CN105621432B - A kind of modified beta molecular sieve and preparation method thereof - Google Patents
A kind of modified beta molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of modified beta molecular sieve and preparation method thereof, modified beta molecular sieve has the following properties that：Body phase silica alumina ratio is 30 ~ 80, wherein superficial layer silica alumina ratio 50 ~ 130, and superficial layer silica alumina ratio is higher than body phase silica alumina ratio 30 ~ 70；400 ~ 800m of specific surface area2/ g, 0.2 ~ 0.60ml/g of pore volume；Infrared 0.1 ~ 0.6mmol/g of acid content；Relative crystallinity 100% ~ 150%.The preparation method of modified beta molecular sieve of the present invention is as follows：Beta-molecular sieve after exchanging ammonium is pre-processed, and is dried, and carries out carbon deposit reaction, and high-temperature roasting processing, then through dealumination treatment, drying, processing of making charcoal, obtains modified beta molecular sieve.The silica alumina ratio of molecular sieve surface layer of the present invention has broad application prospects during being higher than body phase silica alumina ratio, hydrocracking reaction.
Description
Technical field
The present invention relates to a kind of modified beta 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, 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, beta-molecular sieve by
In its unique three-dimensional twelve-ring structure so that it is widely used in hydrocracking process, especially diesel oil hydrogenation modification
Process.But because the property of acidic zeolite carrier causes it especially sensitive to nitride, nitride is readily adsorbed in molecular sieve
Surface and cause molecular sieve to be poisoned, therefore activity is substantially reduced, and is difficult operation steady in a long-term in the industrial production.Also, with
The increase of sour density on molecular sieve, the anti-nitrogen ability of catalyst is remarkably decreased.For this problem, conventional method is to pass through at present
The method of acid site quantity on dealuminzation or dealumination complement silicon processing reduction molecular sieve is carried out to beta-molecular sieve to solve, but the party
Method processing procedure is to carry out dealuminzation simultaneously inside and outside whole molecular sieve, therefore, while the silica alumina ratio of molecular sieve is improved, due to
Acid centre is reduced, and its activity is greatly reduced.So, between improving the anti-nitrogen ability of catalyst and keeping hydrogenation cracking activity
Insoluble contradiction is there is, conventional molecular sieve modified process is difficult while taking into account the two problems.
CN201110350743.8 discloses preparation and the method for modifying of a kind of beta-molecular sieve, and this method passes through hydro-thermal process
Beta-molecular sieve is modified with reference to aluminium salt processing, but silica alumina ratio layer is uniformly distributed inside and outside the obtained beta-molecular sieve of this method, when de-
When aluminium depth is high, reactivity is relatively low, and when either shallow dealumination treatment, then the hydrocracking catalyst less stable prepared.
CN00123130.8 discloses a kind of preparation method of the hydrocracking catalyst containing beta-molecular sieve, β points in the invention
Son sieve processing procedure is acid treatment combination hydrothermal treatment process, it is difficult to meet the requirement of activity and stability simultaneously.
The content of the invention
In view of the shortcomings of the prior art, the present invention puies forward a kind of modified beta molecular sieve and preparation method thereof, modified molecules of the present invention
The silica alumina ratio of the characteristics of sifter device has sial uneven distribution, wherein modified beta molecular sieve superficial layer（Silica alumina ratio described in text is
SiO2/Al2O3Mol ratio）Higher than body phase silica alumina ratio.
The modified beta molecular sieve of the present invention has the following properties that：Body phase silica alumina ratio be 30 ~ 80, wherein superficial layer silica alumina ratio 50 ~
130, preferably 60 ~ 120, superficial layer silica alumina ratio is higher than body phase silica alumina ratio 30 ~ 70, wherein described superficial layer refers to molecular sieve outer surface
To 5 ~ 400nm of inside thickness range, preferably 10 ~ 200nm, wherein superficial layer are primary in beta-molecular sieve before modified；Modified β points
Son sieve sodium oxide molybdena weight/mass percentage composition is less than 1.0%, preferably smaller than 0.5%；400 ~ 800m of modified beta molecular sieve specific surface area2/ g, it is excellent
Select 500 ~ 700m2/g；0.2 ~ 0.60ml/g of pore volume, preferably 0.3 ~ 0.5ml/g；Infrared 0.1 ~ 0.6mmol/g of acid content, preferably
0.2~0.5mmol/g；Relative crystallinity 100% ~ 150%, preferably 120% ~ 140%.
