type molecular sieve, the catalyst contain carrier and negative
Hydrogenation active metal component on this carrier is carried, the carrier contains Y type molecular sieve, faintly acid sial and silica and oxygen
Change aluminium, the hydrogenation active metal component is selected from the molybdenum of group VIB and/or the nickel and/or cobalt of tungsten and group VIII, feature
Be, the pore size distribution of the catalyst meets: the pore volume that bore dia is less than the hole 2nm account for catalyst total pore volume 2%~
50%, bore dia is that the pore volume in the hole 2~100nm accounts for the 20%~85% of catalyst total pore volume, and bore dia is greater than the hole 100nm
Pore volume account for the 3%~70% of catalyst total pore volume.
The invention further relates to application of the catalyst above-mentioned in hydrocarbon ils processing.
According to the present invention, the pore size distribution of the preferably described catalyst meets: it is total that the pore volume that bore dia is less than 2nm accounts for catalyst
The 4%~21% of pore volume, bore dia are that the pore volume of 2~100nm accounts for the 20%~85% of catalyst total pore volume, bore dia
Pore volume greater than 100nm accounts for the 4%~60% of catalyst total pore volume.
Wherein, the Y type molecular sieve is 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)), preferably wherein
USY,PUSY.The molecular sieve can be commercially available commodity, can also use arbitrary prior art preparation.For example,
The disclosed method for preparing USY of ZL00123139.1, the disclosed method for preparing PUSY of Zl200410071122.6, makees here
For 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, hole
Hold is 0.30~0.45 ml/g；The aluminium oxide is gama-alumina.
The catalyst provided according to the present invention, the faintly acid sial can be commercially available commodity or existing using any one
There is technology preparation, infrared B acidacidity 0.01~0.1mmol/g of value, preferably specific surface area are 350~750 meters2/ gram, Kong Rongwei
0.4~1.2 ml/g, further preferably specific surface area is 400~650 meters2/ gram, 0.45~0.95 ml/g of Kong Rongwei
Faintly acid sial.The faintly acid sial can pass through chemical reaction selected from silicon oxide-containing compound and alumina cpd body
A kind of or several, the Siral series such as produced using Sasol company, Germany of acquired silicon-containing alumina, amorphous silicon aluminium
Aluminum silicon powder (Siral-5, Siral-10, Siral-15, Siral-20, Siral-30, Siral-40 etc.) is prepared into for precursor
The silicon-containing alumina arrived.On the basis of faintly acid sial, wherein the content of silica is the 10 weight % of weight %~80, preferably
15 weight of weight %~55 %.
The precursor of the silica is selected from silica solution, loss on ignition is the Silica hydrogel of 0~60 weight %, White Carbon black, ultra-fine
Silica 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 aluminium oxide, with described
On the basis of carrier, the content of the Y type molecular sieve is 3~70 weight %, and the content of aluminium 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 %, the content of aluminium oxide are 15~60 weight %, and faintly acid sial content is 5~60 weight %, and silica contains
Amount is 5~25 weight %.Wherein, when not containing other auxiliary agents in carrier, Y type molecular sieve, faintly acid sial and aluminium oxide contain
The variation of amount and silica meets the sum of each component for absolutely.
On the basis of catalyst, in the catalyst content of carrier be 45~85 weight %, in terms of oxide described in
The content of nickel and/or cobalt is 1~15 weight %, and the content of the molybdenum and/or tungsten in terms of oxide is 5~40 weight %.Into
The content of carrier is 60~80 weight %, the content of the nickel and/or cobalt in terms of oxide in the preferably described catalyst of one step
For 2~10 weight %, the content of the molybdenum and/or tungsten in terms of oxide is 10~35 weight %.
