CN105618122B - A kind of anti-nitrogen hydrocracking catalyst and preparation method thereof - Google Patents
A kind of anti-nitrogen hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of anti-nitrogen hydrocracking catalyst and preparation method thereof, with overall catalyst weight gauge, including following component：Silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal is calculated as 15% ~ 45% with metal oxide；Mass percent of the described modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, and surplus is amorphous silica-alumina and/or aluminum oxide；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio is 8 ~ 30, and wherein superficial layer silica alumina ratio is 20 ~ 80, and superficial layer silica alumina ratio is higher than body phase silica alumina ratio；600 ~ 800m of modified Y molecular sieve specific surface area2/g；0.40 ~ 0.70ml/g of pore volume；Infrared 0.3 ~ 1.5mmol/g of acid content；Relative crystallinity 70 ~ 110%.Hydrocracking catalyst of the present invention has good reactivity and anti-nitrogen ability.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, more particularly to a kind of anti-nitrogen ability adding by force
Hydrogen Cracking catalyst and preparation method thereof.
Background technology
Hydrocracking technology has strong adaptability to raw material, production operation and the big, good product quality of products scheme flexibility etc.
Feature, can feed various heavy inferiors high-quality jet fuel, diesel oil, the lube basestocks for being converted into market in urgent need
And chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern times oil refining and petro chemical industry are most important heavy
One of oily deep processing technique, at home and abroad obtains increasingly extensive application.The core of hydrocracking process is to be hydrocracked to urge
Agent.Hydrocracking catalyst is typical bifunctional catalyst, with hydrogenation and cracking dual-use function.Wherein hydrogenating function leads to
The sulphided state form for often having W, Mo, Ni isoreactivity metal is provided, and cracking function is then provided by molecular sieve, at present, is hydrocracked
The most widely used process is modified Y molecular sieve, but because the property of acidic zeolite carrier causes it special to nitride
Sensitivity, nitride is readily adsorbed in molecular sieve surface and causes molecular sieve to be poisoned, therefore activity is substantially reduced, in the industrial production
It is difficult to operation steady in a long-term.Also, with the increase of sour density on molecular sieve, the anti-nitrogen ability of catalyst is remarkably decreased.For this
One problem, conventional method is by carrying out acid site on dealuminzation or dealumination complement silicon processing reduction molecular sieve to Y molecular sieve at present
The method of quantity is solved, but this method processing procedure is inside and outside whole molecular sieve while carrying out dealuminzation, therefore, is being carried
While the silica alumina ratio of macromolecule sieve, because acid centre is reduced, its activity is greatly reduced.So, resist in raising catalyst
Insoluble contradiction is there is between nitrogen ability and holding hydrogenation cracking activity, conventional molecular sieve modified process is difficult simultaneously
Take into account the two problems.
CN200710158784.0 discloses a kind of hydrocracking catalyst containing Y molecular sieve and preparation method thereof, the hair
Bright middle Y type molecular sieve is to be handled to obtain after hydro-thermal process with the mixed aqueous solution of aluminium salt and acid, and obtained catalyst activity is higher,
But resistance to nitrogen ability is poor.
CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, prepared by the invention
Hydrocracking catalyst has higher resistance to nitrogen ability still, and cracking activity is relatively low.
CN98114489.6 discloses a kind of hydrocracking catalyst of nitrogen-resistant type multiferous middle oil, for heavy distillate one
Section serial hydrocracking produces a large amount of intermediate oils, and cracking zone feeds nitrogen content up to 100 μ g/g, but the catalyst activity
It is poor.
The content of the invention
In view of the shortcomings of the prior art, the present invention carries a kind of anti-nitrogen hydrocracking catalyst and preparation method thereof, the present invention
Hydrocracking catalyst has good reactivity and anti-nitrogen ability.