The preparation method of modified beta molecular sieve of the present invention, including following content：
（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution with sodium form β zeolite powders；
（2）Beta-molecular sieve after exchanging ammonium carries out first dealumination treatment, dries；
（3）Dried beta-molecular sieve is fully contacted with liquid or gaseous unsaturated olefin, is then entered in oxygen-containing atmosphere
Row carbon deposit reacts；
（4）The beta-molecular sieve of carbon deposit carries out quick high-temp calcination process；
（5）Step（4）Molecular sieve after processing carries out second of dealumination treatment；
（6）Step（5）Obtained beta-molecular sieve carries out processing of making charcoal, obtains modified beta molecular sieve after filtering, drying.
Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：By raw material of sodium form β zeolites in ammonia spirit 60 ~
Exchanged at 120 DEG C, preferably 60 ~ 90 DEG C, swap time is 1 ~ 3 hour, exchange times are 1 ~ 4 time, the β boilings after finally being exchanged
Stone Na2O content is less than 3.0%；Wherein the silica alumina ratio of sodium form β zeolites is 20 ~ 30, sodium oxide molybdena weight/mass percentage composition 3% ~ 5%；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 first dealumination treatment process can be one in hydro-thermal process, acid treatment or aluminium salt processing procedure
Plant or several：Wherein, hydrothermal conditions are：Temperature be 400 ~ 600 DEG C, pressure be 0.01 ~ 0.5MPa, processing time be 1.0 ~
4.0 hour；Inorganic acid and/or organic acid used in acid treatment process can be sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, vinegar
One or more in acid, inorganic acid and/or organic acid are calculated as 0.1 ~ 0.7mol/L with H+；Inorganic acid and/or organic acid soln
Compare 3 with the liquid/solid of molecular sieve:1~30:1,30 ~ 80 DEG C of acid treatment temperature, processing time is 0.5 ~ 3 hour；Aluminium salt processing procedure
Aluminium salt used can be the one or more in aluminium chloride, aluminum sulfate or aluminum nitrate, and aluminium salt concentration is 0.05 ~ 2mol/L, aluminium
Salt treatment temperature is 50 ~ 120 DEG C, and processing time is 0.5 ~ 3 hour.
Step（2）Described drying temperature is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
Step（3）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 is immersed in liquefied olefines.Described alkene fully connects with molecular sieve
Touch and typically carry out at normal temperatures, described unsaturated hydrocarbons state phase is phase under normal temperature.
Step（3）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（4）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 to add the beta-molecular sieve of carbon deposit to be warming up in the Muffle furnace of sintering temperature in advance
Roasting.
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 to use inorganic acid and/or organic acid treating step（4）Obtained beta-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 0.3 ~ 2mol/L, preferably 0.6 ~ 1.5mol/L；The liquid/solid mass ratio of sour dealumination treatment process is 3:1~30:1；
60 ~ 120 DEG C for the treatment of temperature, processing time is 0.5 ~ 3 hour.
Ammonium fluosilicate dealumination complement silicon process is by step（4）Obtained beta-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 ~ 2.0mol/L ammonium fluosilicate aqueous solution, in 70 ~ 120 DEG C handle 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, is remained on removing molecular sieve at 400 ~ 600 DEG C
Carbon deposit.
The step of described in the inventive method（3）、（4）It can also replace in the following way：By step（2）Obtained β
Molecular sieve impregnates in organic solvent, then rapid draing；Wherein described organic solvent is selected from alkane, petroleum ether, tetrachloro
Change the one or more in carbon, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene, impregnation method is impregnated using supersaturation, dip time
For 1 ~ 5 hour；Drying temperature is 50 ~ 300 DEG C, and preferably drying temperature is higher than the boiling point of organic solvent, and drying time is 1 ~ 60 point
Clock, preferably 3 ~ 20 minutes.
The present invention carries out microsection component analyzing come measure and calculation molecular sieve surface using transmission electron microscope X-ray electronic spectroscopy
Layer and body phase silica alumina ratio.
The present invention is carried out after dealuminzation pretreatment to beta-molecular sieve, is protected by internal carbon distribution or organic solvent in molecular sieve
The aluminium position in portion, follow-up dealumination treatment process is carried out on the outer surface, after dealuminzation terminates, then high temperature removes the carbon deposit inside molecular sieve
Or organic solvent, recover the acid sites position inside molecular sieve.The inventive method is carried out by selectivity to beta-molecular sieve outer surface
Dealuminzation, the selective silica alumina ratio for improving beta-molecular sieve outer surface.Modified beta molecular sieve of the present invention, which can be used for preparing hydrogenation, to be split
Change catalyst, during the different hydrocracking reactions such as high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion
Have broad application prospects.
