CN104549417B - Boron modified Y-type molecular sieve and preparation method thereof - Google Patents
Boron modified Y-type molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a modified Y-type molecular sieve. The method comprises the following steps: (1) preparing an ammonium fluoroborate solution; (2) placing an industrially produced Y-type molecular sieve into the ammonium fluoroborate solution in the step (1), performing a following dealuminzation boron-supplementing reaction in a slurry system, NH4BF4+Al<3+>+Na<+>=NaAlF4(large particle precipitate) +B<3+>+NH4<+>, and carrying out solid-liquid separation and drying after the reaction is ended; (3) spraying and leaching the ethanol solution of a macromolecular organosilicon compound in the materials dried in the step (2), drying and carrying out hydro-thermal treatment to prepare the modified Y-type molecular sieve. According to the method, a boron-containing compound and the organosilicon compound are adopted to modify the Y-type molecular sieve to prepare a boron-containing modified Y-type molecular sieve containing high and medium strong acid.
Description
Technical field
The present invention relates to a kind of Modified Zeolite Y and preparation method thereof, more particularly to using boron-containing compound with have
The method that organic silicon compound is modified to Y type molecular sieve, prepares high silica alumina ratio, the Modified Zeolite Y of skeleton boracic.
Background technology
Hydrocracking technology has that adaptability to raw material is strong, production operation and the big, good product quality of products scheme flexibility etc.
The charging of various heavy inferiors can be converted into the high-quality jet fuel of market in urgent need, diesel oil, lube basestocks by feature
And chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern oil refining and petro chemical industry are most important heavy
One of oily deep processing technique, at home and abroad obtains increasingly extensive application.But because crude quality is deteriorated year by year, the height of import
Sulphur crude oil increases considerably, and refinery is to increase economic efficiency, and starts commonly used crude oil deep vacuum distillation technology so that reducing pressure
Doing of distillate has brought up to 600 DEG C about by original 520 DEG C, and its density is increasing, boiling range more and more higher, institute's hydrocarbonaceous
The impurity contents such as the molecular weight of molecule is increasing, structure also becomes increasingly complex, sulphur nitrogen also get more and more, and greatly increase hydrogenation and split
Change the difficulty processing, these are proposed higher requirement to hydrocracking technology and hydrocracking catalyst.
In catalytic field, how to prepare with high activity, fine selectivity and long-life effective catalyst are always
People's concern and the problem paid attention to.For with the catalyst of carrier loaded active component, using the carrier of high-specific surface area,
The loaded catalyst of high dispersive can be prepared, thus improving the reactivity worth of catalyst；There is larger pore volume, then in catalyst
Its anti-coking or coking resistivity, and then the service life of prolongation catalyst can be improved, also help catalyst regeneration simultaneously.Carry
The pore volume of high carrier and specific surface area, to giving full play to active constituent catalyst activity, improve catalyst performance, have positive
Meaning.
According to carbonium ion reaction mechanism, in feedstock oil there is the speed of hydrocracking reaction with molecular weight in all kinds of hydrocarbon molecules
Increase and increase, after reaching a maximum, reaction speed begins to decline, and this is due to microporous catalyst, especially with
Zeolite is the catalyst of main acid function, is affected by spreading the effect controlling, that is, when the hydrocarbon molecule diameter of reactant is big
When the orifice diameter of catalyst micropore, reactant molecule cannot with micropore in activated centre directly contact, at this moment diffusion make
With the rate-determining steps of reaction will be become.With the increase of Hydrocracking Raw Oil hydrocarbon molecule, and its structure is also more complicated, uses
The hydrocracking catalyst of typical cell structure is controlled by diffusion is affected more and more obvious, the hydrocarbon molecule of larger molecular weight, especially
It is condensed-nuclei aromatics, is contacted with the activated centre in duct it is impossible to enter into because volume is larger inside catalyst duct.
