CN105618115B - modified Y molecular sieve and preparation method thereof - Google Patents
modified Y molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of modified Y molecular sieve and preparation method thereof, has following property：Body phase silica alumina ratio is 10 ~ 70, and wherein superficial layer silica alumina ratio 7 ~ 30, superficial layer silica alumina ratio are 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 range；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；600 ~ 900m of modified Y molecular sieve specific surface area2/ g, 0.20 ~ 0.70ml/g of pore volume；Infrared 0.3 ~ 1.5mmol/g of acid content.The preparation method of modified Y molecular sieve of the present invention is as follows：Y molecular sieve after exchanging ammonium carries out first dealumination treatment, rapid draing, carries out carbon deposit reaction, high-temperature roasting processing, then through secondary dealumination treatment, drying, processing of making charcoal, obtains modified Y molecular sieve.The silica alumina ratio of molecular sieve surface layer of the present invention will be less than body phase silica alumina ratio, have broad application prospects during hydrocracking reaction.
Description
Technical field
The present invention relates to a kind of modified Y molecular sieve 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, 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.It is hydrocracked in China
Technology is because its raw material adapts to the characteristics of strong, product adjustability is big, therefore, is usually come by oil refining enterprise as a kind of regulating measure
Adapt to the changes in demand in market, when distillate is in great demand between Ru Dang cities field alignment, can some voluminous midbarrels, and market
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 be 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.It is and 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 obtained with after the mixed aqueous solution of aluminium salt and acid processing hydro-thermal process, and obtained catalyst temperature raising is sensitive
Property it is higher, but simultaneously, temperature raising process second pyrolysis substantially increases, and hydrogen consumption significantly rises, 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 provides a kind of modified molecular screen and preparation method thereof, modified point of the present invention
The silica alumina ratio of son sieve superficial layer（Silica alumina ratio described in text is SiO2/Al2O3Mol ratio）To be less than body phase silica alumina ratio, in fecund
Before having wide application during the different hydrocracking reactions such as diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion
Scape.
The modified Y molecular sieve of the present invention, has following property：Body phase silica alumina ratio be 10 ~ 70, wherein superficial layer silica alumina ratio 7 ~
30, preferably 9 ~ 20, superficial layer silica alumina ratio are less than body phase silica alumina ratio 5 ~ 40, wherein described superficial layer refers to molecular sieve outer surface to interior
5 ~ 400nm of portion thickness range, preferably 10 ~ 200nm, more preferably 50 ~ 190nm, superficial layer are primary brilliant in Y molecular sieve before modified
Grain, it is intact with molecular sieve internal cohesion, molecular sieve internal gutter is not blocked；Modified Y molecular sieve lattice constant be 2.425 ~
2.455nm；Sodium oxide molybdena weight/mass percentage composition is less than 1.0%, preferably smaller than 0.5%；600 ~ 900m of modified Y molecular sieve specific surface area2/
G, preferably 650 ~ 850m2/g；0.20 ~ 0.70ml/g of pore volume, preferably 0.3 ~ 0.6ml/g；Infrared 0.3 ~ 1.5mmol/g of acid content,
It is preferred that 0.4 ~ 1.2mmol/g；Relative crystallinity 60% ~ 130%, preferably 70% ~ 120%.
The preparation method of modified Y molecular sieve of the present invention, including following content：
（1）Ammonium Salt Ionic exchange reaction is carried out by former powder of NaY zeolite；
（2）Y molecular sieve after exchanging ammonium carries out first dealumination treatment；
（3）Step（2）Obtained Y molecular sieve rapid draing processing；
（4）Y molecular sieve after rapid draing fully contacts with liquid or gaseous unsaturated olefin, then in oxygen-containing atmosphere
Middle progress carbon deposit reaction；
（5）Step（4）Molecular sieve after processing carries out second of dealumination treatment；
（6）Step（5）Obtained Y molecular sieve obtains modified Y molecular sieve through drying, processing of making charcoal.
Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution using NaY zeolite, 60 ~
At 120 DEG C, at preferably 60 ~ 90 DEG C, exchange 1 ~ 3 hour, exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O contains
Amount is less than 3.0%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt be ammonium chloride,
One or more in ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0
~3.0 mol/L。
Step（2）The first dealumination treatment process can be at hydro-thermal process, acid treatment, aluminium salt processing and ammonium fluosilicate
One or more during reason；Wherein, hydrothermal treatment process is the hydro-thermal in itself vapor or under conditions of being passed through vapor
Treatment conditions are：Treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and processing time is 1.0 ~ 4.0 hours；Acid treatment
Inorganic acid and/or organic acid used in process can be one kind or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid
Kind, inorganic acid and/or organic acid are calculated as the liquid stereoplasm amount of 0.1 ~ 0.7mol/L, inorganic acid and/or organic acid and molecular sieve with H+
Than for 3:1~30:1；30 ~ 80 DEG C of acid treatment temperature, processing time are 0.5 ~ 3 hour；Aluminium salt used in aluminium salt processing procedure can be with
It is 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；Ammonium fluosilicate processing procedure is as follows：Y molecular sieve adds water to be made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, then
Addition concentration is 0.3 ~ 1.2mol/L ammonium fluosilicate aqueous solution, and 0.5 ~ 2 hour, wherein ammonium fluosilicate solution are handled in 50 ~ 80 DEG C
Addition needs 4 ~ 10g of pure fluosilicic acid ammonium to count according to every 100g molecular sieves.
Step（3）100 ~ 300 DEG C of described rapid draing temperature, drying time are 1 ~ 60 minute, preferably 3 ~ 30 minutes.
Step（4）Described unsaturated olefin is C2~C10Positive structure or isomeric olefine, alkadienes；Wherein described alkene
Fully contacted with molecular sieve and refer to that unsaturated olefin is diffused into inside molecular sieve；Gaseous state unsaturated olefin and molecular sieve bow strip
Part is：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.Described alkene and molecular sieve
Fully contact is typically carried out at normal temperatures, and described unsaturated hydrocarbons state phase is phase under normal temperature.
Step（4）Described oxygen-containing atmosphere is the mixing of air, the mixture of oxygen and nitrogen or oxygen and inert gas
One kind in thing, the volume fraction of oxygen in the gas phase are 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（5）Described in second of dealumination treatment process can be sour dealumination process or ammonium fluosilicate dealumination complement silicon mistake
Journey.
Wherein, sour dealumination process is with inorganic acid and/or organic acid treating step（4）Obtained Y molecular sieve；Inorganic acid or
Organic acid is the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, inorganic acid and/or organic acid it is dense
Degree is with H+It is calculated as 0.4 ~ 2.0mol/L；The liquid/solid mass ratio of sour dealumination treatment process is 3:1~30:1；Treatment temperature 60 ~ 120
DEG C, processing time is 0.5 ~ 3 hour.
Ammonium fluosilicate dealumination complement silicon process is by step（4）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 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, in 70 ~ 120 DEG C processing 1 ~ 4 hour, wherein
Ammonium fluosilicate solution addition needs to deposit 9 ~ 30g of ammonium fluosilicate meters according to every 100g molecular sieves.
Step（6）Described treatment conditions of making charcoal are：It is calcined 2 ~ 4 hours at 400 ~ 600 DEG C, removes what is remained on molecular sieve
Carbon deposit.
The step of described in the inventive method（2）、（3）、（4）With（5）It can also replace in the following way：By step
（1）Y molecular sieve after ammonium exchanges carries out dealumination treatment, dries；Impregnate in organic solvent, then rapid draing, drying is laggard
The desiliconization of row alkali is handled.
Wherein, described dealumination treatment can be used in hydro-thermal process, acid treatment, aluminium salt processing or ammonium fluosilicate processing
One or more combination；Hydrothermal treatment process is that hydrothermal conditions are in itself vapor or under conditions of being passed through vapor：
Treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and processing time is 1.0 ~ 6.0 hours；It is inorganic during acid treatment
Acid and/or organic acid are calculated as the solid mass ratio of liquid of 0.4 ~ 2.0mol/L, inorganic acid and/or organic acid and molecular sieve as 3 with H+:1~
30:1；60 ~ 120 DEG C of acid treatment temperature, processing time are 0.5 ~ 3 hour；Aluminium salt used in aluminium salt processing procedure can be chlorination
Aluminium, 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 small
When；Ammonium fluosilicate processing procedure is as follows：Y molecular sieve adds water to be made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, then adds concentration
For 0.6 ~ 2.0mol/L ammonium fluosilicate aqueous solution, handled 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition is pressed
9 ~ 30g of pure fluosilicic acid ammonium is needed to count according to every 100g molecular sieves.