The anti-nitrogen hydrocracking catalyst of the present invention, with overall catalyst weight gauge, including following component：Containing modified Y molecules
The silica-alumina supports 55% ~ 85% of sieve, active metal is calculated as 15% ~ 45% with metal oxide；Described active metal is selected from element week
Group VIII and/or vib metals element in phase table, group VIII active metal can be Ni and/or Co, vib
Active metal can be W and/or Mo, and group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~
40%, in terms of metal oxide；
Mass percent of the described modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, and surplus is
Amorphous silica-alumina and/or aluminum oxide；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio（Described in text
Silica alumina ratio be SiO2/Al2O3Mol ratio）For 8 ~ 30, wherein superficial layer silica alumina ratio 20 ~ 80, preferably 30 ~ 60, superficial layer silica alumina ratio
Higher than body phase silica alumina ratio 20 ~ 70, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness range, it is excellent
10 ~ 200nm, more preferably 50 ~ 190nm are selected, superficial layer is primary in Y molecular sieve crystal grain before modified；Sodium oxide molybdena weight/mass percentage composition
Less than 1.0%, preferably smaller than 0.5%；600 ~ 800m of modified Y molecular sieve specific surface area2/ g, 0.40 ~ 0.70ml/g of pore volume；Meleic acid
0.3 ~ 1.5mmol/g of content, preferably 0.4 ~ 1.2mmol/g；Relative crystallinity 70 ~ 110%.
The specific surface area of the catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
In hydrocracking catalyst of the present invention, the preparation method of described modified Y molecular sieve, including following content：
（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；
（2）To step（1）In obtained ammonium exchange after Y molecular sieve carry out hydro-thermal process；
（3）To step（2）Obtained Y molecular sieve carries out low concentration acid treatment；
（4）To step（3）The Y molecular sieve drying process of gained；
（5）Step（4）Y molecular sieve after drying process is fully contacted with gaseous state or liquid unsaturated olefin, then containing
Carbon deposit reaction is carried out in oxygen atmosphere；
（6）By step（5）The carbon deposit Y molecular sieve quick high-temp calcination process of preparation；
（7）By step（6）Y molecular sieve after obtained roasting carries out sour dealumination treatment；
（8）Step（7）Y molecular sieve through sour dealumination treatment carries out processing of making charcoal, obtains modified Y molecules after filtering, drying
Sieve.
Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution using NaY zeolite, 60 ~
At 120 DEG C, at preferably 60 ~ 90 DEG C, exchange 1 ~ 3 hour, exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O contains
Amount is less than 3.0%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt be ammonium chloride,
One or more in ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0
~3.0 mol/L。
Step（2）The hydrothermal treatment process is the hydro-thermal process bar in itself vapor or under conditions of being passed through vapor
Part is：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and processing time is 1.0 ~ 6.0 hours.
Step（3）The acid used during the low concentration acid treatment is inorganic acid and/or organic acid, selected from sulfuric acid, salt
One or more in acid, nitric acid, citric acid, oxalic acid or acetic acid；The concentration of inorganic acid and/or organic acid is with H+It is calculated as 0.1 ~
0.7mol/L, preferably 0.2 ~ 0.5mol/L.The liquid/solid mass ratio of low concentration acid treatment process is generally 3:1~30:1；Processing
30 ~ 80 DEG C of temperature；Processing time is 0.5 ~ 3 hour.
Step（4）Described drying temperature is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
Step（5）Described unsaturated olefin is alkene, the alkadienes of the positive structure that charcoal atomicity is 2 ~ 10 or isomery；Wherein
Described unsaturated olefin is fully contacted with molecular sieve refers to that gaseous state or liquid unsaturated olefin are diffused into inside molecular sieve；When
During using gaseous state unsaturated olefin, gaseous state unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure；Time of contact
0.1 ~ 2 hour；When using liquid unsaturated hydrocarbons, liquid unsaturated olefin is with molecular sieve contact conditions：Pressure 0.1 ~
1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve answers thorough impregnation in liquefied olefines.Described alkene and molecular sieve are abundant
Contact is typically carried out at normal temperatures, and described unsaturated hydrocarbons state phase is phase under normal temperature.
