CN105618117B - The preparation method of hydrocracking catalyst - Google Patents
The preparation method of hydrocracking catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of hydrocracking catalyst, including following content：Modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, dust technology is added to obtain the silica-alumina supports containing modified Y molecular sieve into extruded moulding after slurry, dry, roasting, then impregnate active component, dry, roasting, obtain hydrocracking catalyst；Wherein described modified Y molecular sieve body phase silica alumina ratio is 9 ~ 50, wherein superficial layer SiO2/Al2O3Silica alumina ratio 30 ~ 120, superficial layer silica alumina ratio are higher than body phase silica alumina ratio；650 ~ 900m of modified Y molecular sieve specific surface area2/ g, 0.30 ~ 0.50ml/g of pore volume.Hydrocracking catalyst of the present invention has good reactivity and anti-nitrogen ability, has broad application prospects during the hydrocracking reactions such as high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst.
Background technology
Hydrocracking technology has strong adaptability to raw material, production operation and the big, good product quality of products scheme flexibility etc.
Feature, various heavy inferiors can be fed to 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, has 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 make it that it is special to nitride
Sensitivity, nitride are readily adsorbed in molecular sieve surface and cause molecular sieve to be poisoned, therefore activity substantially reduces, in the industrial production
It is difficult to run steadily in the 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 to reduce acid site on molecular sieve by carrying out dealuminzation or dealumination complement silicon processing 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 carries out dealuminzation, therefore, carrying
While the silica alumina ratio of macromolecule sieve, because acid centre is reduced, its activity is greatly reduced.So, resist in raising catalyst
There is insoluble contradiction 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 obtained with after the mixed aqueous solution of aluminium salt and acid processing hydro-thermal process, 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 hydrocracking catalyst and preparation method thereof, present invention hydrogenation
Cracking catalyst has good reactivity and anti-nitrogen ability.
The preparation method of the 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, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；The concentration of wherein described dust technology is
3wt%~30wt%；Described drying condition is：Dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：At 400 ~ 700 DEG C
Roasting 1 ~ 5 hour；
2nd, the carrier of step 1 is impregnated using the maceration extract containing active metal, the carrier after dipping is through drying, roasting
Burn, obtain hydrocracking catalyst；The solid mass ratio of liquid wherein impregnated is 1.5：1~3：1, soaked using saturation well known in the art
The mode of stain is carried out, and the content of group vib metallic compound is calculated as 20 ~ 60g/100ml, VIII by corresponding oxide in maceration extract
The content of race's metallic compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can root in maceration extract
Need to adjust accordingly according to product；Wherein described drying condition is：Dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition
For：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C；
Wherein modified Y molecular sieve lattice constant is 2.420 ~ 2.455nm；Molecular sieve body phase silica alumina ratio（Specifically described herein
Silica alumina ratio is SiO2/Al2O3Mol ratio）For 9 ~ 50, wherein superficial layer SiO2/Al2O3Silica alumina ratio 30 ~ 120, preferably 50 ~ 100, table
Surface layer silica alumina ratio is higher than body phase silica alumina ratio 20 ~ 90, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness
Scope is spent, preferably 10 ~ 200nm, more preferably 50 ~ 190nm, superficial layer is primary in Y molecular sieve crystal grain, complete with molecular sieve internal cohesion
It is good, molecular sieve internal gutter is not blocked；Sodium oxide molybdena weight/mass percentage composition is less than 1.0%, preferably smaller than 0.5%；Modified Y molecular sieve ratio
650 ~ 900m of surface area2/ g, 0.30 ~ 0.50ml/g of pore volume；Infrared 0.3 ~ 1.0mmol/g of acid content, preferably 0.4 ~ 0.8mmol/
g；Relative crystallinity 90% ~ 130%.
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）Step（1）In obtained ammonium exchange after Y molecular sieve carry out dealumination complement silicon processing
（3）To step（Y molecular sieve after 2 processing carries out hydro-thermal process；
（4）To step（3）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution, is dried；
（5）Step（6）Obtained Y molecular sieve impregnates in organic solvent, then rapid draing；
（6）By step（7）Obtained molecular sieve carries out dealumination complement silicon processing；
（7）Step（6）Y molecular sieve after processing is filtered, dry, roasting, obtains modified Y molecular 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）Described in dealumination complement silicon processing be method well known to those skilled in the art, conventional fluorine can be used
Ammonium silicate dealumination complement silicon method, by step（1）Obtained Y molecular sieve adds water to be made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, so
Afterwards, it is 0.3 ~ 1.2mol/L ammonium fluosilicate aqueous solution to add concentration, is handled 0.5 ~ 2 hour in 50 ~ 80 DEG C；Wherein ammonium fluosilicate
Solution addition needs 4 ~ 10g of pure fluosilicic acid ammonium to count according to every 100g molecular sieves；Other are such as SiCl4Gas phase dealumination complement silicon is also fitted
With.
