CN105618114B - A kind of preparation method of hydrocracking catalyst composition - Google Patents
A kind of preparation method of hydrocracking catalyst composition Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of hydrocracking catalyst composition, 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 into extruded moulding after slurry, 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 obtains hydrocracking catalyst through drying, roasting；Wherein modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio is 10 ~ 90, superficial layer silica alumina ratio 6 ~ 30.Hydrocracking catalyst prepared by the inventive method has good temperature raising sensitiveness and operating flexibility, is had broad application prospects during hydrocracking reaction.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst composition.
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.It is hydrocracked in China
Technology adapts to the characteristics of strong, product adjustability is big due to its raw material, therefore, is usually come by oil refining enterprise as a kind of regulating measure
The changes in demand in market is adapted to, can some voluminous midbarrels, and market when distillate is in great demand between Ru Dang cities field alignment
When in great demand to heavy naphtha then can voluminous heavy naphtha, therefore, the operating condition such as air speed, pressure on hydrocracking unit
In the case of being relatively fixed, the temperature raising sensitiveness of hydrocracking catalyst is particularly important for device flexible operating, in addition, for
Setter, because hydrogen supply is relatively fixed, therefore, hydrogen gas consumption should be reduced as far as possible during device temperature raising
Fluctuation so as to being more beneficial for device even running while flexible operating, these are all carried for the research and development of hydrocracking catalyst
Higher requirement is gone out.
At present, it is modified Y molecular sieve that hydrocracking process is the most widely used, inside and outside conventional processing method molecular sieve
Distribution of silicon and aluminium is uniform, and acid centre is uniformly distributed, and when reducing Y molecular sieve silica alumina ratio, improves Y molecular sieve acid site density,
Temperature raising sensitiveness is improved, but simultaneously, second pyrolysis is also significantly increased, and hydrogen consumption is substantially improved.And it is deep when being carried out to Y molecular sieve
Degree processing, when sour density is too low, catalyst temperature raising sensitiveness is again poor.
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 temperature raising is sensitive
Property it is higher, but simultaneously, temperature raising process second pyrolysis substantially increases, and hydrogen consumption is notable to be risen, and is unfavorable for industrial hydrocracking unit
Temperature raising process apparatus even running.
CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, prepared by the invention
Hydrocracking catalyst temperature raising sensitiveness is poor.
The content of the invention
In view of the shortcomings of the prior art, the present invention puies forward a kind of preparation method of hydrocracking catalyst composition, the present invention
Hydrocracking catalyst composition prepared by method has good temperature raising sensitiveness and operating flexibility, in hydrocracking reaction mistake
Had broad application prospects in journey.
The preparation method of the hydrocracking catalyst composition of the present invention, including following content：
First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed, add dust technology into extrusion after slurry into
Type, 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；
The concentration of dust technology wherein described in step one is 3wt% ~ 30wt%；Described drying condition 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；
Group VIII and/or vib metals member of the active metal in the periodic table of elements wherein described in step 2
One or more in element；Group VIII active metal can be Ni and/or Co, vib active metal can be W and/or
Mo；The liquid-solid ratio wherein impregnated is 1.5：1~3：1, carried out by the way of saturation well known in the art dipping, VIB in maceration extract
The content of race's metallic compound is calculated as 20 ~ 60g/100ml by corresponding oxide, and the content of group VIII metallic compound is by corresponding
The concentration that oxide is calculated as metallic compound in 3 ~ 20g/100ml, maceration extract can need to adjust accordingly according to product；
Drying condition wherein described in step 2 is：Dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition is：400 ~
It is calcined 1 ~ 5 hour at 700 DEG C；
Mass percent of the wherein described modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, remaining
Measure as amorphous silica-alumina and/or aluminum oxide；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio（Wen Zhong
Described silica alumina ratio is SiO2/Al2O3Mol ratio）For 10 ~ 90, preferably 20 ~ 60, superficial layer silica alumina ratio 6 ~ 30, preferably 8 ~ 20, table
Surface layer silica alumina ratio is less than body phase silica alumina ratio 5 ~ 40, 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 are primary in Y molecular sieve crystal grain before modified；Sodium oxide molybdena quality
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/ of pore volume
g；Infrared 0.3 ~ 1.0mmol/g of acid content, preferably 0.4 ~ 0.8mmol/g；Relative crystallinity 90 ~ 130%.