Step（5）Described oxygen-containing atmosphere is air, the mixture or oxygen of oxygen and nitrogen and the mixing of inert gas
One kind in thing, the volume fraction of oxygen in the gas phase is 10% ~ 100%, preferably air；Carbon deposit reaction condition is：Reaction temperature
50 ~ 500 DEG C of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.
Step（6）Described quick high-temp roasting condition is：Sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 points
Clock, preferably 5 ~ 20 minutes.General processing procedure is that the Y molecular sieve of carbon deposit is directly added into the horse for being warming up to sintering temperature in advance
Not it is calcined in stove or other firing equipments.
Step（7）Described in sour dealumination treatment process for conventional method, the i.e. mixing with inorganic acid and/or organic acid it is molten
Liquid process step（6）Obtained Y molecular sieve.Step（6）The inorganic acid or organic acid that acid treatment process is used be sulfuric acid, hydrochloric acid,
The concentration of one or more in nitric acid, citric acid, oxalic acid or acetic acid, inorganic acid and/or organic acid is with H+It is calculated as 0.3 ~ 2mol/
L, preferably 0.6 ~ 1.5mol/L；The liquid/solid mass ratio of sour dealumination treatment process is 3:1~30:1；60 ~ 120 DEG C for the treatment of temperature；Place
The reason time is 0.5 ~ 3 hour.
Step（8）Described treatment conditions of making charcoal are：It is calcined 2 ~ 4 hours, is remained on removing molecular sieve at 400 ~ 600 DEG C
Carbon deposit.
The preparation method of the anti-nitrogen hydrocracking catalyst of the present invention, including following content：
First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, add dust technology
Extruded moulding after into slurry, is dried, roasting obtains the silica-alumina supports containing modified Y molecular sieve；
2nd, the carrier of step one is impregnated using the maceration extract containing active metal, the carrier after dipping is through drying, roasting
Burn, obtain hydrocracking catalyst；In the inventive method, the concentration of the dust technology described in step one is 3wt% ~ 30wt%；It is described
Drying condition be：Dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
In the inventive method, the liquid-solid ratio of the dipping to step one carrier described in step 2 is 1.5：1~3：1, using this
The mode that saturation known to field impregnates is carried out, in maceration extract the content of group vib metallic compound be calculated as 20 by corresponding oxide ~
60g/100ml, the content of group VIII metallic compound is calculated as metallizing in 3 ~ 20g/100ml, maceration extract by corresponding oxide
The concentration of compound can need to adjust accordingly according to product.
In the inventive method, the described drying condition described in step 2 is：Dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting
Burning condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
Hydrocracking catalyst of the present invention can be applied to high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion etc.
Different hydrocracking reaction processes, general operational requirement(GOR) is：6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature,
0.1 ~ 2.0h of feed volume air speed-1, hydrogen to oil volume ratio is 500：1~2000：1.
The present invention carries out microsection component analyzing come measure and calculation molecular sieve surface using transmission electron microscope X-ray electronic spectroscopy
Layer and body phase silica alumina ratio.
The present invention that is, first in air atmosphere, makes to be adsorbed in by being modified Y molecular sieve processing under heating condition
The unsaturated hydrocarbons such as alkene, alkadienes on Y molecular sieve abundant carbon deposit inside and outside molecular sieve, then, is gone by quick high-temp roasting
Except carbon deposit on molecular sieve surface, the aluminium position inside molecular sieve is by carbon deposit covering protection, and follow-up acid dealumination treatment process is main outside
Carried out on surface, it is acid-treated after, then high-temperature roasting removes the carbon deposit of molecular sieve internal residual, recovers the acidity inside molecular sieve
Point position.The inventive method carries out sour dealumination treatment to Y molecular sieve outer surface by selectivity, improves Y molecular sieve outer surfaces
Silica alumina ratio, can keep close anti-nitrogen ability compared to hydrocracking catalyst prepared by conventional method modified molecular screen
In the case of improve catalyst reaction activity or it is identical activity on the premise of improve hydrocracking catalyst anti-nitrogen ability.This
Outside, it is selective to Y molecular sieve outer surface dealumination treatment, the secondary hole number of molecular sieve outer surface is added, is conducive to macromolecular
Diffusion of the raw material in the haptoreaction of molecular sieve surface and a pyrolysis product, it is to avoid excessive second pyrolysis occurs, and improves liquid
Yield.