The drying process process：90 ~ 300 DEG C of dryings 2 ~ 10 hours；Described organic solvent is selected from alkane, oil
One or more in ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene, impregnation method are impregnated using supersaturation, leaching
The stain time is 1 ~ 5 hour；Rapid draing temperature is 50 ~ 300 DEG C, and preferably drying temperature is higher than the boiling point of organic solvent, fast rapid-curing cutback
The dry time is 1 ~ 60 minute, preferably 3 ~ 20 minutes.
The alkali lye that described alkali desiliconization processing procedure uses is the aqueous solution of sodium hydroxide or potassium hydroxide, wherein alkali lye
Concentration is 0.1wt% ~ 2wt%.50 ~ 100 DEG C of base extraction temperature, processing time are 0.5 ~ 4 hour, alkali lye/molecular sieve liquid stereoplasm
Amount is than being 5:1~10:1.
The inventive method is handled Y molecular sieve by unsaturated olefin or organic solvent, is then used again internal de-
Aluminium or the mode of outside desiliconization, while internal high silica alumina ratio is kept, the selective Y molecular sieve outer surfaces that reduce
Silica alumina ratio.Modified Y molecular sieve of the present invention can be used for preparing hydrocracking catalyst, high-yield diesel oil, more producing chemical industry raw material and
Have broad application prospects during the different hydrocracking reaction such as catalytic diesel oil hydro-conversion.
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）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 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.
（4）Take step（3）The molecular sieve of gained is dried 8 minutes in 140 DEG C；
（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）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, and then, adding concentration is
0.6mol/L ammonium fluosilicate solution 100ml, 80 DEG C are handled 2 hours；
（7）Through step（6）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, after 550 DEG C are calcined 4 hours,
Obtain modified Y molecular sieve, numbering Y-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 with Na in the Y molecular sieve after exchange2O is calculated as 2.0%.
（2）To step（1）600 DEG C of obtained Y molecular sieve, hydro-thermal process 3 hours under 0.1MPa；
（3）Step（2）The molecular sieve of gained is according to liquid-solid ratio 7:1 and H+Concentration is that 1.0mol/L hydrochloric acid mixed solution mixes
Close, 95 DEG C are handled 2 hours；
（4）Step（3）The dry 2h of 250 DEG C of gained molecular sieve；
（5）Take toluene solvant soaking step（4）The molecular sieve of gained 3 hours；
（6）Step（5）130 DEG C of molecular sieve drying 25 minutes after processing；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with 1.2% sodium hydroxide solution, 80 DEG C of processing
3 hours；
（8）Through step（7）Y molecular sieve after alkali process, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering Y-2.
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）To step（1）520 DEG C of obtained Y molecular sieve, hydro-thermal process 3 hours under 0.1MPa；
（3）Step（2）Sieve is according to liquid-solid ratio 8:1 and 0.5mol/L citric acid solution（Concentration is with H+Meter）Mixing, then
50 DEG C are warming up to, isothermal reaction 2 hours；
（4）Step（3）130 DEG C of molecular sieve drying 40 minutes after processing；
（5）Take heptene soaking step（4）The molecular sieve of gained 4 hours, then, 180 DEG C of heating 30 are small in air atmosphere
When；
（6）Step（5）The molecular sieve of gained is according to liquid-solid ratio 7:1 and H+Concentration is that 1.0mol/L hydrochloric acid mixed solution mixes
Close, 95 DEG C are handled 2 hours；
（7）Through step（6）Y molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 4 hours, changed
Property Y molecular sieve, numbering Y-3.
Embodiment 4
Molecular sieve modified processing procedure：
（1）The NaY molecular sieve original powder 200g 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, and then, adding concentration is
0.8mol/L ammonium fluosilicate solution 100ml, 80 DEG C are handled 1.5 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 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）Molecular sieve after processing is in 150 DEG C of dry 8h；
（6）Take normal octane solvent soaking step（5）The molecular sieve of gained 2 hours；
（7）Step（6）Molecular sieve after processing is dried 12 minutes in 140 DEG C；
（8）Step（7）The Y molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with 0.6% sodium hydroxide solution, at 95 DEG C
Reason 2 hours；
（9）Through step（8）Y molecular sieve after alkali process, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering Y-4.
Embodiment 5
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 1.5 hours under 0.1MPa；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 7:1 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）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, and then, adding concentration 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,
Obtain modified Y molecular sieve, numbering Y-5.
Embodiment 6
（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
0.7mol/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 is stirred with distilled water, 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, and then, adding concentration 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,
Obtain modified Y molecular sieve, numbering Y-6.