Embodiment
Below by embodiment, the present invention is further described, but is not so limited the present invention.
Embodiment 1
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 1.5mol/L with concentration is solid according to liquid
Than 4:1 mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 2.5%；
（2）To step（1）540 DEG C of obtained beta-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）First by step（3）The dry 3h of 200 DEG C of gained molecular sieve, then, takes heptene soaking step（3）The molecule of gained
Sieve 2 hours, then, is heated 20 hours in air atmosphere at 150 DEG C；
（5）Step（4）Molecular sieve after processing, which is directly placed into, to be previously heated in 450 DEG C of Muffle furnace, is calcined 8 minutes；
（6）Step（5）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with H+ concentration 0.8mol/L hydrochloric acid solution, and 90
Constant temperature handles 2h at DEG C；
（7）Through step（6）After beta-molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, obtain real
The molecular sieve of example 1 is applied, numbering is β -1.
Embodiment 2
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 1.2mol/L with concentration is solid according to liquid
Than 3:1 mixing, 95 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 1.5%；
（2）Step（1）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, then heats to 50 DEG C, is stirring
The citric acid solution 300ml that H+ is calculated as 0.3mol/L, isothermal reaction 2 hours are added during mixing.
（3）First by step（2）The dry 3h of 120 DEG C of gained molecular sieve, then, takes heptene soaking step（2）The molecule of gained
Sieve 4 hours, then, is heated 15 hours in air atmosphere at 300 DEG C；
（4）Step（3）Molecular sieve after processing, which is directly placed into, to be previously heated in 500 DEG C of Muffle furnace, is calcined 20 minutes；
（5）Step（4）The molecular sieve of gained is according to liquid-solid ratio 5:1 and H+Concentration 1.0mol/L hydrochloric acid solution mixing, 95
Constant temperature handles 2h at DEG C；
（6）Through step（5）After beta-molecular sieve molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours,
The molecular sieve of embodiment 2 is obtained, numbering is β -2.
Embodiment 3
（1）Take laboratory prepare sodium form beta-molecular sieve molecular screen primary powder 200g, the ammonium nitrate for being 1.0mol/L with concentration by
According to liquid-solid ratio 3:1 mixing, 65 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as
2.2%；
（2）Step（1）530 DEG C of the beta-molecular sieve of gained, hydro-thermal process 3 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
0.4mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.
（4）First by step（3）The dry 6h of 150 DEG C of gained molecular sieve, then, takes hexadiene soaking step（3）Point of gained
Son sieve 2 hours, then, is heated 15 hours in air atmosphere at 200 DEG C；
（5）Step（4）Molecular sieve after processing, which is directly placed into, to be previously heated in 500 DEG C of Muffle furnace, is calcined 5 minutes；
（6）Step（5）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, then heats to 70 DEG C, is stirring
The acetum 300ml that H+ is calculated as 0.8mol/L, isothermal reaction 2 hours are added during mixing.；
（7）Through step（6）After beta-molecular sieve after citric acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, obtain
The molecular sieve of embodiment 3 is obtained, numbering is β -3
Embodiment 4
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 2.0mol/L with concentration is solid according to liquid
Than 4:1 mixing, 90 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 1.8%；
（2）To step（1）580 DEG C of obtained beta-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 75 DEG C, is stirring
0.7mol/L aluminum sulfate solution 300ml, isothermal reaction 2 hours are added during mixing.
（4）First by step（3）The dry 3h of 200 DEG C of gained molecular sieve, then, takes hexadiene soaking step（3）Point of gained
Son sieve 2 hours, then, in air atmosphere, 150 DEG C are heated 20 hours；
（5）Step（4）Molecular sieve after processing, which is directly placed into, to be previously heated in 480 DEG C of Muffle furnace, is calcined 30 minutes；
（6）Step（5）The molecular sieve of gained is according to liquid-solid ratio 5:1 and H+Concentration 0.9mol/L hydrochloric acid solution mixing, 85
Constant temperature handles 3h at DEG C；
（7）Through step（6）After beta-molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, obtain real
The molecular sieve of example 4 is applied, numbering is β -4.
Embodiment 5
Molecular sieve modified processing procedure：
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 1.0mol/L with concentration is solid according to liquid
Than 3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 2.0%.