Brief description of the drawings
Fig. 1 is the transmission electron microscope of modified Y molecular sieve prepared by embodiment 3（TEM）Photo.
Embodiment
Below by embodiment, the present invention is further described, but is not so limited the present invention.
Embodiment 1
Molecular sieve modified processing procedure：
（1）The former powder 200g of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 0.5mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.5%；
（2）To step（1）Obtained Y molecular sieve is at 540 DEG C, hydro-thermal process 2 hours under 0.1Mpa；
（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 and 0.3mol/L citric acid solution（Concentration is with H+Meter）
300ml is mixed, and then heats to 40 DEG C, isothermal reaction 2 hours；
（4）Step（3）The drying 8 hours of 150 DEG C of gained molecular sieve；
（5）Take step（4）The molecular sieve of gained is positioned in the closed container full of butylene atmosphere, control pressure 0.3MPa
Fully contact 20 minutes, then, is heated 15 hours in air atmosphere at 200 DEG C；
（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 450 DEG C of Muffle furnace, is calcined 10 minutes；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 10:1 and concentration 0.6mol/L hydrochloric acid solution（Concentration is with H+
Meter）Mix, constant temperature is handled 2 hours at 80 DEG C；
（8）Through step（7）After Y molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering is Y-1.
It is 40, molecule that Y-1 molecular sieve transmission electron microscope EDAX results, which determine its outer surface to the silica alumina ratio of 80nm thickness,
The silica alumina ratio of sieve nest phase is 10.XRD analysis result shows that its lattice constant is 2.448nm, relative crystallinity 90%, specific surface area
740m2/ g, pore volume 0.45ml/g, it is 0.95mmol/g that infrared analysis result, which determines Y-1 meleic acids amount,.
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 430g and nickel nitrate 440g is taken to configure 1000ml leachings after being dissolved in water
Active metal is with WO in stain solution, gained dipping solution3It is respectively 36g/100ml and 11g/100ml with NiO cubages, it is molten
Liquid numbering RY-1；
（2）Y-1 60g are taken to be mixed with 40g macroporous aluminium oxides, addition 4g/100ml dust technologies are mixed in a mixer to roll
To extrudable shape, extruded moulding obtains carrier T-1 on banded extruder；
（3）Take T-1 60g to add 120ml RY-1 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast
Burn 3 hours, obtain hydrocracking catalyst, numbering is Cat-1.
Embodiment 2
Molecular sieve modified processing procedure：
（1）The former powder of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 0.8mol/L with concentration is according to liquid-solid ratio 3:1
Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.0%.
（2）To step（1）560 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1Mpa；
（3）Step（2）Sieve is according to liquid-solid ratio 8:1 and 0.5mol/L citric acid solution（Concentration is with H+Meter）400ml is mixed,
Then heat to 50 DEG C, isothermal reaction 2 hours；
（4）Step（3）The drying 4 hours of 200 DEG C of gained molecular sieve；
（5）Take heptene soaking step（4）The molecular sieve of gained 4 hours, then in air atmosphere, 200 DEG C of heating 22 are small
When；
（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 500 DEG C of Muffle furnace, is calcined 12 minutes；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 7:1 and H+Concentration is mixed for 1.0mol/L hydrochloric acid mixed solution
Close, 95 DEG C are handled 2 hours；
（8）Through step（7）After Y molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering is Y-2.
