CN105536856B - A kind of hydrocracking catalyst and preparation method thereof - Google Patents
A kind of hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of 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 15% ~ 45%, wherein active metal is in terms of metal oxide；Described active metal is selected from group VIII and/or vib metals element；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；The silica alumina ratio of modified Y molecular sieve body phase is 8 ~ 30, wherein superficial layer silica alumina ratio 20 ~ 100, and superficial layer silica alumina ratio is higher than body phase silica alumina ratio, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness range；650 ~ 900m of specific surface area2/g；0.30 ~ 0.50ml/g of pore volume；Lattice constant is 2.425 ~ 2.455；Infrared 0.3 ~ 1.2mmol/g of acid content；Relative crystallinity 80% ~ 120%.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.
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 provides a kind of hydrocracking catalyst and preparation method thereof, and the present invention adds
Hydrogen Cracking catalyst has good reactivity and anti-nitrogen ability.
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；Y points of wherein described modification
Mass percent of the son sieve in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, and surplus is amorphous silica-alumina and/or oxidation
Aluminium；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio（Silica alumina ratio described in text is SiO2/Al2O3
Mol ratio）For 8 ~ 30, wherein superficial layer silica alumina ratio 20 ~ 100, preferably 40 ~ 80, 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, preferably 10 ~ 200nm, more preferably
50 ~ 190nm, superficial layer is primary in Y molecular sieve crystal grain before modified, intact with molecular sieve internal cohesion, does not block in molecular sieve
Portion duct；Sodium oxide molybdena weight/mass percentage composition is less than 1.0%, preferably smaller than 0.5%；650 ~ 900m of modified Y molecular sieve specific surface area2/
g；0.30 ~ 0.50ml/g of pore volume；Infrared 0.3 ~ 1.2mmol/g of acid content, preferably 0.4 ~ 1.0mmol/g；Relative crystallinity 80% ~
120%。
Group VIII and/or vib metals element of the described active metal in the periodic table of elements, group VIII
Active metal can be Ni and/or Co, and 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.
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）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution；
（4）To step（3）The Y molecular sieve drying process of gained；
（5）By liquid or gaseous unsaturated olefin and step（4）The Y molecular sieve of drying process is fully contacted, Ran Hou
Carbon deposit reaction is carried out in oxygen-containing atmosphere；
（6）By step（5）The carbon deposit Y molecular sieve quick high-temp calcination process of preparation；
（7）By step（6）Obtained molecular sieve carries out dealumination complement silicon processing；
（8）Step（7）Y molecular sieve after being handled through dealumination complement silicon carries out processing of making charcoal, obtains pre- after filtering, drying
The Y molecular sieve of processing.
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%；The wherein SiO of NaY zeolite raw material2/Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt
It is the one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, 0.3 ~ 6.0mol/ of ammonium salt aqueous solution concentration
L, 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）Aluminium salt used in described aluminium salt processing procedure can be aluminium chloride, aluminum sulfate, aluminum nitrate etc..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 unsaturated olefin is the positive structure or isomeric olefine, alkadienes that charcoal atomicity is 2 ~ 10；Wherein institute
The alkene stated fully is contacted with molecular sieve refers to that unsaturated olefin is diffused into inside molecular sieve；When use gaseous state unsaturated olefin
When, gaseous state unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, 0.1 ~ 2 hour time of contact；When using liquid
During state unsaturated hydrocarbons, liquid unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 is small
When, molecular sieve answers thorough impregnation in liquefied olefines.Described alkene is fully contacted with molecular sieve typically to be carried out at normal temperatures, institute
The unsaturated hydrocarbons state phase stated 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 dealumination complement silicon be processed as method well known to those skilled in the art, can be using conventional fluorine
Ammonium silicate dealumination complement silicon method, i.e., first by step（6）Obtained Y molecular sieve, which adds water, is 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
The methods such as silicon are mended to be also suitable.
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 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；Wherein the concentration of dust technology be 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 hours；
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；The liquid-solid ratio wherein impregnated is 1.5：1~3：1, impregnated using saturation well known in the art
Mode is carried out, and the content of group vib metallic compound is calculated as 20 ~ 60g/100ml, group VIII gold by corresponding oxide in maceration extract
The concentration that the content of category compound is calculated as metallic compound in 3 ~ 20g/100ml, maceration extract by corresponding oxide can be according to production
Product need to adjust accordingly；Wherein described drying condition is：Dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting 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.