Step（3）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（4）Aluminium salt used in described aluminium salt processing procedure be one kind in aluminium chloride, aluminum sulfate or aluminum nitrate or
Several, aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and 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 organic solvent be selected from alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene,
One or more in ethylbenzene, impregnation method are impregnated using supersaturation, and dip time is 1 ~ 5h；Drying temperature is 50 ~ 300 DEG C,
It is preferred that drying temperature is higher than the boiling point of organic solvent, drying time is 1 ~ 60 minute, preferably 3 ~ 20 minutes.
Step（6）Described in dealumination complement silicon processing be method well known to those skilled in the art, conventional fluorine can be used
Ammonium silicate dealumination complement silicon method, i.e., first by step（5）Obtained Y molecular sieve adds water to be made into the water sample mixing of liquid-solid ratio 3 ~ 6, then,
It is that 0.8 ~ 2mol/L ammonium fluosilicates aqueous solution is handled 1 ~ 4 hour in 70 ~ 100 DEG C to add concentration.Other are such as SiCl4Gas phase dealuminzation
Silicon is mended to be also suitable.Preferred steps（6）Dealumination complement silicon processing depth is higher than step（2）Dealumination complement silicon processing.
Step（7）Described roasting condition is：It is calcined 2 ~ 4 hours at 400 ~ 600 DEG C.
The hydrocracking catalyst of the present invention, with overall catalyst weight gauge, including following component：Containing modified Y molecular sieve
Silica-alumina supports 55% ~ 85%, active metal 15% ~ 45%, wherein active metal is in terms of metal oxide；Described modified Y molecular sieve
Mass percent in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, and surplus is amorphous silica-alumina and/or aluminum oxide；Institute
Group VIII and/or vib metals element of the active metal stated in the periodic table of elements, group VIII active metal can
To be Ni and/or Co, vib active metal can be W and/or Mo, and group VIII active metallic content is 3% ~ 15%, the
Group vib active metallic content is 10% ~ 40%, in terms of metal oxide；The specific surface area of the catalyst is 200 ~ 400m2/ g,
Pore volume is 0.2 ~ 0.5ml/g.
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) are：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 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.
In the inventive method, by being modified processing to Y molecular sieve, i.e., first in the organic solvent of water is not readily dissolved in
Dipping, be then rapidly heated drying, rapidly removes molecular sieve outer layer organic solvent, organic molten inside molecular sieve so as to remain
Agent, the framework silicon-aluminum inside such molecular sieve are protected, therefore, in follow-up ammonium fluosilicate dealumination complement silicon processing procedure, mainly
Carry out on the outer surface, after ammonium fluosilicate is treated, then conventional drying is carried out to modified Y, is calcined and can remove in molecular sieve
Organic solvent.The inventive method carries out dealumination complement silicon to Y molecular sieve outer surface by selectivity, and selective improves Y points
The silica alumina ratio of son sieve outer surface, it can keep close compared to hydrocracking catalyst prepared by conventional method modified molecular screen
Catalyst reaction activity is improved in the case of anti-nitrogen ability or the anti-of hydrocracking catalyst is improved on the premise of identical activity
Nitrogen ability.
Brief description of the drawings
Fig. 1 is the transmission electron microscope of modified Y molecular sieve prepared by embodiment 1（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 NaY molecular sieve original powder 200g 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）Step（1）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, adding concentration is
0.5mol/L ammonium fluosilicate solution 100ml, 60 DEG C are handled 1.0 hours；
（3）To step（2）550 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 5:1 is stirred with distilled water, then heats to 80 DEG C, is stirring
0.5mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（5）Step（4）The dry 8h of 150 DEG C of gained molecular sieve
（6）Take normal heptane solvent soaking step（5）The molecular sieve of gained 2 hours；
（7）Step（6）Molecular sieve after processing is dried 8 minutes in 130 DEG C；
（8）Step（7）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, adding concentration is
0.8mol/L ammonium fluosilicate solution 200ml, 80 DEG C are handled 2 hours；
（9）Through step（8）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Obtain modified Y molecular sieve, numbering Y-1
It is 58 that Y-1 molecular sieve transmission electron microscope EDAX results, which determine its outer surface to the silica alumina ratio of 80nm thickness, molecule
The silica alumina ratio of sieve nest phase is 15.XRD analysis result shows that its lattice constant is 2.436 nm, relative crystallinity 107%.Pore volume
0.36ml/g, specific surface area 820m2/ g, infrared analysis result measure Y-1 meleic acids amount is 0.70mmol/g.