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 ammonium fluosilicate dealumination complement silicon processing；
（3）To step（2）Y molecular sieve after processing carries out hydro-thermal process；
（4）To step（3）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution；
（5）Y molecular sieve rapid draing processing after aluminum salt solution processing；
（6）By liquid or gaseous unsaturated olefin and step（5）The Y molecular sieve that rapid draing is obtained fully is contacted, so
Carbon deposit reaction is carried out in oxygen-containing atmosphere afterwards；；
（7）By step（6）Obtained molecular sieve carries out ammonium fluosilicate dealumination complement silicon processing；
（8）Step（7）Y molecular sieve after being handled through ammonium fluosilicate dealumination complement silicon carries out the place that makes charcoal after filtering, drying
Reason, 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%；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）Described ammonium fluosilicate dealumination complement silicon process is：By step（1）Obtained Y molecular sieve, which adds water, is made into liquid
Gu mass ratio 3：1~6：1 water sample mixing, then, addition concentration are 0.3 ~ 1.2mol/L ammonium fluosilicate aqueous solution, in 50 ~ 80 DEG C
Processing 0.5 ~ 2 hour；Wherein ammonium fluosilicate solution addition needs 4 ~ 10g of pure fluosilicic acid ammonium to count according to every 100g molecular sieves；
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（5）Rapid draing treatment conditions are：Drying temperature is 100 ~ 300 DEG C, and drying time is 1 ~ 60 minute, preferably
3 ~ 20 minutes.
Step（6）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（6）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（7）Ammonium fluosilicate dealumination complement silicon process is：By step（6）Obtained Y molecular sieve, which adds water, is made into liquid stereoplasm amount
Than 3：1~6：1 water sample mixing, then, addition concentration be 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, in 70 ~ 120 DEG C handle 1 ~
4 hours, wherein ammonium fluosilicate solution addition needed to deposit 9 ~ 30g of ammonium fluosilicate meters according to every 100g molecular sieves；Preferred steps（7）
Ammonium fluosilicate dealumination complement silicon processing depth is higher than step（2）The processing of ammonium fluosilicate dealumination complement silicon.
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.
Hydrocracking catalyst of the present invention can be applied to flexibly production industrial chemicals or intermediate oil etc. it is different plus
Hydrogen cracking reaction process, general operational requirement(GOR) is：6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, feed volume
0.1 ~ 2.0h of air speed-1, hydrogen to oil volume ratio is 500：1~2000：1.
In the inventive method, the Y molecular sieve used hydrocracking catalyst carries out specially treated, i.e., first carry out either shallow fluorine
Ammonium silicate processing, hydro-thermal process and aluminium salt processing, then carry out rapid draing to Y molecular sieve wet feed after processing and remove its surface
Water, makes to be adsorbed in the unsaturated hydrocarbons such as alkene, alkadienes outside Y molecular sieve in molecular sieve in air atmosphere, under heating condition
Aluminium position outside outside fully carbon deposit, such molecular sieve is by carbon deposit covering protection, therefore, follow-up ammonium fluosilicate dealumination complement silicon processing
During, mainly internally carry out, after ammonium fluosilicate is treated, then the carbon deposit of residual outside molecular sieve is removed in high-temperature roasting, extensive
Acid sites position outside compound molecule sieve.The inventive method carries out dealumination complement silicon by selectivity to Y molecular sieve inside, identical
On the premise of silica alumina ratio, the selective silica alumina ratio for reducing molecular sieve outer surface adds the acid site of molecular sieve outer surface
Meanwhile, the high silica alumina ratio feature inside molecular sieve is remained, is urged compared to being hydrocracked for conventional method modified molecular screen preparation
Agent can significantly improve device liquid under temperature raising sensitiveness, the operating flexibility of catalyst, same conversion and receive and chemical hydrogen consumption
All make moderate progress.
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）Step（1）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, adds concentration and 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 1.5 hours under 0.1MPa；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 7:1 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.