Organic additive can be contained in the catalyst, the organic additive is selected from oxygen-containing and/or nitrogenous organic
One or more of object, on the basis of catalyst, the content of organic additive is 2~20 weight % in the catalyst.Into
The one step preferably oxygen containing organic matter is selected from one or more of Organic Alcohol, organic acid, and nitrogenous organic matter is selected from organic
One or more of amine, organic ammonium salt.The more preferred oxygen containing organic matter is selected from ethylene glycol, glycerine, molecular weight
200~1500 polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- hexamethylene two
One or more of amine tetraacethyl, citric acid, tartaric acid, malic acid, wherein it is preferred that ethylene glycol, glycerine, polyethylene glycol and
Citric acid；Nitrogenous organic matter is selected from ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, three second of nitrilo-
One or more of acid, EDTA and its ammonium salt.
In the present invention, to meet the requirements the pore size distribution of final catalyst, the carrier is preferably by including the following steps
Method preparation: (1) Y type molecular sieve with boehmite, silica predecessor, peptizing agent and water is mixed, obtains a kind of mixing
Object, the dosage of each component make the amount of peptizing agent substance and powder weight ratio 0.28 × 10 in the mixture-4~4.8 ×
10-4Mol/g, the ratio between weight and the amount of peptizing agent substance of water are 2.0 × 103~30 × 103G/mol, the powder weight are
The amount of the sum of the Y type molecular sieve, boehmite and faintly acid aluminum weight, the peptizing agent substance refers to the peptization
H proton molal quantity is measured in agent；The lubricant is one of sesbania powder, graphite or two kinds, on the basis of powder weight,
Lubricant content in powder is 1~9 weight %；(2) it by mixture kneading that step (1) obtains, molding, drying and roasts
It burns, obtains carrier, wherein the boehmite includes PB1, with X-ray diffraction characterization, the κ 1 and κ 2 of the PB1 meets 1 < κ
1≤3 and 1 < κ 2≤3, the κ of the further preferred PB11For 1.2~2.3, κ2It is 1.02~1.4.Wherein, κ 1=h2/h1,2 κ
=h3/h2, h1, h2 and h3 be respectively in the x-ray diffraction spectra of PB1 2 angles θ be 24 °~30 °, 35 °~41 ° and 46 °~52 °
Three diffraction maximums peak height.
Wherein, further preferably the specific surface area of the PB1 is 100~350 meters2/ gram, 0.7~1.2 milliliter of Kong Rongwei/
Gram, the specific surface area of the further preferred PB1 is 150~280 meters2/ gram, 0.85~1.12 ml/g of Kong Rongwei.It is preferred that
The dosage of each component makes the amount and powder weight of the peptizing agent substance in the mixture in the step (1) of support preparation method
Measuring ratio is 0.7 × 10-4~4.0 × 10-4Mol/g, the ratio between weight and the amount of peptizing agent substance of water are 2.0 × 103~15 ×
103g/mol.In the present invention, the catalyst multi-stage porous pore size distribution measures with the following method: using N2 adsorption method (BET
Method) measure in catalyst that diameter is less than the hole 2nm pore volume B1 and diameter is the hole 2~100nm pore volume B2, and surveyed using mercury injection method
It obtains diameter in catalyst and is greater than the hole 100nm pore volume H1, the sum of three is catalyst total pore volume V.With υ1It is small to represent bore dia
Pore volume in the hole of 2nm accounts for the percentage of catalyst total pore volume, wherein υ1=B1/V；With υ2Represent 2~100nm of bore dia
The pore volume in hole accounts for the percentage of catalyst total pore volume, wherein υ2=B2/V；With υ3Represent the hole that bore dia is greater than the hole 100nm
Volume accounts for the percentage of catalyst total pore volume, wherein υ3=H1/V.
Kong Rong, specific surface area of the boehmite etc., be by the boehmite in 600 DEG C roast 4 hours after,
It characterizes to obtain by BET N2 adsorption.