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
Stain solution, active metal is with WO in 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 mix 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 Cat-1.
Embodiment 2
Molecular sieve modified processing procedure：
（1）The NaY molecular sieve original powder for taking laboratory to prepare, with the ammonium nitrate that concentration is 0.8mol/L according to liquid-solid ratio 3:1
Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are calculated as 2.0% with Na2O in the Y molecular sieve after exchange.
（2）Step（1）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with distilled water, and then, adding concentration is
0.7mol/L ammonium fluosilicate solution 120ml, 70 DEG C are handled 1.0 hours；
（3）To step（2）580 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 6:1 is stirred with distilled water, then heats to 90 DEG C, is stirring
0.8mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（5）Step（4）The dry 4h of 200 DEG C of gained molecular sieve；
（6）Take toluene solvant soaking step（5）The molecular sieve of gained 3 hours；
（7）Step（6）140 DEG C of molecular sieve drying 20 minutes after processing；
（8）Step（7）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, addition concentration is 1mol/L
Ammonium fluosilicate solution 300ml, 95 DEG C are handled 2 hours；
（9）Through step（8）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Obtain modified Y molecular sieve, numbering 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
Stain solution, active metal is with WO in gained dipping solution3It is respectively 40g/100ml and 12g/100ml with NiO cubages, it is molten
Liquid numbering RY-2；
（2）Y-2 30g are taken to be mixed with 70g macroporous aluminium oxides, addition 4g/100ml dust technologies mix in a mixer to 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 Cat-2.
Y-2 molecular sieve transmission electron microscope EDAX results determine its outer surface to 150nm thickness, the silica alumina ratio of superficial layer
80, the silica alumina ratio of molecular sieve body phase is 24.XRD analysis result shows that its lattice constant is 2.429 nm, relative crystallinity 102%,
Pore volume 0.38ml/g, specific surface area 790m2/ g, infrared analysis result measure Y-2 meleic acids amount is 0.46mmol/g.
Embodiment 3
Molecular sieve modified processing procedure：
（1）The NaY molecular sieve original powder for taking laboratory to prepare, with the ammonium nitrate that concentration is 0.8mol/L 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）Step（1）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with distilled water, and then, adding concentration is
0.6mol/L ammonium fluosilicate solution 120ml, 80 DEG C are handled 1.5 hours；
（3）To step（2）580 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 6:1 is stirred with distilled water, then heats to 90 DEG C, is stirring
0.8mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（5）Step（4）The dry 2h of 250 DEG C of gained molecular sieve；
（6）Take xylene solvent soaking step（5）The molecular sieve of gained 4 hours；
（7）Step（6）200 DEG C of molecular sieve drying 17 minutes after processing；
（8）Step（7）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, adding concentration is
0.8mol/L ammonium fluosilicate solution 250ml, 90 DEG C are handled 2 hours；
（9）Through step（8）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Obtain modified Y molecular sieve, numbering 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
Stain solution, active metal is with WO in 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 mix 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 Cat-3.
Y-3 molecular sieve transmission electron microscope EDAX results determine its outer surface to 190nm thickness, the silica alumina ratio of superficial layer
For 76, the silica alumina ratio of molecular sieve body phase is 25.XRD analysis result shows that its lattice constant is 2.428 nm, relative crystallinity
103%, pore volume 0.38ml/g, specific surface area 760m2/ g, infrared analysis result measure Y-3 meleic acids amount is 0.45mmol/g.
Embodiment 4
（1）The NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 0.5mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 65 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 2.6%；
（2）Step（1）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, adding concentration is
0.5mol/L ammonium fluosilicate solution 100ml, 60 DEG C are handled 1.0 hours；
（3）To step（2）520 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 5:1 is stirred with distilled water, then heats to 80 DEG C, is stirring
0.5mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（5）Step（4）The dry 9h of 100 DEG C of gained molecular sieve；
（6）Take normal octane solvent soaking step（5）The molecular sieve of gained 2 hours；
（7）Step（6）Molecular sieve after processing is dried 5 minutes in 150 DEG C；
（8）Step（7）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, adding concentration is
0.8mol/L ammonium fluosilicate solution 150ml, 95 DEG C are handled 2 hours；
（9）Through step（8）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Obtain modified Y molecular sieve, numbering Y-4
It is 62 that Y-4 molecular sieve transmission electron microscope EDAX results, which determine its outer surface to the silica alumina ratio of 60nm thickness, point
The silica alumina ratio of sub- sieve nest phase is 14.XRD analysis result shows that its lattice constant is 2.437 nm, relative crystallinity 107%, pore volume
0.36ml/g, specific surface area 810m2/ g, infrared analysis result measure Y-4 meleic acids amount is 0.72mmol/g.