In the inventive method, the Y molecular sieve used hydrocracking catalyst carries out specially treated, i.e., first in air gas
Make the unsaturated hydrocarbons such as the alkene being adsorbed on Y molecular sieve, alkadienes abundant carbon deposit inside and outside molecular sieve in atmosphere, under heating condition,
Then, accumulated the aluminium position inside the charcoal deposited on the method burn-up molecular sieve surface being calcined by quick high-temp, such molecular sieve
Charcoal covering protection, therefore, in follow-up ammonium fluosilicate dealumination complement silicon processing procedure, is mainly carried out, at ammonium fluosilicate on the outer surface
After reason, then the carbon deposit of molecular sieve internal residual is removed in high-temperature roasting, recovers the acid sites position inside molecular sieve.The inventive method
By selectivity to Y molecular sieve outer surface carry out dealumination complement silicon, the selective silica alumina ratio for improving Y molecular sieve outer surfaces,
It can be carried compared to hydrocracking catalyst prepared by conventional method modified molecular screen in the case where keeping close anti-nitrogen ability
High catalyst reactivity or the anti-nitrogen ability that hydrocracking catalyst is improved on the premise of identical activity.
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 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）530 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；
（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, then heats to 80 DEG C, is stirring
0.5mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（4）Step（3）The dry 8h 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 butadiene atmosphere, control pressure
0.3MPa is fully contacted 20 minutes, then, is heated 15 hours at 200 DEG C in air atmosphere；
（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 5:1 mixes with distilled water, then, adds concentration and is
0.8mol/L ammonium fluosilicate solution 100ml, 90 DEG C are handled 2 hours；
（8）Through step（7）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Modified Y molecular sieve is obtained, numbering is Y-1.
Y-1 molecular sieve transmission electron microscope EDAX results determine its outer surface to 80nm thickness, and superficial layer silica alumina ratio is 40,
Molecular sieve body phase silica alumina ratio is 10.5.XRD analysis result shows that its lattice constant is 2.445nm, relative crystallinity 98%.Pore volume
0.36ml/g, specific surface area 740m2/ g, it is 0.98mmol/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）Gained molecular sieve is according to liquid-solid ratio 6:1 mixes with distilled water stirring, then heats to 90 DEG C, is stirring
0.8mol/L aluminum sulfate solution 600ml, isothermal reaction 2 hours are added during mixing.
（4）Step（3）The dry 4h of 200 DEG C of gained molecular sieve；
（5）Take heptene soaking step（4）The molecular sieve of gained 2 hours, then, 250 DEG C of heating 20 are small in air atmosphere
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 15 minutes；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, adds concentration and is
1.5mol/L ammonium fluosilicate solution 150ml, 95 DEG C are handled 2 hours；
（8）Through step（7）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Modified Y molecular sieve is obtained, 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）Y-2 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-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.
Y-2 molecular sieve transmission electron microscope EDAX results determine its outer surface to 150nm thickness, and superficial layer silica alumina ratio is
65, molecular sieve body phase silica alumina ratio is 14.XRD analysis result shows that its lattice constant is 2.436nm, relative crystallinity 95%.Pore volume
0.38 ml/g, specific surface area 670m2/ g, it is 0.70mmol/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 0.8mol/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）550 DEG C of obtained Y molecular sieve, hydro-thermal process 1.5 hours under 0.1MPa；
（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 6:1 mixes with distilled water stirring, then heats to 90 DEG C, is stirring
0.8mol/L aluminum sulfate solution 600ml, isothermal reaction 2 hours are added during mixing.
（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, 300 DEG C of heating 12 are small in air atmosphere
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 5:1 mixes with distilled water, then, adds concentration and is
1.0mol/L ammonium fluosilicate solution 150ml, 95 DEG C are handled 3 hours；
（8）Through step（7）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Modified Y molecular sieve is obtained, 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.