But hydrocracking catalyst inner surface occupies more than the 90% of effect active surface area, the catalytic active center overwhelming majority is distributed in
On the inner surfaces of pores of catalyst, thus those height do polycyclic heavy constituent can not be hydrogenated with, cracking reaction, and be retained in
In hydrocracking tail oil.It is higher that this results in the BMCI value being hydrocracked as conversion oil, T90, T95 and do and raw material oil phase
More inconspicuous than reducing, sometimes even raise, the product quality of obtained hydrocracking tail oil product is poor；Further, since it is thick
PAH can not occur ring-opening reaction, and easily causes condensed-nuclei aromatics to assemble, and causes green coke, carbon distribution, impact catalyst uses the longevity
Life.At present, industrial part enter heavy hydrogenated cracked stock oil device produce hydrocracking tail oil do and raw material oil phase
Ratio does not reduce, and have even also increases, and device does not reach expection service cycle, studies carefully its main cause it is simply that by institute
The Hydrocracking Raw Oil that the catalyst pore structure using is not suitable for processing containing macromolecule hydrocarbon causes.Molecular sieve is that hydrogenation splits
Change the main acidic cracking components of catalyst, its pore structure is the most key factor of impact catalyst performance.Therefore, research how
Improve the pore structure of Y type molecular sieve, improve pore volume and the average pore size of molecular sieve, increase secondary pore ratio, have very positive
Meaning.
Synthesis NaY and HY can not meet the use requirement of catalyst due to activity, pore structure and stability aspect, so must
It must be modified processing.Aluminium atom content in Y zeolite catalysis performance and zeolite and state are the closest, therefore, molecule
Sieve dealuminzation is the topmost modified method of Y type molecular sieve, and the dealuminzation mode of Y zeolite is a lot, but is summed up and takes off nothing more than hydro-thermal
Aluminium and two kinds of chemical dealuminization.Patent US3293192 and US3449070 provide be NaY zeolite is exchanged through ammonium, high-temperature roasting
The USY zeolite standby with secondary ammonium exchange system, this zeolite has preparation method simply, has certain resistant to ammonia stability and certain two
Secondary aperture, this zeolite was once extensively applied with the hydrocracking catalyst combining oily company, showed preferable catalytic performance, but
This molecular sieve nitrogen resistance is poor, and less and its structural stability is inadequate for pore volume and aperture, is gradually substituted by hydrophobic zeolite.
US4503023 and US5013699 describes the hydrophobic molecule sieve of two methods route preparation respectively, and the former adopts NaY zeolite to use
Ammonium fluosilicate carries out the dealumination complement silicon mode of liquid phase, prepares molecular sieve crystallinity height, and silica alumina ratio is high, has certain resistance to organic nitrogen
The ability of poisoning, but because its structure is excessively complete, almost do not have secondary pore, pore volume and aperture relatively small yet；The latter adopts
Hydro-thermal process is combined with strong acid dealuminzation, prepared there are abundant secondary apertures, high-crystallinity, the modified Y type of high silica alumina ratio divide
Son sieve, but the method preparation Y type molecular sieve due to by strong acid action face structure destroy more serious, cause zeolite composition and
The inhomogeneities of structure, has a certain impact to catalytic performance.Patent CN96119840.0 changes further to patent US5013699
Enter, its strong acid is changed into certain cushioning liquid, reduce the severity of process, improve the performance of molecular sieve, prepared one kind
There is abundant secondary pore, high-crystallinity, high-specific surface area and high silica alumina ratio, and the good modified Y type of structure and composition uniformity divides
Son sieve, typically in 1.7nm ~ 2.0nm, secondary pore ratio is 46.0% ~ 50%, pore volume 0.40mL/g ~ 0.50mL/g, compares table in its aperture
Area 800m2/g ~850m2/ g, relative crystallinity 90% ~ 96%, silica alumina ratio 8 ~ 12, adopt in patent CN03133815.1
This molecular sieve, show when processing the Hydrocracking Raw Oil doing less than 530 DEG C very high activity, in selective and
Open-loop performance.But after process height does feedstock oil, after the heavy decompressed wax oil of deep vacuum distillation isolation technics, due to
In catalyst, the sour ratio of the middle strong acid of Cracking Component, B is not high, not enough to the conversion capability of super large hydrocarbon molecules, to polycyclic heavy
The selective opening of component is indifferent, and device real-world operation effect is undesirable.