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.For example, one kind disclosed in CN100999328B using aluminum sulfate and
The boehmite of the boehmite method preparation of sodium metaaluminate neutralisation preparation can meet requirement of the invention, here as
Reference.
In the present invention, the molding is preferably extruded moulding.
Inventors have found that in carrier molding, when preparing carrier especially with extrusion method, the dosage of peptizing agent and water
The pore size distribution of final molding carrier is had an impact.Make in the mixture when according to the dosage of the method for the present invention control each component
Peptizing agent substance amount and powder weight ratio be 0.7 × 10-4~4.0 × 10-4Mol/g, the weight and peptizing agent substance of water
The ratio between amount be 2.0 × 103~15 × 103When g/mol, the pore size distribution relative distribution of obtained carrier.Will be by with this
When the catalyst of the carrier preparation of attribute is used for hydrocracking reaction, catalyst has better weight activity, and (Unit Weight is urged
The activity of agent).
In the present invention, the method for the drying and roasting is conventional method, for example, using baking oven, mesh belt, converter heating side
Method is dried, and drying condition includes 50~350 DEG C of temperature, preferably 70~200 DEG C, and the time 1~24 hour, preferably 2~6 is small
When；It being roasted using baking oven, mesh belt, converter heating means, roasting condition includes 350~800 DEG C of temperature, and preferably 400~700
DEG C, the time 0.5~6 hour, preferably 1~4 hour.
According to catalyst provided by the invention, the content selected from VIII group and the metal component selected from group vib is to add
Hydrogen handles the usual content of catalyst, for example, the catalyst contains 1~15 weight on the basis of catalyst and in terms of oxide
Measure the group VIII metal component of %, the group vib metal component of 5~40 weight %；Preferably comprise the VIII group gold of 2~10 weight %
Belong to component, the group vib metal component of 10~35 weight %.The group vib metal is selected from one or more of Cr, Mo or W, excellent
Mo and/or W is selected, the group VIII metal group is selected from one or more of Fe, Co or Ni, 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, when catalyst of the invention further contains
When having organic compound, further include the steps that introducing organic compound, the organic compound can be with group VIII metal one
It rises and introduces, can also be introduced after introducing group VIII metal, and be dried, preferably by organic matter and group VIII metal
Mixed solution is configured to by way of dipping while being introduced, is dried later.The selection of the drying temperature and time removes
It is insufficient to allow group VIII metal salt or complex compound to decompose outer, should also allow to retain in the catalyst most of introduced organic
Object, such as retain 50% or more organic matter, it is highly preferred that retaining 70% or more organic matter.Its method can be existing skill
The method that any one in art can realize above-mentioned purpose.For example, heat drying, is dried under reduced pressure and heats combination and be dried under reduced pressure
Method.When the drying means 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 DEG C.For example, in one preferred embodiment, the drying temperature is 70 DEG C~180 DEG C.
It is described on the basis of the catalyst when preparing the catalyst containing organic compound according to the present invention
The content of organic additive is 2~20 weight % in catalyst.
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 hydrotreating or the hydro-upgrading of all kinds of hydrocarbon oil crude materials.For hydrotreating
Or the reaction condition of hydro-upgrading is usual hydrotreating or hydro-upgrading reaction condition, such as reaction Wen Weidu 200~420
DEG C, further preferably 220~400 DEG C, pressure be 2~18MPa, further preferably 2~15MPa, liquid hourly space velocity (LHSV) be 0.3~
10 hours-1, further preferably 0.3~5 hour-1, hydrogen to oil volume ratio is 50~5000, further preferably 50~4000, institute
State the ratio that hydrogen to oil volume ratio refers to the volume flow rate of hydrogen and 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 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 provides catalyst and is hydrocracked performance with better.
Specific embodiment
The present invention is described further for the following examples.
The invention will be further described by the following examples.
In experiment, XRD is carried out on the D5005 type X-ray diffractometer of Siemens, Cu target, Ka radiation, solid
Detector, 40kV, 40mA, step-scan, 0.02 ° of stride, 5~70 ° of scanning range.