Y-3 molecular sieve transmission electron microscope EDAX results determine its outer surface to 190nm thickness, and superficial layer silica alumina ratio is
60, molecular sieve body phase silica alumina ratio is 16.XRD analysis result shows that its lattice constant is 2.433nm, relative crystallinity 95%.Pore volume
0.38 ml/g, specific surface area 680m2/ g, it is 0.68mmol/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 0.6mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 80 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）540 DEG C of obtained Y molecular sieve, hydro-thermal process 1 hour under 0.1MPa；
（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, then heats to 80 DEG C, is stirring
0.5mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（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 3 hours, then, 150 DEG C of heating 25 in air atmosphere
Hour；
（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 40 minutes；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, adds concentration and is
1.0mol/L ammonium fluosilicate solution 100ml, 80 DEG C are handled 2 hours；
（8）Through step（7）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 2 hours,
Modified Y molecular sieve is obtained, numbering is Y-4.
Y-4 molecular sieve transmission electron microscope EDAX results determine its outer surface to 180nm thickness, and superficial layer silica alumina ratio is
38, molecular sieve body phase silica alumina ratio is 11.5.XRD analysis result shows that its lattice constant is 2.440nm, relative crystallinity 98%.Hole
Hold 0.36ml/g, specific surface area 750m2/ g, it is 0.89mmol/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-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-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 is 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 10.XRD analysis result shows that its lattice constant is 2.446nm, relative crystallization
Degree 95%, pore volume 0.33ml/g, specific surface area 720m2/ g, meleic acid amount is 1.0 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 is 16.XRD analysis result shows that its lattice constant is 2.438, relative crystallinity
90%, pore volume 0.38ml/g, specific surface area 690m2/ g, meleic acid amount is 0.68 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 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.
Embodiment 1 and the catalyst stability contrast test of comparative example 1 under the oily high nitrogen-containing of the refining stage of table 4 generation.
Embodiment 2 and the catalyst stability contrast test of comparative example 2 under the oily high nitrogen-containing of the refining stage of table 5 generation.
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 80ppm, 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 (20)
1. a kind of hydrocracking catalyst, it is characterised in that：With overall catalyst weight gauge, including following component：Containing modified Y molecules
The silica-alumina supports 55% ~ 85% of sieve, active metal 15% ~ 45%, wherein active metal is in terms of metal oxide；Described active metal
The one or more in group VIII and/or vib metals element in the periodic table of elements；Wherein described modification Y
Mass percent of the molecular sieve in silica-alumina supports is 15% ~ 90%, and surplus is amorphous silica-alumina and/or aluminum oxide；Described changes
Property Y molecular sieve lattice constant be 2.425 ~ 2.455nm；Body phase silica alumina ratio is 8 ~ 30, wherein superficial layer silica alumina ratio 20 ~ 100, surface
Layer silica alumina ratio is 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
Scope, superficial layer is primary in Y molecular sieve crystal grain before modified；650 ~ 900m of modified Y molecular sieve specific surface area2/g；Pore volume 0.30 ~
0.50mL /g；Infrared 0.3 ~ 1.2mmol/g of acid content；Relative crystallinity 80% ~ 120%；Wherein described 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 modified Y molecular sieve refers to molecular sieve outer surface
To inside 10 ~ 200nm thickness ranges.
3. according to the catalyst described in claim 1, it is characterised in that：The superficial layer of modified Y molecular sieve refers to molecular sieve outer surface
To inside 50 ~ 190nm thickness ranges.
4. according to the catalyst described in claim 1 or 2 or 3, it is characterised in that：Group VIII active metal is Ni and/or Co,
Vib active metal is W and/or Mo；In terms of metal oxide, group VIII active metallic content is 3% ~ 15%, vib
Active metallic content is 10% ~ 40%.
5. according to the catalyst described in claim 1 or 2 or 3, it is characterised in that：The specific surface area of the catalyst be 200 ~
400m2/ g, pore volume is 0.2 ~ 0.5mL/g.