Content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of Modified Zeolite Y and its preparation side
Method.The method is modified process using boron-containing compound and organo-silicon compound to Y type molecular sieve to be prepared senior middle school's strong acid and contains
The boracic modified Y type molecular sieve of amount.
The property of Modified Zeolite Y of the present invention is as follows：Specific surface 500m2/g~900m2/ g, preferably 600 ~ 800m2/ g,
Total pore volume 0.20ml/g ~ 0.6ml/g, average pore size 1.9 ~ 3.0nm, relative crystallinity 80% ~ 110%, silica alumina ratio 5 ~ 30, excellent
Select 10 ~ 20, cell parameter is 2.425 ~ 2.445nm, middle strong acid ratio 50% ~ 90%, boron oxide content≤4.0wt%, preferably≤
2.5wt%.
The preparation method of Modified Zeolite Y of the present invention, comprises the steps：
（1）Prepare fluoboric acid ammonia solution；
（2）Industrial production Y molecular sieve is taken to put into step（1）Fluoboric acid ammonia solution in, slurry system occur following dealuminzation
Mend boron reaction：NH4BF4+ Al3++Na+=NaAlF4(bulky grain precipitation)+B3++NH4 +, after terminating, carry out separation of solid and liquid, drying；
（3）To step（2）The ethanol solution of macromolecular organo-silicon compound, drying, water is sprayed in dried material
Modified Zeolite Y of the present invention is prepared after heat treatment.
The inventive method, step（1）Fluoboric acid ammonia solution process for preparation is as follows：Appropriate fluoboric acid ammonia is taken to be dissolved in the steaming of stirring
In distilled water, temperature is 30 ~ 60 DEG C, and through filtering, making the stable concentration of clear is 0.2 ~ 4.0mol/L, and optimum is
The fluoboric acid ammonia solution of 0.5 ~ 2.0mol/L.
The inventive method, step（2）Industrial production Y molecular sieve is low sodium Y molecular sieve, Na2O content be 0.4wt% ~
2.0wt%, optimum 0.8wt% ~ 1.5wt%.
The inventive method, step（2）Middle making beating solid-to-liquid ratio 3:1~10:1,80 ~ 100 DEG C of temperature of pulling an oar, beating time 30 ~
240Min.Pulping process can be carried out in the presence of ultrasonic wave, and ultrasonic frequency is 40～100kHz, and power presses liquor capacity
It is calculated as 2～40W/mL, the performance of Modified Zeolite Y can be improved using ultrasonic wave making beating further.
The inventive method, step（2）60 ~ 180 DEG C of middle baking temperature, preferably 100～150 DEG C, time 3 ~ 8h.
The inventive method, step（3）Middle macromolecular organosilicon can be methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, methyl
Containing hydrogen silicone oil, methyl phenyl silicone oil, silicon ether, one or more of organosilicon such as siloxanes.Organosilicon adopts ethanol as molten
Agent, the amount spraying organosilicon is 1 according to silicon-containing compound quality/molecular sieve quality:20~1:100 meters.Step（3）Be dried temperature
Spend for 60 ~ 100 DEG C, time 3 ~ 8h.
The inventive method, step（3）After drying, hydro-thermal process is carried out in tube furnace, is 400 DEG C ~ 750 DEG C, water in temperature
Hydro-thermal process 30 ~ 300min under the conditions of steam pressure 0.05 ~ 1.0Mpa.
The present invention utilizes the close feature of aluminium congeners boron chemical property, using boron-containing compound, Y type molecular sieve is entered
Row is processed, and the boron element on framework of molecular sieve is substituted aluminium element so that the acidity of Y type molecular sieve and hole structural property obtain
Significantly improve.