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, the dry 3hr of 120 DEG C of temperature of divulging information in baking oven obtains boehmite PB1-2.The h1 of PB1-2, h2, h3, k1, k2With
And its Kong Rong 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
The dry 3hr of DEG C temperature, obtains boehmite PB1-3.The h1 of PB1-3, h2, h3, k1, k2And its hole appearance is listed in table 1.
The boehmite of SB:Sasol company production, trade name SB powder.The h1 of SB, h2, h3, k1, k2And its Kong Rong
It is listed in table 1.
1 boehmite XPS of table characterization
Wherein, SB be not able to satisfy the present invention claims.
Comparative example 1
By 366.7 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, calculates residue with the ratio of original powder, similarly hereinafter) and 66 grams super steady point
Son sieve LAY (production of middle Effect of Catalysis In Petrochemistry agent branch company Chang Ling catalyst plant, trade names LAY lattice constant 24.58, Kong Rong
0.39ml/g, butt 0.75, similarly hereinafter), 132 grams of faintly acid sial (German Condea company production, trade name Sira-40, Kong Rong
0.88ml/g, specific surface 468m2/ g, silica weight content 40%, infrared B acidacidity value 0.04mmol/g, butt
0.76), 11 grams of sesbania powder, 300g silica solution (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, dioxide-containing silica
25%, silica particle diameter 9-11nm), 36.1ml purity be 65% concentrated nitric acid (molar concentration 14.4mol/L, under
Together), 299ml deionized water is uniformly mixed, and is extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry 3 hours,
600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carrier composition is shown in Table 2.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 63ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst R-1.On the basis of catalyst total amount, R-1
The mass fraction (for calculated value, similarly hereinafter) of middle metal component 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, 11.14 grams of sesbania powder, 132
Gram faintly acid sial (German Condea company production, trade name Sira-40, Kong Rong 0.88ml/g, specific surface 468m2/ g, dioxy
SiClx weight content 40%, infrared B acidacidity value 0.04mmol/g, butt 0.76), (Beijing flying dragon horse economy and trade of 300g silica solution
Effective company, trade name JN-25, dioxide-containing silica 25%, silica particle diameter 9-11nm), 41.7ml purity be
65% concentrated nitric acid, 361ml deionized water are uniformly mixed, and are extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of bakings
Dry 3 hours, 600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carrier composition is shown in Table 2.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 72ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst R-2.On the basis of catalyst total amount, each gold
The mass fraction (for calculated value, similarly hereinafter) for belonging to component is listed in table 2.
Comparative example 3
By 367 grams of boehmite SB powder and 16 grams, 132 grams 66 grams of super stable molecular sieve LAY, sesbania powder faintly acid sial
(German Condea company production, trade name Sira-40, Kong Rong 0.88ml/g, specific surface 468m2/ g, silica weight content
40%, infrared B acidacidity value 0.04mmol/g, butt 0.76), 300g silica solution (Beijing effective company of flying dragon horse economy and trade, commodity
Name JN-25, dioxide-containing silica 25%, silica particle diameter 9-11nm), 29.3ml purity be 65% concentrated nitric acid,
299ml deionized water is uniformly mixed, and is extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry 3 hours, 600 DEG C
Roasting temperature 3 hours, carrier is obtained, catalyst carrier composition is shown in Table 2.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 78ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst R-3.On the basis of catalyst total amount, each gold
The mass fraction (for calculated value, similarly hereinafter) for belonging to component is listed in table 2.