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml leachings after being dissolved in water
Active metal is with WO in stain solution, gained dipping solution3It is respectively 40g/100ml and 12g/100ml with NiO cubages, it is molten
Liquid numbering RY-2；
（2）Take Y-230g to be mixed with 70g macroporous aluminium oxides, add 4g/100ml dust technologies mix in a mixer roll to
Extrudable shape, extruded moulding obtains carrier T-2 on banded extruder；
（3）Take T-2 60g to add 120ml RY-2 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast
Burn 3 hours, obtain hydrocracking catalyst, numbering is Cat-2.
It is 60, molecule that Y-2 molecular sieve transmission electron microscope EDAX results, which determine its outer surface to the silica alumina ratio of 120nm thickness,
The silica alumina ratio of sieve nest phase is 13.XRD analysis result shows that its lattice constant is 2.434nm, relative crystallinity 87%, specific surface area
680m2/ g, pore volume 0.50ml/g, it is 0.72mmol/g that infrared analysis result, which determines Y-2 meleic acids amount,.
Embodiment 3
Molecular sieve modified processing procedure：
（1）The former powder of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 0.5mol/L with concentration is according to liquid-solid ratio 5:1
Mixing, 90 DEG C exchange 1.5 hours, repeat this process 2 times, and Na contents are calculated as 1.8% with Na2O in the Y molecular sieve after exchange.
（2）To step（1）550 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1Mpa；
（3）Step（2）Sieve is according to liquid-solid ratio 8:1 and 0.5mol/L citric acid solution（Concentration is with H+Meter）400ml is mixed,
Then heat to 60 DEG C, isothermal reaction 2 hours；
（4）Step（3）The dry 2h of 250 DEG C of gained molecular sieve；
（5）Take heptene soaking step（4）The molecular sieve of gained 4 hours, then in air atmosphere, 200 DEG C of heating 10 are small
When；
（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 500 DEG C of Muffle furnace, is calcined 30 minutes；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 7:1 and H+Concentration is mixed for 1.0mol/L hydrochloric acid mixed solution
Close, 80 DEG C are handled 2 hours；
（8）Through step（7）After Y molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering is Y-3.
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml leachings after being dissolved in water
Active metal is with WO in stain solution, gained dipping solution3It is respectively 40g/100ml and 12g/100ml with NiO cubages, it is molten
Liquid numbering RY-3；
（2）Y-3 30g are taken to be mixed with 70g macroporous aluminium oxides, addition 4g/100ml dust technologies are mixed in a mixer to roll
To extrudable shape, extruded moulding obtains carrier T-3 on banded extruder；
（3）Take T-3 60g to add 120ml RY-3 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast
Burn 3 hours, obtain hydrocracking catalyst, numbering is Cat-3.
It is 56, molecule that Y-3 molecular sieve transmission electron microscope EDAX results, which determine its outer surface to the silica alumina ratio of 190nm thickness,
The silica alumina ratio of sieve nest phase is 14.XRD analysis result shows that its lattice constant is 2.433nm, relative crystallinity 85%, specific surface area
680m2/ g, pore volume 0.52ml/g, it is 0.69mmol/g that infrared analysis result, which determines Y-3 meleic acids amount,.
Embodiment 4
Molecular sieve modified processing procedure：
（1）The former powder 200g of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 0.5mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 75 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.2%；
（2）To step（1）Obtained Y molecular sieve is at 550 DEG C, hydro-thermal process 2 hours under 0.1Mpa；
（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 and 0.3mol/L citric acid solution（Concentration is with H+Meter）
300ml is mixed, and then heats to 40 DEG C, isothermal reaction 2 hours；
（4）Step（3）The dry 9h of 100 DEG C of gained molecular sieve；
（5）Take hexadiene soaking step（4）The molecular sieve of gained 2 hours, then 150 DEG C of heating 15 are small in air atmosphere
When；
（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 400 DEG C of Muffle furnace, is calcined 10 minutes；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 15:1 and concentration 0.6mol/L hydrochloric acid solution（Concentration is with H+
Meter）Mix, constant temperature is handled 2 hours at 90 DEG C；
（8）Through step（7）After Y molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering is Y-4
It is 43, molecule that Y-4 molecular sieve transmission electron microscope EDAX results, which determine its outer surface to the silica alumina ratio of 50nm thickness,
The silica alumina ratio of sieve nest phase is 10.5.XRD analysis result shows that its lattice constant is 2.445nm, and relative crystallinity 89% compares surface
Product 720m2/ g, pore volume 0.47ml/g, it is 0.92mmol/g that infrared analysis result, which determines Y-4 meleic acids amount,.