Comparative example 1
（1）The NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 0.7mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 75 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.3%；
（2）To step（1）570 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 is stirred with distilled water, then heats to 85 DEG C, is stirring
0.6mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（4）Step（3）Y molecular sieve after aluminum sulfate processing, 120 DEG C of drying 2 hours, after 550 DEG C of roastings 2 hours, acquisition
Modified Y molecular sieve, numbering BY-1.
Comparative example 2
（1）The NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 2.0mol/L with concentration is according to liquid-solid ratio
6:1 mixing, 95 DEG C exchange 3 hours, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.0%；
（2）Step（1）Obtained Y molecular sieve is at 580 DEG C, hydro-thermal process 3 hours under 0.1Mpa；
（3）Step（2）The molecular sieve of gained is according to liquid-solid ratio 5:1 and H+Concentration 1.2mol/L hydrochloric acid solution mixing, 90
Constant temperature handles 2h at DEG C；
（4）Through step（3）Y molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed
Property Y molecular sieve, numbering BY-2.
Embodiment 1 ~ 6 and the physicochemical property of the modified Y molecular sieve of comparative example 1 ~ 2 are listed in the table below 1.
Embodiment 7
（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；
（2）The molecular sieve that respectively prepared by the molecular sieve of Example 1 ~ 6 and the method for comparative example 1 ~ 2, with aluminum oxide according to 50:50
Ratio be mixed with carrier, be respectively labeled as ZY-1, ZY-2, ZY-3, ZY-4, ZY-5, ZY-6, ZBY-1, ZBY-2；
（3）Maceration extract RY impregnates respectively（2）Middle carrier, obtain catalyst be designated as respectively Cat-1, Cat-2, Cat-3,
Cat-4, Cat-5, Cat-6, BCat-1 and BCat-2.
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 ~ 6 and comparative example respectively
1 ~ 2 hydrocracking catalyst prepared, feedstock property, appreciation condition and evaluation result are listed in 2 ~ table of table 6.
The embodiment of table 1 and comparative example molecular sieve analysis result.
The raw material oil nature of table 2.
The appreciation condition of table 3.
The evaluation result of table 4.
The embodiment 1 of table 5 is investigated with the catalyst differential responses temperature of comparative example 1 to be tested.
The embodiment 2 of table 6 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
Catalyst prepared by method has more preferable operating flexibility, and product changes in distribution amplitude is larger during 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
Caused by secondary cracking significantly reduce, accordingly, with respect to the catalyst of comparative example 1, the catalyst of embodiment 1 during temperature raising hydrogen consume
Increasing degree is smaller, is more beneficial for the quiet run of device.Embodiment 2 and the contrast test of the catalyst of comparative example 2 then show, real
Applying the catalyst of example 2 has more preferable temperature raising sensitiveness, is more than 350 DEG C during reaction temperature is improved to 380 DEG C from 372 DEG C
Cut conversion ratio improves about 15 percentage points, and comparative example 2 only improves about 7 percentage points, compared to the catalyst of comparative example 2, implements
The catalyst of example 2 shows bigger operating space.Therefore, all in all catalyst of the present invention shows good temperature raising sensitivity
Property, device operating flexibility and relatively low chemical hydrogen consumption.
Claims (29)
1. a kind of modified Y molecular sieve, it is characterised in that there is following property：Body phase silica alumina ratio is 10 ~ 70, superficial layer silica alumina ratio 7 ~
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 5 ~ 400nm of inside
Thickness range, superficial layer is primary in Y molecular sieve crystal grain before modified；Modified Y molecular sieve lattice constant be 2.425 ~
2.455nm；600 ~ 900m of modified Y molecular sieve specific surface area2/ g, 0.20 ~ 0.70ml/g of pore volume；Infrared acid content 0.3 ~
1.5mmol/g；Relative crystallinity 60% ~ 130%；Described silica alumina ratio is SiO2/Al2O3Mol ratio.
2. according to the molecular sieve described in claim 1, it is characterised in that：Described superficial layer refers to molecular sieve outer surface to inside 10
~ 200nm thickness range.
3. the preparation method of the modified Y molecular sieve described in a kind of claim 1 or 2, it is characterised in that including following content：（1）
Ammonium Salt Ionic exchange reaction is carried out by former powder of NaY zeolite；（2）Y molecular sieve after exchanging ammonium carries out first dealumination treatment；
（3）Step（2）Obtained Y molecular sieve rapid draing processing；（4）Y molecular sieve and liquid or gaseous insatiable hunger after rapid draing
Fully contacted with alkene, carbon deposit reaction is then carried out in oxygen-containing atmosphere；（5）Step（4）Molecular sieve after processing carries out second
Secondary dealumination treatment；（6）Step（5）Obtained Y molecular sieve obtains modified Y molecular sieve through drying, processing of making charcoal.