2 carrier of table and catalyst characterization
Powder weight refers to the sum of Y type molecular sieve, faintly acid sial and boehmite weight；The amount of peptizing agent substance is
H proton molal quantity is measured 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, 16 grams of sesbania powder,
131.6 grams of faintly acid sial (German Condea company production, trade name Sira-40, Kong Rong 0.88ml/g, specific surface 468m2/
G, silica weight content 40%, infrared B acidacidity value 0.04mmol/g, butt 0.76), 300g silica solution (Beijing flying dragon
The effective company of horse economy and trade, trade name JN-25, dioxide-containing silica 25%, silica particle diameter 9-11nm), 20.5ml it is pure
It is uniformly mixed to spend the concentrated nitric acid for 65%, 409.7ml deionized water, is extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters,
120 DEG C dry 3 hours, 600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carrier composition is shown in Table 2.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 78ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst C-1.On the basis of catalyst total amount, each gold
The mass fraction (for calculated value, similarly hereinafter) for belonging to 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, 16 grams of sesbania powder,
131.6 grams of faintly acid sial (German Condea company production, trade name Sira-40, Kong Rong 0.88ml/g, specific surface 468m2/
G, silica weight content 40%, infrared B acidacidity value 0.04mmol/g, butt 0.76), 300g silica solution (Beijing flying dragon
The effective company of horse economy and trade, trade name JN-25, dioxide-containing silica 25%, silica particle diameter 9-11nm), 6.7ml purity
For 65% concentrated nitric acid, 598.4ml deionized water be uniformly mixed, being extruded into circumscribed circle diameter is 1.6 millimeters of trilobal item, 120
DEG C drying 3 hours, 600 DEG C roasting temperature 3 hours, obtain carrier, catalyst carrier composition is shown in Table 2.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 110ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst C-2.On the basis of catalyst total amount, respectively
The mass fraction (for calculated value, similarly hereinafter) of metal component 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 (middle Effect of Catalysis In Petrochemistry
The production of agent branch company Chang Ling catalyst plant, trade name USY-5,1.2 weight % of phosphorus pentoxide content, lattice constant 24.44, hole
Hold 0.40ml/g, butt 0.81), 16 grams, 65.8 grams faintly acid sial of sesbania powder (production of German Condea company, trade name
Sira-40, Kong Rong 0.88ml/g, specific surface 468m2/ g, silica weight content 40%, infrared B acidacidity value
0.04mmol/g, butt 0.76), (Beijing effective company of flying dragon horse economy and trade, trade name JN-25, silica contain 300g silica solution
Amount 25%, silica particle diameter 9-11nm), the concentrated nitric acid that 27ml purity is 65%, the mixing of 366.5ml deionized water it is equal
Even, being extruded into circumscribed circle diameter is 1.6 millimeters of trilobal item, and 120 DEG C dry 3 hours, 600 DEG C roasting temperature 3 hours, must carry
Body, catalyst carrier composition are shown in Table 2.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 100ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst C-3.On the basis of catalyst total amount, respectively
The mass fraction (for calculated value, similarly hereinafter) of metal component 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 the nitric acid that purity is 65% when extrusion is used
Amount is 7.5ml, and water consumption is 566ml.
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., Jiangsu, nickel oxide content are 51 weight %),
10.5g citric acid 110ml aqueous solution dipping, 180 DEG C are dried 10 hours, obtain catalyst C-4.On the basis of catalyst total amount, C-4
The mass fraction (for calculated value, similarly hereinafter) of middle metal component is listed in table 2.
Catalyst pores distribution characterization result is listed in table 3.
3 catalyst pores of table distribution characterization
Embodiment 5
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.
4 raw material oil nature of table
In this example, the evaluation method of catalyst is: by catalyst breakage at 2~3 millimeters of diameter of particle, at 30 milliliters
20 milliliters of catalyst are packed into fixed bed reactors.It is first pressed under a hydrogen atmosphere with the kerosene containing 2 weight % carbon disulfide before reaction
Vulcanized according to following procedure, then switches reaction raw materials reaction.
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.