The present invention utilizes boron atom to replace topmost acid centre on molecular sieve and is coordinated in undersaturated aluminum-oxygen tetrahedron
Aluminium atom, formed and undersaturated boron oxygen tetrahedron, because boron atom amount is less, chemical property be equally coordinated on framework of molecular sieve
More active, therefore in molecular sieve surface is formed more, strong acid center, substantially increase the acid strength of modified molecular screen.
The present invention realizes dealuminzation in the liquid phase and mends boron reaction, and boron element uniformly replaces part skeleton in the structure of molecular sieve
Aluminium, is conducive to improving the middle strong acid ratio of molecular sieve, improves molecular sieve pore passage structure, give full play to the catalytic of molecular screen material
Energy.
In the molecular sieve modified procedure of the present invention, during boron mended by dealuminzation, do not have after still having the removing of part framework aluminum
There is the supplement obtaining boron atom, substantial amounts of hole can be caused, form secondary pore, the therefore pore passage structure of molecular sieve can obtain substantially
Improvement.
The present invention impregnates macromolecular organo-silicon compound in molecular sieve pore passage, and under hydrothermal high-temperature environment, compound divides
Solution, provides silicon source for molecular sieve dealumination complement silicon process so that framework of molecular sieve structure keeps complete, after structure cell shrinks, still permissible
Keep higher degree of crystallinity and stability, total acid content reduces simultaneously, and acid enhancing.
Larger molecular organicses in molecular sieve pore passage of the present invention, in hydrothermal treatment process, expanded by heating decomposes, to molecule
The microcellular structure of sieve has good reaming effect, and the silicon column that organosilicon remains after Roasting Decomposition simultaneously carries out to microcellular structure propping up
Support or partial destruction, substantially increase the ratio of macroporous structure so that the average pore size of modified molecular screen significantly increases.
The method of modifying of the present invention all belongs to conventional process, does not have special installation and environmental requirement, and raw material can obtain fully
Using whole modifying process technological process is short, and operating procedure is simple.
Specific embodiment
The preparation method of the modified Y molecular sieve of the present invention, specifically includes following steps：
（1）Take appropriate fluoboric acid ammonia crystal, be gradually added in the distilled water that temperature is 30 ~ 60 DEG C of stirrings, filter out solution
In impurity, make the stable fluoboric acid ammonia solution of clear.
（2）Take industrial production low sodium Y molecular sieve, sodium oxide content 0.5 ~ 2.0wt%, insert the fluoboric acid under stirring
Ammonia solution, solid-to-liquid ratio 3:1~10:1, solution temperature rises to 80 ~ 100 DEG C, can open Ultrasound Instrument, mixed serum is placed in ultrasonic
Under ripple irradiates, ultrasonic frequency is 40～100kHz, and power is calculated as 2～40W/m by liquor capacity.Occur as follows in slurry system
Boron reaction mended by dealuminzation：
NH4BF4+ Al3++Na+=NaAlF4(bulky grain precipitation)+B3++NH4 +
Slurries are filtered, solid-liquor separation simultaneously, will filter by reaction time 30 ~ 240Min, slurries and solid particle precipitate and separate
Cake is dried process, 60 ~ 180 DEG C of temperature, time 3 ~ 8h.
（3）Prepare the ethanol solution of the compounds such as organic silicone oil, organic silicone oil is dropped to the ethanol of stirring at normal temperature state
In, treat solution clear.Take step（2）Prepare molecular sieve, insert and spray in tank, spray the second of the organo-silicon compound of metering
Alcoholic solution, after organic solvent homogeneous immersion molecular sieve, sprays end.Process is dried to molecular sieve after dipping, temperature 60 ~
100 DEG C, time 1 ~ 8h；Molecular sieve after drying is placed in pipe type water heat-treatment furnace, temperature programming to treatment temperature, treatment temperature
For 400 DEG C ~ 750 DEG C, water vapour pressure 0.05 ~ 1.0Mpa, process 30 ~ 300min, prepare this modified molecular screen.