4. in accordance with the method for claim 3, 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, after obtaining exchange
NaY zeolite, Na2O content 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 is the one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration 0.3 ~
6.0mol/L。
5. in accordance with the method for claim 3, it is characterised in that：Step（2）The first dealumination treatment process is at hydro-thermal
One or more in reason, acid treatment, aluminium salt processing and ammonium fluosilicate processing procedure.
6. in accordance with the method for claim 5, it is characterised in that：Hydrothermal treatment process is in itself vapor or is passed through water steaming
Under conditions of gas, hydrothermal conditions are：Treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, processing time 1.0
~ 4.0 hours.
7. in accordance with the method for claim 5, it is characterised in that：Acid treatment process uses inorganic acid and/or organic acid, wherein
Described inorganic acid is the one or more in sulfuric acid, hydrochloric acid or nitric acid, and organic acid is one kind in citric acid, oxalic acid or acetic acid
It is or a variety of；Inorganic acid and/or organic acid are with H+The liquid for being calculated as 0.1 ~ 0.7mol/L, inorganic acid and/or organic acid and molecular sieve is consolidated
Mass ratio is 3:1~30:1；30 ~ 80 DEG C of acid treatment temperature, processing time are 0.5 ~ 3 hour.
8. in accordance with the method for claim 5, it is characterised in that：Aluminium salt used in aluminium salt processing procedure is aluminium chloride, sulfuric acid
One or more in aluminium or aluminum nitrate, aluminium salt concentration are 0.05 ~ 2mol/L；Treatment temperature is 50 ~ 120 DEG C, and processing time is
0.5 ~ 3 hour.
9. in accordance with the method for claim 5, it is characterised in that：Ammonium fluosilicate processing procedure is as follows：Y molecular sieve adds water to be made into
The solid mass ratio 3 of liquid：1~6：1 water sample mixing, it is 0.3 ~ 1.2mol/L ammonium fluosilicate aqueous solution then to add concentration, in 50 ~ 80 DEG C
Processing 0.5 ~ 2 hour, wherein ammonium fluosilicate solution addition need 4 ~ 10g of pure fluosilicic acid ammonium to count according to every 100g molecular sieves.
10. in accordance with the method for claim 3, it is characterised in that：Step（3）100 ~ 300 DEG C of described rapid draing temperature,
Drying time is 1 ~ 60 minute.
11. in accordance with the method for claim 3, it is characterised in that：Step（4）Described unsaturated olefin is C2~C10Just
Structure or isomeric olefine, alkadienes；Gaseous state unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, time of contact
0.1 ~ 2 hour；Liquid unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, 0.5 ~ 4 hour time of contact,
Molecular sieve thorough impregnation is in liquefied olefines.
12. in accordance with the method for claim 3, it is characterised in that：Step（4）Described oxygen-containing atmosphere be air, oxygen with
One kind in the mixture of inert gas, the volume fraction of oxygen in the gas phase are 10% ~ 100%.
13. in accordance with the method for claim 3, it is characterised in that：Carbon deposit reaction condition is：50 ~ 500 DEG C of reaction temperature, instead
It is 1 ~ 50 hour between seasonable.
14. in accordance with the method for claim 3, it is characterised in that：Step（5）Described in second of dealumination treatment process be acid
Dealumination process or ammonium fluosilicate dealumination complement silicon process.
15. in accordance with the method for claim 14, it is characterised in that：Sour dealumination process is with inorganic acid and/or organic acid
Manage step（4）Obtained Y molecular sieve；Described inorganic acid is the one or more in sulfuric acid, hydrochloric acid or nitric acid, and organic acid is lemon
One or more in lemon acid, oxalic acid or acetic acid；The concentration of inorganic acid and/or organic acid is with H+It is calculated as 0.4 ~ 2.0mol/L；Acid
The liquid/solid mass ratio of dealumination treatment process is 3:1~30:1；60 ~ 120 DEG C for the treatment of temperature, processing time are 0.5 ~ 3 hour.
16. in accordance with the method for claim 14, it is characterised in that：Ammonium fluosilicate dealumination complement silicon process is by step（4）
To Y molecular sieve add water to be made into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, it is 0.8 ~ 2.0mol/L fluosilicic acid then to add concentration
Aqueous ammonium, handled in 70 ~ 120 DEG C 1 ~ 4 hour, wherein ammonium fluosilicate solution addition needs pure according to every 100g molecular sieves
9 ~ 30g of ammonium fluosilicate is counted.