Cracking reaction: reaction temperature is 355 DEG C, reaction pressure 6.4MPa, and liquid hourly space velocity (LHSV) (LHSV) is 1 hour-1, hydrogen oil
Volume ratio is 800, stablizes sampling analysis after 20 hours.Raw material and response sample carry out vacuum distillation separation, calculate and are greater than 350 DEG C
Fraction percentage composition.With the activity of the conversion ratio evaluation catalyst of Unit Weight catalyst, calculation method is as follows:
Wherein, m1To be greater than 350 DEG C of fraction amounts, m in raw material2It is greater than 350 DEG C of fraction amounts, m in oil to generatecFor catalyst
Loadings.
5 catalyst performance evaluation of table
With the conversion ratio of reference catalyst R-1 for 100%, the relative activity of other catalyst is calculated.The catalyst of evaluation
And its results are shown in Table 5.
The result shows that relative to reference catalyst, the relative activity of catalyst provided by the invention generally improve 10% with
On.
Claims (20)
1. a kind of multi-stage porous hydrocracking catalyst containing Y type molecular sieve, containing carrier and load on this carrier plus hydrogen it is living
Property metal component, the carrier contains Y type molecular sieve and faintly acid sial and silica and aluminium oxide, the hydrogenation activity gold
Category group is selected from the molybdenum of group VIB and/or the nickel and/or cobalt of tungsten and group VIII, which is characterized in that the hole of the catalyst
Distribution meets: the pore volume that bore dia is less than the hole 2nm accounts for the 2% ~ 50% of catalyst total pore volume, and bore dia is the hole 2 ~ 100nm
Pore volume accounts for the 20% ~ 85% of catalyst total pore volume, and the pore volume that bore dia is greater than the hole 100nm accounts for the 3% of catalyst total pore volume
~70%。
2. catalyst according to claim 1, which is characterized in that the pore size distribution of the catalyst meets: bore dia is less than
The pore volume in the hole 2nm accounts for the 4% ~ 21% of catalyst total pore volume, and bore dia is that the pore volume in the hole 2 ~ 100nm accounts for the total hole body of catalyst
Long-pending 20% ~ 85%, the pore volume that bore dia is greater than the hole 100nm account for the 4% ~ 60% of catalyst total pore volume.
3. catalyst according to claim 1, which is characterized in that the Y type molecular sieve be selected from HY, REY, PY, USY,
PUSY；The aluminium oxide is gama-alumina.
4. catalyst according to claim 3, which is characterized in that the Y type molecular sieve is selected from USY, PUSY.
5. catalyst according to claim 1 or 3, which is characterized in that the lattice constant of the Y type molecular sieve be 2.460 ~
2.430, specific surface area is 550 ~ 700 meters2/ gram, 0.30 ~ 0.45 ml/g of Kong Rongwei.
6. catalyst according to claim 1, which is characterized in that on the basis of the carrier, the Y type molecular sieve contains
Amount is 3 ~ 70 weight %, and the content of aluminium oxide is 10 ~ 85 weight %, and faintly acid sial content is 5 ~ 60 weight %, the content of silica
For 4 ~ 30 weight %.
7. catalyst according to claim 5, which is characterized in that on the basis of the carrier, the Y type molecular sieve contains
Amount is 5 ~ 60 weight %, and the content of aluminium oxide is 15 ~ 60 weight %, and faintly acid sial content is 5 ~ 60 weight %.
8. according to claim 1 or catalyst described in 6 any one, which is characterized in that the precursor of the silica is selected from
One of silica solution, the Silica hydrogel that loss on ignition is 0 ~ 60 weight %, White Carbon black, superfine silicon dioxide are several, are with carrier
Benchmark, silica content are 5 ~ 25 weight %.
9. catalyst according to claim 1, which is characterized in that on the basis of catalyst, carrier in the catalyst
Content is 45 ~ 85 weight %, and the content of the nickel and/or cobalt in terms of oxide is 1 ~ 15 weight %, in terms of oxide described in
The content of molybdenum and/or tungsten is 5 ~ 40 weight %.