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
Stain solution, active metal is with WO in 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 mix 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-4 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 Cat-4.
Comparative example 1
Using a kind of wide variety of hydrocracking catalyst of industry, BCat-1 is counted as, except modified Y in its catalyst formulation
Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 1, the Y molecular sieve that catalyst BCat-1 is used
Matter is as follows：Molecular sieve SiO2/Al2O3 Mol ratio is 15.XRD analysis result shows that its lattice constant is 2.438 nm, relative knot
Brilliant degree 95%, pore volume 0.33ml/g, specific surface area 730m2/ g, meleic acid amount are 0.66 mmol/g.
Comparative example 2
Using a kind of wide variety of hydrocracking catalyst of industry, BCat-2 is counted as, except modified Y in its catalyst formulation
Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 2, the Y molecular sieves that catalyst BCat-2 is used
Matter is as follows：Molecular sieve SiO2/Al2O3 Mol ratio 26.XRD analysis result shows that its lattice constant is 2.427nm, relative crystallinity
88%, pore volume 0.38ml/g, specific surface area 680m2/ g, meleic acid amount are 0.48 mmol/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 are 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 100ppm, the reactivity of embodiment 1 and the catalyst of embodiment 2 is higher, and with the duration of runs
It is more obvious to extend this advantage.
Claims (15)
1. a kind of preparation method of hydrocracking catalyst, it is characterised in that including following content：First, by modified Y molecular sieve, nothing
Sizing sial and/or aluminum oxide are well mixed, and are added dust technology into extruded moulding after slurry, are dried, roasting is obtained containing modified Y molecules
The silica-alumina supports of sieve；2nd, the carrier of step 1 is impregnated using the maceration extract containing active metal, the carrier after dipping is through dry
Dry, roasting, obtains hydrocracking catalyst；Modified Y molecular sieve lattice constant wherein described in step 1 for 2.420 ~
2.455nm；Molecular sieve body phase silica alumina ratio is 9 ~ 50, wherein superficial layer SiO2/Al2O3Silica alumina ratio 30 ~ 120, superficial layer silica alumina ratio are high
In body phase silica alumina ratio 20 ~ 90, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness range, surface
Layer is primary in Y molecular sieve crystal grain before modified；650 ~ 900m of modified Y molecular sieve specific surface area2/ g, 0.30 ~ 0.50mL of pore volume/
g；Infrared 0.3 ~ 1.0mmol/g of acid content；Relative crystallinity 90% ~ 130%；Described silica alumina ratio is SiO2/Al2O3Mol ratio；Institute
Group VIII and/or vib metals element of the active metal stated in the periodic table of elements,
With overall catalyst weight gauge, active metal 15% ~ 45%, wherein active metal is in terms of metal oxide；Y points of described modification
Mass percent of the son sieve in silica-alumina supports is 15% ~ 90%.
2. in accordance with the method for claim 1, it is characterised in that：Drying condition described in step 1 is：At 80 ~ 120 DEG C
Dry 1 ~ 5 hour；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C；The liquid stereoplasm wherein impregnated described in step 2
Amount is than being 1.5：1~3：1, carried out by the way of saturation dipping, the content of group vib metallic compound presses corresponding oxygen in maceration extract
Compound is calculated as 20 ~ 60g/100mL, and the content of group VIII metallic compound is calculated as 3 ~ 20g/100mL by corresponding oxide.
3. in accordance with the method for claim 1, it is characterised in that：Drying condition described in step 2 is：At 90 ~ 150 DEG C
Dry 2 ~ 8 hours；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
4. in accordance with the method for claim 1, it is characterised in that：The preparation method of modified Y molecular sieve described in step 1, bag
Include following content：（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；（2）Step（1）In obtain
Ammonium exchange after Y molecular sieve carry out ammonium fluosilicate dealumination complement silicon processing；（3）To step（2）Y molecular sieve after processing enters water-filling
Heat treatment；（4）To step（3）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution, is dried；（5）Step（4）Obtained Y points
Son sieve impregnates in organic solvent, then rapid draing；（6）By step（5）Obtained molecular sieve carries out ammonium fluosilicate dealuminzation benefit
Silicon processing；（7）Step（6）Y molecular sieve after processing is filtered, dry, roasting, obtains modified Y molecular sieve；Step（5）It is described
One or more of the organic solvent in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene or dimethylbenzene, dipping
Mode is impregnated using supersaturation, and dip time is 1 ~ 5 hour.