（2）Step（1）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, then heats to 60 DEG C, is stirring
H is added during mixing+It is calculated as 0.3mol/L citric acid solution 300ml, isothermal reaction 2 hours.
（3）Step（2）The dry 4h of 200 DEG C of gained molecular sieve；
（4）Take toluene solvant soaking step（3）The molecular sieve of gained 3 hours；
（5）Step（4）130 DEG C of molecular sieve drying 15 minutes after processing；
（6）Step（5）The molecular sieve of gained is according to liquid-solid ratio 5:1 and H+Concentration 0.8mol/L hydrochloric acid solution mixing, 80
Constant temperature handles 2h at DEG C；
（7）Through step（6）After beta-molecular sieve molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours,
The molecular sieve of embodiment 6 is obtained, numbering is β -5.
Embodiment 6
Molecular sieve modified processing procedure：
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 1.0mol/L with concentration is solid according to liquid
Than 3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 2.0%.
（2）To step（1）560 DEG C of obtained beta-molecular sieve, hydro-thermal process 3 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 85 DEG C, is stirring
0.6mol/L aluminum sulfate solution 300ml, isothermal reaction 2 hours are added during mixing.
（4）Step（3）The dry 4h of 200 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 30 minutes after processing；
（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 5:1 and H+Concentration 0.9mol/L hydrochloric acid solution mixing, 80
Constant temperature handles 3h at DEG C；
（8）Through step（7）After beta-molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, obtain real
The molecular sieve of example 5 is applied, numbering is β -6.
Comparative example 1
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 2.0mol/L with concentration is solid according to liquid
Than 6:1 mixing, 90 DEG C exchange 3 hours, repeat this process 2 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 1.8%；
（2）Step（1）Obtained beta-molecular sieve is at 590 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 mixes with H+ concentration 0.5mol/L hydrochloric acid solution, and 90
Constant temperature handles 2h at DEG C；
（4）Through step（3）After beta-molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, compared
Compared with the molecular sieve of example 1, numbering is B-1.
Comparative example 2
（1）The former powder 200g of sodium form beta-molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 2.0mol/L with concentration is solid according to liquid
Than 6:1 mixing, 90 DEG C exchange 3 hours, repeat this process 2 times, and Na contents are with Na in the beta-molecular sieve after exchange2O is calculated as 1.8%；
（2）Step（1）Obtained beta-molecular sieve is at 560 DEG C, hydro-thermal process 2 hours under 0.1MPa；
（3）Step（2）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with H+ concentration 0.4mol/L citric acid solution,
Constant temperature handles 2h at 80 DEG C；
（4）Through step（3）After beta-molecular sieve after acid treatment, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, compared
Compared with the molecular sieve of example 2, numbering is B-2.
The physicochemical property of embodiment 1 ~ 6 and the modified beta molecular sieve of comparative example 1 ~ 2 is listed in the table below 1.
Embodiment 7
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 478g and nickel nitrate 488g is taken to configure 1000ml leachings after being dissolved in water
Active metal is respectively 40g/100ml and 12g/100ml with WO3 and NiO cubages in stain solution, gained dipping solution, 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 and unformed
Sial is according to 1:1:2 ratio is mixed with carrier, be respectively labeled as Z-1, Z-2, Z-3, Z-4, Z-5, Z-6, ZB-1,
ZB-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 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 ~ 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 physicochemical property of the embodiment of table 1 and comparative example molecular sieve.
The raw material oil nature of table 2.
The appreciation condition of table 3.
The evaluation result of table 4.
Embodiment 2 and the catalyst stability contrast test of comparative example 1 under the oily high nitrogen-containing of the refining stage of table 5 generation.
Embodiment 3 and the catalyst stability contrast test of comparative example 2 under the oily high nitrogen-containing of the refining stage of table 6 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 compared with comparative example while high activity is kept, and anti-nitrogen ability is apparently higher than comparative example catalyst.
Claims (19)
1. a kind of modified beta molecular sieve, it is characterised in that：Modified beta molecular sieve has the following properties that：Body phase silica alumina ratio is 30 ~ 80, its
Middle superficial layer silica alumina ratio 50 ~ 130, superficial layer silica alumina ratio is higher than body phase silica alumina ratio 30 ~ 70, wherein described superficial layer refers to molecular sieve
Outer surface is to 5 ~ 400nm of inside thickness range, and wherein superficial layer is primary in beta-molecular sieve before modified；Modified beta molecular sieve compares table
400 ~ 800m2/g of area, 0.2 ~ 0.60ml/g of pore volume；Infrared 0.1 ~ 0.6mmol/g of acid content；Relative crystallinity 100% ~ 150%；
Described silica alumina ratio is SiO2/Al2O3Mol ratio.