10. catalyst according to claim 8, which is characterized in that on the basis of catalyst, carrier in the catalyst
Content is 60 ~ 80 weight %, and the content of the nickel and/or cobalt in terms of oxide is 2 ~ 10 weight %, in terms of oxide described in
The content of molybdenum and/or tungsten is 10 ~ 35 weight %.
11. catalyst according to claim 1, which is characterized in that contain organic additive in the catalyst, described has
Machine additive is selected from one or more of oxygen containing organic matter and/or nitrogenous organic matter, described to urge on the basis of catalyst
The content of organic additive is 2 ~ 20 weight % in agent.
12. catalyst according to claim 11, which is characterized in that the oxygen containing organic matter is selected from Organic Alcohol, organic
One or more of acid, nitrogenous organic matter are selected from one or more of organic amine, organic ammonium salt.
13. catalyst according to claim 11, which is characterized in that the oxygen containing organic matter is selected from ethylene glycol, the third three
Alcohol, the polyethylene glycol that relative molecular mass is 200 ~ 1500, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, three second of amino
One or more of acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid；Nitrogenous organic matter is selected from second
One of diamines, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, nitrilotriacetic acid, EDTA and its ammonium salt or
It is several.
14. catalyst according to claim 1, which is characterized in that the preparation method of the carrier includes the following steps:
(1) Y type molecular sieve is mixed with faintly acid sial, boehmite, silica predecessor, peptizing agent, lubricant and water, is obtained
A kind of mixture, the dosage of each component make the amount of peptizing agent substance and powder weight ratio 0.28 × 10 in the mixture-4~
4.8×10-4Mol/g, the ratio between weight and the amount of peptizing agent substance of water are 2.0 × 103~30×103G/mol, the powder weight
Amount is the sum of the Y type molecular sieve, boehmite and faintly acid aluminum weight, and the amount of the peptizing agent substance refers to described
H proton molal quantity is measured in peptizing agent；The lubricant is one of sesbania powder, graphite or two kinds, is with powder weight
Benchmark, lubricant content in powder is 1 ~ 9 weight %；(2) the mixture kneading that obtains step (1), molding, drying
And roast, obtain carrier.
15. catalyst according to claim 14, which is characterized in that the boehmite includes PB1, with X-ray diffraction
Characterization, the κ 1 and κ 2 of the PB1 meet 1 < of < κ 1≤3 and 1 κ 2≤3, wherein 1=h2/h1 of κ, κ 2=h3/h2, h1, h2 and h3 point
It Wei be not 24 at 2 angles θ in the x-ray diffraction spectra of PB1o~30o、35o~41oWith 46o~52oThree diffraction maximums peak height.
16. catalyst according to claim 15, which is characterized in that with X-ray diffraction characterization, the κ 1 of the PB1 is 1.2 ~
2.3 κ 2 is 1.02 ~ 1.4.
17. catalyst according to claim 15, 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.
18. catalyst according to claim 16, 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.
19. catalyst according to claim 14, which is characterized in that the dosage of each component makes described in the step (1)
The amount and powder weight ratio of peptizing agent substance in mixture are 0.7 × 10-4~4.0×10-4Mol/g, the weight and glue of water
The ratio between amount of vehicle substance is 2.0 × 103~15×103g/mol。
20. application of described in any item catalyst in hydrocarbon ils processing according to claim 1 ~ 18.
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| CN109847790B (en) * | 2017-11-30 | 2020-09-04 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application of catalyst in ethylene-butylene disproportionation reaction |
| 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 |
| CN112058304B (en) * | 2019-11-20 | 2023-04-25 | 榆林学院 | Dual-function catalyst capable of adjusting solid acidity, preparation method and application thereof |
| 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 |
| CN114433177B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and method for producing low BMCI value tail oil and high-yield aviation kerosene |
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