5. in accordance with the method for claim 4, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：With
NaY zeolite is raw material, wherein SiO in NaY molecular sieve2/Al2O3Mol ratio is 3 ~ 6；Wherein ammonium salt is ammonium chloride, ammonium nitrate, sulphur
One or more in sour ammonium, ammonium acetate or ammonium oxalate, 0.3 ~ 6.0mol/L of ammonium salt aqueous solution concentration；Handed at 60 ~ 120 DEG C
Change, swap time is 1 ~ 3 hour, and exchange times are 1 ~ 4 time.
6. in accordance with the method for claim 4, it is characterised in that：Step（2）Described ammonium fluosilicate dealumination complement silicon process is：
By step（1）Obtained Y molecular sieve adds water to be made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, then, add concentration be 0.3 ~
The 1.2mol/L ammonium fluosilicate aqueous solution, handled 0.5 ~ 2 hour in 50 ~ 80 DEG C；Wherein ammonium fluosilicate solution addition is according to every
100g molecular sieves need 4 ~ 10g of pure fluosilicic acid ammonium to count.
7. in accordance with the method for claim 4, it is characterised in that：Step（3）The hydrothermal treatment process is steamed in itself water
Gas is passed through under conditions of vapor, and hydrothermal conditions are：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, processing
Time is 1.0 ~ 6.0 hours.
8. in accordance with the method for claim 4, it is characterised in that：Step（4）Aluminium salt used in described aluminium salt processing procedure
It is the one or more in aluminium chloride, aluminum sulfate or aluminum nitrate, aluminium salt concentration is 0.05 ~ 2mol/L；Treatment temperature is 50 ~ 120
DEG C, processing time is 0.5 ~ 3 hour.
9. in accordance with the method for claim 4, it is characterised in that：Step（4）Described drying temperature is 90 ~ 300 DEG C, is dried
Time is 2 ~ 10 hours.
10. in accordance with the method for claim 4, it is characterised in that：Step（5）Described drying temperature is 50 ~ 300 DEG C, is done
The dry time is 1 ~ 60 minute.
11. in accordance with the method for claim 4, it is characterised in that：Step（6）Ammonium fluosilicate dealumination complement silicon process is：Will step
Suddenly（5）Obtained Y molecular sieve adds water to be made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, it is 0.8 ~ 2.0mol/ then to add concentration
The L ammonium fluosilicate aqueous solution, handled 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition is according to every 100g molecular sieves
9 ~ 30g of ammonium fluosilicate is needed to count.
12. in accordance with the method for claim 4, it is characterised in that：Step（6）Ammonium fluosilicate dealumination complement silicon processing depth is higher than
Step（2）The processing of ammonium fluosilicate dealumination complement silicon.
13. in accordance with the method for claim 4, it is characterised in that：Step（7）Described roasting condition is：At 400 ~ 600 DEG C
Roasting 2 ~ 4 hours.
14. the hydrocracking catalyst prepared according to the method described in claim 1 ~ 13 any claim, it is characterised in that：
With overall catalyst weight gauge, including following component：Silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal 15% ~ 45%,
Wherein active metal is in terms of metal oxide；Mass percent of the described modified Y molecular sieve in silica-alumina supports be 15% ~
90%, surplus is amorphous silica-alumina and/or aluminum oxide；Group VIII of the described active metal in the periodic table of elements and/or
Vib metals element；The specific surface area of the catalyst is 200 ~ 400m2/ g, pore volume are 0.2 ~ 0.5mL/g.
15. the hydrocracking catalyst prepared according to the method described in claim 1 ~ 13 any claim, applied to fecund
The hydrocracking reaction process of diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion, operating condition are：Reaction pressure 6.0 ~
20.0MPa, 350 ~ 420 DEG C of reaction temperature, 0.1 ~ 2.0h of feed volume air speed-1, hydrogen to oil volume ratio 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 |
| US5856608A (en) * | 1997-02-21 | 1999-01-05 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
| CN1253988A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst 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 |
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Patent Citations (5)
| 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 |
| US5856608A (en) * | 1997-02-21 | 1999-01-05 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
| CN1253988A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst 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 |
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