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 430g and nickel nitrate 440g is taken to configure 1000ml leachings after being dissolved in water
Active metal is with WO in stain solution, gained dipping solution3It is respectively 36g/100ml and 11g/100ml with NiO cubages, it is molten
Liquid numbering RY-4；
（2）Y-4 60g are taken to be mixed with 40g macroporous aluminium oxides, addition 4g/100ml dust technologies are mixed in a mixer to roll
To extrudable shape, extruded moulding obtains carrier T-4 on banded extruder；
（3）Take T-4 60g to add 120ml RY-1 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast
Burn 3 hours, obtain hydrocracking catalyst, numbering is Cat-4.
Comparative example 1
Comparative example 1 is counted as BCat-1, in its catalyst formulation using a kind of wide variety of hydrocracking catalyst of industry
In addition to modified Y molecular sieve, remaining composition and method for preparing catalyst are same as Example 1, and catalyst BCat-1 uses modified Y
Molecular sieve property is as follows：The silica alumina ratio of molecular sieve is 11.XRD analysis result shows that its lattice constant is 2.446nm, relative crystallization
Degree 89%, pore volume 0.42ml/g, specific surface area 720m2/ g, meleic acid amount is 1.0mmol/g.
Comparative example 2
Comparative example 2 is counted as BCat-2, in its catalyst formulation using a kind of wide variety of hydrocracking catalyst of industry
In addition to modified Y molecular sieve, remaining composition and method for preparing catalyst are same as Example 2, and catalyst BCat-2 uses modified Y
Molecular sieve property is as follows：The silica alumina ratio of molecular sieve is 13.XRD analysis result shows that its lattice constant is 2.433nm, relative crystallization
Degree 87%.Pore volume 0.46ml/g, specific surface area 700m2/ g, meleic acid amount is 0.68mmol/g.
Embodiment 5
The reactivity worth of catalyst is prepared in order to investigate embodiment and comparative example, catalyst is carried out on midget plant
Evaluation test, evaluating apparatus is connected once by flow using single hop, an anti-filling it is industrial it is wide variety of be hydrocracked it is pre-
Handle catalyst FF-36（Sinopec Fushun Petrochemical Research Institute）, two instead load according to embodiment 1 ~ 4 and comparative example respectively
1 ~ 2 hydrocracking catalyst prepared, feedstock property, appreciation condition and evaluation result are listed in 1 ~ table of table 5.
The raw material oil nature of table 1.
The appreciation condition of table 2.
The evaluation result of table 3.
The embodiment 1 of table 4 and the catalyst stability contrast test of comparative example 1.
The embodiment 2 of table 5 and the catalyst stability contrast test of comparative example 2.
Contrast test of the embodiment 1 ~ 2 with the catalyst of comparative example 1 ~ 2 on evaluating apparatus shows, using the inventive method system
Standby catalyst is distributed with comparative example catalyst prod and property is suitable, and anti-nitrogen ability is stronger, contains generating oily nitrogen in refining stage
When being operated under conditions of amount 50ppm, the reactivity of embodiment 1 and the catalyst of embodiment 2 is higher, and prolonging with the duration of runs
Long this advantage is more obvious.