2. according to the beta-molecular sieve described in claim 1, it is characterised in that：Modified beta molecular sieve superficial layer refers to molecular sieve outer surface extremely
10 ~ 200nm of inside thickness range.
3. the preparation method of the modified beta molecular sieve described in a kind of claim 1 or 2, it is characterised in that including following content：（1）
Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution with sodium form β zeolite powders；（2）Beta-molecular sieve after exchanging ammonium carries out first
Dealumination treatment, is dried；（3）Dried beta-molecular sieve is fully contacted with liquid or gaseous unsaturated olefin, then oxygenous
Carbon deposit reaction is carried out in atmosphere；（4）The beta-molecular sieve of carbon deposit carries out quick high-temp calcination process；（5）Step（4）Molecule after processing
Sieve carries out second of dealumination treatment；（6）Step（5）Obtained beta-molecular sieve carries out processing of making charcoal, changed after filtering, drying
Property beta-molecular sieve.
4. 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 or aluminium salt processing procedure.
5. in accordance with the method for claim 4, it is characterised in that：Hydrothermal conditions are：Temperature is 400 ~ 600 DEG C, pressure
For 0.01 ~ 0.5MPa, processing time is 1.0 ~ 4.0 hours.
6. in accordance with the method for claim 4, it is characterised in that：Inorganic acid and/or organic acid used in acid treatment process are
One or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, acetic acid, inorganic acid and/or organic acid are with H+It is calculated as 0.1 ~
The liquid/solid of 0.7mol/L, inorganic acid and/or organic acid soln and molecular sieve compares 3:1~30:1；30 ~ 80 DEG C of acid treatment temperature, place
The reason time is 0.5 ~ 3 hour.
7. in accordance with the method for claim 4, 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 is 0.05 ~ 2mol/L；Aluminium salt treatment temperature is 50 ~ 120 DEG C, during processing
Between be 0.5 ~ 3 hour.
8. in accordance with the method for claim 3, it is characterised in that：Step（2）Described drying temperature is 90 ~ 300 DEG C, is dried
Time is 2 ~ 10 hours.
9. in accordance with the method for claim 3, it is characterised in that：Step（3）Described unsaturated olefin is C2~C10Positive 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 hours；Liquid unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, 0.5 ~ 4 hour time of contact, molecule
Sieve is immersed in liquefied olefines.
10. in accordance with the method for claim 3, it is characterised in that：Step（3）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%；Carbon deposit reaction condition is：50 ~ 500 DEG C of reaction temperature, the reaction time is 1 ~ 50 hour.
11. in accordance with the method for claim 3, it is characterised in that：Step（4）Described quick high-temp roasting condition is：Roasting
It is 400 ~ 600 DEG C to burn temperature, and roasting time is 2 ~ 50 minutes.
12. 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.
13. in accordance with the method for claim 12, it is characterised in that：Sour dealumination process is with inorganic acid and/or organic acid
Manage step（4）Obtained beta-molecular sieve；Inorganic acid or organic acid are one in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid
Plant or a variety of, the concentration of inorganic acid and/or organic acid is with H+It is calculated as 0.3 ~ 2mol/L；The liquid/solid quality of sour dealumination treatment process
Than for 3:1~30:1,60 ~ 120 DEG C for the treatment of temperature, processing time is 0.5 ~ 3 hour.
14. in accordance with the method for claim 12, it is characterised in that：Ammonium fluosilicate dealumination complement silicon process is by step（4）
To beta-molecular sieve add water and 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, is handled 1 ~ 4 hour, wherein ammonium fluosilicate solution addition needs to deposit according to every 100g molecular sieves in 70 ~ 120 DEG C
9 ~ 30g of ammonium fluosilicate is counted.
15. 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.
16. in accordance with the method for claim 3, it is characterised in that：Described step（3）、（4）In the following way instead of：
By step（2）Obtained beta-molecular sieve impregnates in organic solvent, then rapid draing.
17. in accordance with the method for claim 16, it is characterised in that：Wherein described organic solvent is selected from alkane, oil
One or more in ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene.
18. in accordance with the method for claim 16, it is characterised in that impregnation method is impregnated using supersaturation, dip time is 1 ~
5 hours.
19. in accordance with the method for claim 16, it is characterised in that：Drying temperature is 50 ~ 300 DEG C, and drying time is 1 ~ 60
Minute.
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