6. according to the catalyst described in claim 1 or 2 or 3, it is characterised in that：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
Y molecular sieve after obtained ammonium is exchanged carries out hydro-thermal process；（3）To step（2）Y molecular sieve aluminum salt solution after hydro-thermal process
Processing；（4）To step（3）The Y molecular sieve drying process of gained；（5）By liquid or gaseous unsaturated olefin and step（4）It is dry
The Y molecular sieve of dry processing is fully contacted, and carbon deposit reaction is then carried out in oxygen-containing atmosphere；（6）By step（5）The carbon deposit Y of preparation
Molecular sieve quick high-temp calcination process；（7）By step（6）Obtained molecular sieve carries out dealumination complement silicon processing；（8）Step（7）Through
Y molecular sieve after dealumination complement silicon processing carries out make charcoal processing, the Y molecular sieve pre-processed after filtering, drying.
7. according to the catalyst described in claim 6, it is characterised in that：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, at 60 ~ 120 DEG C, exchanges 1 ~ 3 hour, exchange times are 1 ~ 4 time, are exchanged
NaY zeolite afterwards, Na2O content is less than 3.0%；The wherein SiO of NaY zeolite raw material2/Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena quality
Percentage composition 6% ~ 7%；Ammonium salt is the one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt water
0.3 ~ 6.0mol/L of solution concentration.
8. 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.
9. according to the catalyst described in claim 6, it is characterised in that：Step（3）Aluminium used in described aluminium salt processing procedure
Salt is the one or more in aluminium chloride, aluminum sulfate or aluminum nitrate, and aluminium salt concentration is 0.05 ~ 2mol/L；Treatment temperature be 50 ~
120 DEG C, processing time is 0.5 ~ 3 hour.
10. according to the catalyst described in claim 6, it is characterised in that：Step（4）Described drying temperature is 90 ~ 300 DEG C,
Drying time is 2 ~ 10 hours.
11. according to the catalyst described in claim 6, it is characterised in that：Step（5）Described unsaturated olefin is charcoal atomicity
For 2 ~ 10 positive structure or isomeric olefine, alkadienes.
12. according to the catalyst described in claim 6, it is characterised in that：Step（5）Described gaseous state unsaturated olefin and molecule
Sieving contact conditions is：0.1 ~ 1.0MPa of pressure, 0.1 ~ 2 hour time of contact；Liquid unsaturated olefin and molecular sieve contact conditions
For：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%；Carbon deposit reaction condition is：50 ~ 500 DEG C of reaction temperature, the reaction time is 1 ~ 50 hour.
14. 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.
15. according to the catalyst described in claim 6, it is characterised in that：Step（7）Described in dealumination complement silicon processing procedure
For：First by step（6）Obtained Y molecular sieve, which adds water, is made into the water sample mixing of liquid-solid ratio 3 ~ 6, then, and addition concentration is 0.8 ~ 2mol/
The L ammonium fluosilicates aqueous solution is handled 1 ~ 4 hour in 70 ~ 100 DEG C.
16. 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.
17. the preparation method of the hydrocracking catalyst described in a kind of claim 1, it is characterised in that including following content：First,
Modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, dust technology is added into extrusion after slurry
Shaping, is dried, roasting obtains the silica-alumina supports containing modified Y molecular sieve；2nd, using the maceration extract containing active metal to step one
Carrier is impregnated, and the carrier after dipping obtains hydrocracking catalyst through drying, roasting.
18. in accordance with the method for claim 17, it is characterised in that：Drying condition described in step one is：At 80 ~ 120 DEG C
Lower drying 1 ~ 5 hour；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
19. in accordance with the method for claim 17, it is characterised in that：Drying condition described in step 2 is：At 90 ~ 150 DEG C
Lower drying 2 ~ 8 hours；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
20. the hydrocracking catalyst described in a kind of claim 1 is applied to high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil
The hydrocracking reaction process of hydro-conversion, it is characterised in that operating condition is：6.0 ~ 20.0MPa of reaction pressure, reaction temperature
350 ~ 420 DEG C, 0.1 ~ 2.0h of feed volume air speed-1, hydrogen to oil volume ratio is 500：1~2000：1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5856608A (en) * | 1997-02-21 | 1999-01-05 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
| 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 |
| CN102049283A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
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| KR101307226B1 (en) * | 2004-12-17 | 2013-09-12 | 할도르 토프쉐 에이/에스 | Hydrocracking process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856608A (en) * | 1997-02-21 | 1999-01-05 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
| 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 |
| CN102049283A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
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