（5）Take step（4）The molecular sieve of gained is dried 5 minutes in 140 DEG C；
（6）Take step（5）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；
（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
0.9mol/L ammonium fluosilicate solution 200ml, 75 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 4 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, the SiO of superficial layer2/Al2O3
Mol ratio is 14, molecular sieve SiO2/Al2O3 Mol ratio is 30.XRD analysis result shows that its lattice constant is 2.432nm, relatively
Crystallinity 107%.Pore volume 0.36ml/g, specific surface area 810m2/ g, infrared analysis result determines Y-1 meleic acid amounts and is
0.63mmol/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
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）Step（1）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with distilled water, then, adds concentration and is
0.7mol/L ammonium fluosilicate solution 120ml, 70 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 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.
（5）Step（4）130 DEG C of molecular sieve drying 30 minutes after processing；
（6）Take heptene soaking step（5）The molecular sieve of gained 4 hours, then, 250 DEG C of heating 12 are small in air atmosphere
When；
（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 300ml, 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 4 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 50g are taken to be mixed with 50g 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 160nm thickness, the SiO of superficial layer2/
Al2O3Mol ratio is 7.0, molecular sieve SiO2/Al2O3 Mol ratio is 43.XRD analysis result shows that its lattice constant is
2.426nm, relative crystallinity 102%.Pore volume 0.38 ml/g, specific surface area 780m2/ g, it is infrared that infrared analysis result determines Y-2
Acid amount is 0.48mmol/g.
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）Step（1）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with distilled water, then, adds concentration and is
0.5mol/L ammonium fluosilicate solution 120ml, 60 DEG C are handled 1.5 hours；
（3）To step（2）530 DEG C of obtained Y molecular sieve, hydro-thermal process 1.5 hours under 0.1MPa；
（4）Step（3）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 1.5 hours are added during mixing.
（5）Step（4）200 DEG C of molecular sieve drying 30 minutes after processing；
（6）Take heptene soaking step（5）The molecular sieve of gained 4 hours, then, 180 DEG C of heating 20 are small in air atmosphere
When；
（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 250ml, 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-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 50g are taken to be mixed with 50g 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 180nm thickness, the SiO of superficial layer2/
Al2O3Mol ratio is 8.5, molecular sieve SiO2/Al2O3 Mol ratio is 40.XRD analysis result shows that its lattice constant is
2.429nm, relative crystallinity 103%.Pore volume 0.39 ml/g, specific surface area 820m2/ g, it is infrared that infrared analysis result determines Y-3
Acid amount is 0.50mmol/g.
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）Step（1）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, adds concentration and is
0.6mol/L ammonium fluosilicate solution 100ml, 65 DEG C are handled 1.0 hours；
（3）To step（2）550 DEG C of obtained Y molecular sieve, hydro-thermal process 1.0 hours under 0.1MPa；
（4）Step（3）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.
（5）Step（4）Molecular sieve after processing is dried 9 minutes in 130 DEG C；
（6）Take hexadiene soaking step（5）The molecular sieve of gained 4 hours, then, 150 DEG C of heating 35 in air atmosphere
Hour；
（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, 80 DEG C are handled 1.5 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 90nm thickness, the SiO of superficial layer2/Al2O3
Mol ratio is 15, molecular sieve SiO2/Al2O3 Mol ratio is 28.XRD analysis result shows that its lattice constant is 2.438nm, relatively
Crystallinity 106%.Pore volume 0.36ml/g, specific surface area 750m2/ g, infrared analysis result determines Y-4 meleic acid amounts and is
0.66mmol/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
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 65g are taken to be mixed with 35g 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 23.XRD analysis result shows that its lattice constant is 2.441nm, relative crystallization
Degree 88%, pore volume 0.36ml/g, specific surface area 720m2/ g, meleic acid amount is 0.73 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 32.XRD analysis result shows that its lattice constant is 2.426nm, relative crystallization
Degree 92%, pore volume 0.39ml/g, specific surface area 690m2/ g, meleic acid amount is 0.55 mmol/g.