Claims (19)
1. a kind of anti-nitrogen hydrocracking catalyst, it is characterised in that：With overall catalyst weight gauge, including following component：Containing modified Y
The silica-alumina supports 55% ~ 85% of molecular sieve, active metal is calculated as 15% ~ 45% with metal oxide；Described active metal is selected from member
The one or more in group VIII and/or vib metals element in plain periodic table；Described modified Y molecular sieve is in silicon
Mass percent in alumina supporter is 15% ~ 90%, and surplus is amorphous silica-alumina and/or aluminum oxide；Modified Y molecular sieve lattice constant
For 2.425 ~ 2.455nm；Body phase silica alumina ratio is 8 ~ 30, and wherein superficial layer silica alumina ratio is 20 ~ 80, and superficial layer silica alumina ratio is than body phase silicon
Aluminum ratio is high by 20 ~ 70, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness range, superficial layer is primary
In Y molecular sieve before modified；600 ~ 800m of modified Y molecular sieve specific surface area2/g；0.40 ~ 0.70mL/g of pore volume；Infrared acid content
0.3~1.5mmol/g；Relative crystallinity 70 ~ 110%；The silica alumina ratio is SiO2/Al2O3Mol ratio.
2. according to the catalyst described in claim 1, it is characterised in that：The superficial layer of described modified Y molecular sieve refers to molecular sieve
Outer surface to 10 ~ 200nm of inside thickness range.
3. according to the catalyst described in claim 1, it is characterised in that：The superficial layer of described modified Y molecular sieve refers to molecular sieve
Outer surface to 50 ~ 190nm of inside thickness range.
4. according to the catalyst described in claim 1, it is characterised in that：The specific surface area of catalyst is 200 ~ 400m2/ g, pore volume
For 0.2 ~ 0.5mL/g.
5. according to the catalyst described in claim 1, it is characterised in that：Group VIII active metal is Ni and/or Co, VIB
Race's active metal is W and/or Mo, and group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~
40%, in terms of metal oxide.
6. according to the catalyst described in claim 1, it is characterised in that：The preparation method of described modified Y molecular sieve, including such as
Lower content：（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；（2）To step（1）In obtain
Y molecular sieve after ammonium is exchanged carries out hydro-thermal process；（3）To step（2）Obtained Y molecular sieve carries out low concentration acid treatment；（4）It is right
Step（3）The Y molecular sieve drying process of gained；（5）Step（4）Y molecular sieve and gaseous state or liquid after drying process is unsaturated
Alkene is fully contacted, and carbon deposit reaction is then carried out in oxygen-containing atmosphere；（6）By step（5）The carbon deposit Y molecular sieve of preparation is quickly high
Warm calcination process；（7）By step（6）Y molecular sieve after obtained roasting carries out sour dealumination treatment；（8）Step（7）Through sour dealuminzation
The Y molecular sieve of processing carries out processing of making charcoal, obtains modified Y molecular sieve after filtering, drying.
7. according to the catalyst described in claim 6, it is characterised in that：Step（2）The hydrothermal treatment process is in itself water
Steam is passed through under conditions of vapor, and hydrothermal conditions are：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, place
The reason time is 1.0 ~ 6.0 hours.
8. according to the catalyst described in claim 6, it is characterised in that：Step（3）Used during the low concentration acid treatment
Acid be inorganic acid and/or organic acid, the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid；Nothing
The concentration of machine acid and/or organic acid is with H+It is calculated as 0.1 ~ 0.7mol/L；The liquid/solid mass ratio of low concentration acid treatment process is 3:
1~30:1,30 ~ 80 DEG C for the treatment of temperature, processing time is 0.5 ~ 3 hour.
9. according to the catalyst described in claim 6, it is characterised in that：Step（4）Described drying temperature is 90 ~ 300 DEG C, is done
The dry time is 2 ~ 10 hours.
10. according to the catalyst described in claim 6, it is characterised in that：Step（5）Described unsaturated olefin is charcoal atomicity
Alkene, the alkadienes of positive structure or isomery for 2 ~ 10.