17. in accordance with the method for claim 3, it is characterised in that：Step（6）Described treatment conditions of making charcoal are：400~600
It is calcined 2 ~ 4 hours at DEG C.
18. in accordance with the method for claim 3, it is characterised in that：Described step（2）、（3）、（4）With（5）Using as follows
Mode replaces：By step（1）Y molecular sieve after ammonium exchanges carries out dealumination treatment, dries；Impregnate in organic solvent, then soon
Rapid-curing cutback is dry, and alkali desiliconization processing is carried out after drying；Described organic solvent be selected from alkane, petroleum ether, carbon tetrachloride, benzene, toluene,
One or more in ethylbenzene or dimethylbenzene.
19. in accordance with the method for claim 18, it is characterised in that：Described dealumination treatment using hydro-thermal process, acid treatment,
One or more combination in aluminium salt processing or ammonium fluosilicate processing.
20. in accordance with the method for claim 19, it is characterised in that：Hydrothermal treatment process is in itself vapor or is passed through water
Under conditions of steam, hydrothermal conditions are：Treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and processing time is
1.0 ~ 6.0 hours.
21. in accordance with the method for claim 19, it is characterised in that：Inorganic acid and/or organic acid are with H during acid treatment+Meter
For 0.4 ~ 2.0mol/L, inorganic acid and/or the solid mass ratio of the liquid of organic acid and molecular sieve are 3:1~30:1；Acid treatment temperature 60 ~
120 DEG C, processing time is 0.5 ~ 3 hour.
22. in accordance with the method for claim 19, it is characterised in that：Aluminium salt used in aluminium salt processing procedure is aluminium chloride, sulphur
One or more in sour aluminium or aluminum nitrate, aluminium salt concentration are 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, processing time
For 0.5 ~ 3 hour.
23. in accordance with the method for claim 19, it is characterised in that：Ammonium fluosilicate processing procedure is as follows：Y molecular sieve adds water to match somebody with somebody
Into the solid mass ratio 3 of liquid：1~6：1 water sample mixing, it is 0.6 ~ 2.0mol/L ammonium fluosilicate aqueous solution then to add concentration, in 70 ~
120 DEG C are handled 1 ~ 4 hour, and wherein ammonium fluosilicate solution addition needs 9 ~ 30g of pure fluosilicic acid ammonium to count according to every 100g molecular sieves.
24. in accordance with the method for claim 18, it is characterised in that：The drying process process：90 ~ 300 DEG C of dryings 2 ~ 10
Hour.
25. in accordance with the method for claim 18, it is characterised in that：Impregnation method is impregnated using supersaturation, dip time 1
~ 5 hours.
26. in accordance with the method for claim 18, it is characterised in that：Rapid draing temperature is 50 ~ 300 DEG C, during rapid draing
Between be 1 ~ 60 minute.
27. according to the method described in claim 18 or 26, it is characterised in that：Rapid draing temperature is higher than organic solvent boiling point,
Fast drying time is 3 ~ 20 minutes.
28. in accordance with the method for claim 18, it is characterised in that：The alkali lye that described alkali desiliconization processing procedure uses is hydrogen
The concentration of the aqueous solution of sodium oxide molybdena or potassium hydroxide, wherein alkali lye is 0.1wt% ~ 2wt%；50 ~ 100 DEG C of base extraction temperature, place
It is 0.5 ~ 4 hour to manage the time, and the solid mass ratio of alkali lye/molecular sieve liquid is 5:1~10:1.
29. the modified Y molecular sieve described in a kind of claim 1 or 2 is hydrogenated with high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil
Application during the hydrocracking reaction of conversion.
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| CN106669786B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil hydrocracking catalyst and preparation method thereof |
| CN108114737B (en) * | 2016-11-28 | 2020-03-17 | 中国石油化工股份有限公司 | Hydrogenation saturation catalyst, preparation method and application thereof |
| CN106669776A (en) * | 2017-01-05 | 2017-05-17 | 兰州理工大学 | Preparation method of toluene alkylation catalyst prepared from benzene |
| CN116060091A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method and application thereof |
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| KR101307226B1 (en) * | 2004-12-17 | 2013-09-12 | 할도르 토프쉐 에이/에스 | Hydrocracking process |
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| 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 |
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