Embodiment 5
The reactivity worth of catalyst is prepared in order to investigate embodiment 1 ~ 4 and comparative example 1 ~ 2, to catalyst on midget plant
Evaluation test is carried out, evaluating apparatus is connected once by flow using single hop, an anti-filling regular refiner catalyst, two anti-points
The hydrocracking catalyst according to embodiment 1 ~ 4 and the preparation of the method for comparative example 1 ~ 2 is not loaded, and evaluation result is listed in 1 ~ table of table 4.
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 is investigated with the catalyst differential responses temperature of comparative example 1 to be tested.
The embodiment 2 of table 5 is investigated with the catalyst differential responses temperature of comparative example 2 to be tested.
Show by using contrast test of the embodiment 1 with the catalyst of comparative example 1 on evaluating apparatus, using present invention side
Product changes in distribution amplitude is larger during catalyst prepared by method has more preferable operating flexibility, temperature raising, can switch progress
Voluminous naphtha and the less operation of production naphtha both of which, simultaneously as the present invention uses specific process modified Y molecular sieve,
While improving acid centre outside molecular sieve, the high silica alumina ratio inside molecular sieve is remained, acid centre is less, temperature raising process
The secondary cracking caused is significantly reduced, accordingly, with respect to the catalyst of comparative example 1, and the catalyst of embodiment 1 hydrogen during temperature raising consumes
Increase and liquid receipts fall are smaller, are more beneficial for the quiet run of device.Embodiment 2 is with the catalyst of comparative example 2 to having a competition
Test, show, the catalyst of embodiment 2 causes the catalyst of embodiment 2 to have more due to the higher acid site quantity of molecular sieve outer surface
Good temperature raising sensitiveness, is more than 350 DEG C of cut conversion ratios raisings about during reaction temperature is improved to 380 DEG C from 372 DEG C
15 percentage points, and comparative example 2 only improves 6 percentage points, compared to the catalyst of comparative example 2, the catalyst of embodiment 2 shows bigger
Product distribution flexibility.Therefore, all in all catalyst of the present invention shows good temperature raising sensitiveness, device operation flexibly
Property and higher liquid yield.
Claims (17)
1. a kind of preparation method of hydrocracking catalyst composition, it is characterised in that including following content：First, will be modified Y points
Son is sieved, amorphous silicon aluminium and/or aluminum oxide are well mixed, adds dust technology into extruded moulding after slurry, is dried, roasting is obtained containing and changed
The silica-alumina supports of property Y molecular sieve；2nd, the carrier of step one is impregnated using the maceration extract containing active metal, after dipping
Carrier obtains hydrocracking catalyst through drying, roasting；
Mass percent of the modified Y molecular sieve in silica-alumina supports wherein described in step one is 15% ~ 90%, and surplus is amorphous
Sial and/or aluminum oxide；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio is 10 ~ 90, superficial layer silicon
Aluminum ratio 6 ~ 30, superficial layer silica alumina ratio is less than body phase silica alumina ratio 5 ~ 40, wherein described superficial layer refers to molecular sieve outer surface to inside
10 ~ 200nm thickness range, superficial layer is primary in Y molecular sieve crystal grain before modified；Modified Y molecular sieve specific surface area 650 ~
900m2/ g, 0.30 ~ 0.50ml/g of pore volume；Infrared 0.3 ~ 1.0mmol/g of acid content；Relative crystallinity 90% ~ 130%.
2. in accordance with the method for claim 1, it is characterised in that：Described drying condition is：1 ~ 5 is dried at 80 ~ 120 DEG C
Hour；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
3. in accordance with the method for claim 1, it is characterised in that：Active metal described in step 2 is in the periodic table of elements
Group VIII and/or vib metals element in one or more；Group VIII active metal is Ni and/or Co, the
Group vib active metal is W and/or Mo；The liquid-solid ratio wherein impregnated is 1.5：1~3：1, carried out by the way of saturation impregnates；Leaching
The content of group vib metallic compound is calculated as 20 ~ 60g/100ml by corresponding oxide in stain liquid, group VIII metallic compound
Content is calculated as 3 ~ 20g/100ml by corresponding oxide.
4. 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.