11. according to the catalyst described in claim 6 or 10, it is characterised in that：Step（5）The gaseous state unsaturated olefin is with dividing
Son sieves contact conditions：0.1 ~ 1.0MPa of pressure；0.1 ~ 2 hour time of contact.
12. according to the catalyst described in claim 6 or 10, it is characterised in that：Step（5）The liquid unsaturated olefin is with dividing
Son sieves contact conditions：0.1 ~ 1.0MPa of pressure, 0.5 ~ 4 hour time of contact, molecular sieve thorough impregnation is in liquefied olefines.
13. according to the catalyst described in claim 6, it is characterised in that：Step（5）Described oxygen-containing atmosphere is air, oxygen
With one kind in the mixture or oxygen of nitrogen and the mixture of inert gas, the volume fraction of oxygen in the gas phase be 10% ~
100%。
14. according to the catalyst described in claim 6, it is characterised in that：Step（5）Described carbon deposit reaction condition is：Reaction
50 ~ 500 DEG C of temperature, the reaction time is 1 ~ 50 hour.
15. according to the catalyst described in claim 6, it is characterised in that：Step（6）Described quick high-temp roasting condition is：
Sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 minutes.
16. according to the catalyst described in claim 6, it is characterised in that：Step（7）Inorganic acid or have that acid treatment process is used
Machine acid is the concentration of the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, inorganic acid and/or organic acid
With H+It is calculated as 0.3 ~ 2mol/L；The liquid/solid mass ratio of sour dealumination treatment process is 3:1~30:1；60 ~ 120 DEG C for the treatment of temperature, place
The reason time is 0.5 ~ 3 hour.
17. according to the catalyst described in claim 6, it is characterised in that：Step（8）Described treatment conditions of making charcoal are：400~
It is calcined 2 ~ 4 hours at 600 DEG C.
18. the preparation method of the anti-nitrogen hydrocracking catalyst described in a kind of claim 1, it is characterised in that in following
Hold：First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, add dust technology into slurry
Extruded moulding, dries 1 ~ 5 hour at 80 ~ 120 DEG C, is then calcined 1 ~ 5 hour at 400 ~ 700 DEG C afterwards, obtains containing modified Y points
The silica-alumina supports of son sieve；2nd, the carrier of step one is impregnated using the maceration extract containing active metal, the carrier after dipping exists
Dried at 90 ~ 150 DEG C 2 ~ 8 hours, be then calcined 1 ~ 5 hour at 400 ~ 700 DEG C, obtain hydrocracking catalyst.
19. a kind of hydrocracking catalyst described in claim 1 adds in high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil
Application during the hydrocracking reaction of hydrogen conversion, it is characterised in that：Operating condition is：6.0 ~ 20.0Mpa of reaction pressure, instead
Answer 350 ~ 420 DEG C of temperature, 0.1 ~ 2.0h of feed volume air speed-1, hydrogen to oil volume ratio is 500：1~2000：1.
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|---|---|---|---|---|
| US5030780A (en) * | 1990-07-26 | 1991-07-09 | Union Oil Company Of California | Aromatic saturation process with a silica-alumina and zeolite catalyst |
| CN101134567A (en) * | 2007-07-26 | 2008-03-05 | 复旦大学 | High-stability large aperture ordered meso-porous carbon material and preparation method thereof |
| CN101450319A (en) * | 2007-12-04 | 2009-06-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst for moderate oil and preparation thereof |
| CN101543783A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
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| CA2601982C (en) * | 2004-12-17 | 2013-04-30 | Haldor Topsoe A/S | Two-catalyst hydrocracking process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030780A (en) * | 1990-07-26 | 1991-07-09 | Union Oil Company Of California | Aromatic saturation process with a silica-alumina and zeolite catalyst |
| CN101134567A (en) * | 2007-07-26 | 2008-03-05 | 复旦大学 | High-stability large aperture ordered meso-porous carbon material and preparation method thereof |
| CN101450319A (en) * | 2007-12-04 | 2009-06-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst for moderate oil and preparation thereof |
| CN101543783A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
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