5. in accordance with the method for claim 1, it is characterised in that：The preparation method of described modified Y molecular sieve includes as follows
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 hand over
Y molecular sieve after changing carries out ammonium fluosilicate dealumination complement silicon processing；（3）To step（2）Y molecular sieve after processing is carried out at hydro-thermal
Reason；（4）To step（3）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution；（5）Y molecular sieve after aluminum salt solution processing is fast
Fast drying process；（6）By liquid or gaseous unsaturated olefin and step（5）The Y molecular sieve that rapid draing is obtained fully is contacted,
Then carbon deposit reaction is carried out in oxygen-containing atmosphere；（7）By step（6）Obtained molecular sieve is carried out at ammonium fluosilicate dealumination complement silicon
Reason；（8）Step（7）Y molecular sieve after being handled through ammonium fluosilicate dealumination complement silicon carries out processing of making charcoal, obtained after filtering, drying
Modified Y molecular sieve.
6. in accordance with the method for claim 5, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：With
NaY zeolite be raw material in ammonium salt aqueous solution, at 60 ~ 120 DEG C, exchange 1 ~ 3 hour, exchange times be 1 ~ 4 time, obtain after exchange
NaY zeolite, Na2O content is less than 3.0%.
7. in accordance with the method for claim 5, it is characterised in that：Step（2）Described ammonium fluosilicate dealumination complement silicon process is：
By step（1）Obtained Y molecular sieve, which adds water, is 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, is 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.
8. in accordance with the method for claim 5, 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.
9. in accordance with the method for claim 5, 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.
10. in accordance with the method for claim 5, it is characterised in that：Step（5）Rapid draing treatment conditions are：Drying temperature
For 100 ~ 300 DEG C, drying time is 1 ~ 60 minute.
11. in accordance with the method for claim 5, it is characterised in that：Step（6）Described unsaturated olefin is that carbon number is
2 ~ 10 positive structure or isomeric olefine, alkadienes.
12. according to the method described in claim 5 or 11, it is characterised in that：Gaseous state unsaturated olefin and molecular sieve contact conditions
For：0.1 ~ 1.0MPa of pressure, 0.1 ~ 2 hour time of contact；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.
13. in accordance with the method for claim 5, it is characterised in that：Step（6）Described oxygen-containing atmosphere be 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. in accordance with the method for claim 5, it is characterised in that：Step（6）Described carbon deposit reaction condition is：Reaction temperature
50 ~ 500 DEG C of degree, the reaction time is 1 ~ 50 hour.
15. in accordance with the method for claim 5, it is characterised in that：Step（7）Described ammonium fluosilicate dealumination complement silicon process
For：By step（6）Obtained Y molecular sieve, which adds water, is made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, then add concentration be 0.8 ~
The 2.0mol/L ammonium fluosilicate aqueous solution, is handled 1 ~ 4 hour, wherein ammonium fluosilicate solution addition is according to every in 70 ~ 120 DEG C
100g molecular sieves need 9 ~ 30g of ammonium fluosilicate to count.
16. according to the method described in claim 5 or 15, it is characterised in that：Step（7）Ammonium fluosilicate dealumination complement silicon handles depth
Higher than step（2）The processing of ammonium fluosilicate dealumination complement silicon.
17. in accordance with the method for claim 5, it is characterised in that：Step（8）Described treatment conditions of making charcoal are：400~600
It is calcined 2 ~ 4 hours at DEG C.
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|---|---|---|---|---|
| US5259948A (en) * | 1991-04-29 | 1993-11-09 | Uop | Hydrocarbon conversion process using a novel silicon enhanced amorphous silica-alumina |
| CN1178721A (en) * | 1996-10-09 | 1998-04-15 | 中国石油化工总公司抚顺石油化工研究院 | High silicon high crystallinity Y type molecular sieve and its preparing method |
| CN101343068A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Y type molecular sieve and method of preparing the same |
| CN101380588A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5259948A (en) * | 1991-04-29 | 1993-11-09 | Uop | Hydrocarbon conversion process using a novel silicon enhanced amorphous silica-alumina |
| CN1178721A (en) * | 1996-10-09 | 1998-04-15 | 中国石油化工总公司抚顺石油化工研究院 | High silicon high crystallinity Y type molecular sieve and its preparing method |
| CN101343068A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Y type molecular sieve and method of preparing the same |
| CN101380588A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
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