Analysis method of the present invention：Specific surface and pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and structure cell ginseng
Number adopts x-ray diffraction method, and silica alumina ratio adopts chemical method, and meleic acid amount, B acid amount and L acid amount adopt pyridine adsorption infrared light
Spectrometry, wherein B acid amount is meleic acid amount with the summation of L acid amount, the total acid content that middle strong acid is desorbed between being 250 ~ 350 DEG C.
The following examples are used for illustrating in greater detail the present invention, but the scope of the present invention is not limited solely to these embodiments
Scope.
Embodiment 1
Measure 219.0g fluoboric acid ammonia to be gradually added in the 2000mL distilled water of 50 DEG C of stirrings, prepare fluoboric acid ammoniacal liquor
Solution.Take 500g industrial production low sodium ammonium Y molecular sieve（Na2O content is 1.1%, degree of crystallinity 102%, and lattice constant is
2.475nm）, molecular sieve is added gradually in the fluoboric acid ammonia spirit stirring, slurry temperature improves to 95 DEG C, processes
60min；Slurries and solid particle first（Cryolite）Separate, then carrying out separation of solid and liquid, filter cake is carried out at 120 DEG C
It is dried, time 6h；Take above-mentioned 500g molecular sieve, by 200mL organic silicone oil ethanol solution（Concentration 18.4gSiO2/100mL）Uniformly
Spray on molecular sieve.Process, 80 DEG C of temperature, time 3h are dried to molecular sieve after dipping；Organo-silicon compound will be contained
Molecular sieve carry out hydro-thermal process, 550 DEG C for the treatment of temperature, pressure 0.05MPa, process 90min, that is, prepare modified point of the present invention
Son sieve, numbering is BCY-1.
Embodiment 2
Sodium ammonium Y low in example 1 is changed to SSY molecular sieve, fluoboric acid ammonia solution concentration is adjusted to 15.2g/100mL, making beating
Solid-to-liquid ratio is 1:5, temperature 70 C of pulling an oar, beating time is 2h, and organosilicon is changed into siloxanes, and with example 1, numbering is BCY- to other
2.
Embodiment 3
Fluoboric acid ammonia solution concentration in example 1 is adjusted to 6.8g/100mL, making beating solid-to-liquid ratio is 1:6, temperature of pulling an oar
90 DEG C, beating time is 4h, and organosilicon is changed into phenyl silicone oil, and hydrothermal conditions are adjusted to 650 DEG C for the treatment of temperature, pressure
0.1MPa, processes 120min, other is with example 1, numbering BCY-3.
Embodiment 4
Carry out in the presence of pulping process in example 1 is placed in ultrasonic wave, ultrasonic frequency is 40kHz, power is pressed molten
Liquid amasss and is calculated as 10W/mL, and, with embodiment 1, numbering is BCY-4 for remaining.
Comparative example 1
Ammonium fluoroborate in example 1 is changed to the ammonium fluosilicate of same molar ratio, other, with example 1, obtains molecular sieve
Numbering BJY-1.
Comparative example 2
Organosilicon in example 1 is sprayed processing procedure cancel, other, with example 1, obtains molecular sieve numbering BJY-2.
The molecular sieve property of embodiment and comparative example gained is shown in Table 1.
Table 1 embodiment and the property of comparative example gained molecular sieve
Claims (11)
1. a kind of preparation method of Modified Zeolite Y is it is characterised in that comprise the steps：
（1）Prepare ammonium fluoroborate solution；
（2）Industrial production Y molecular sieve is taken to put into step（1）Ammonium fluoroborate solution in, slurry system occurs following dealuminzation to mend boron
Reaction：NH4BF4+ Al3++Na+=NaAlF4+B3++NH4 +, after terminating, carry out separation of solid and liquid, drying；
（3）To step（2）The ethanol solution of macromolecular organo-silicon compound is sprayed, at drying, hydro-thermal in dried material
Modified Zeolite Y is obtained after reason；
Specific surface area 500m of described Modified Zeolite Y2/g~900m2/ g, total pore volume 0.20ml/g ~ 0.6ml/g, average pore size
1.9 ~ 3.0nm, relative crystallinity 80% ~ 110%, silica alumina ratio 5 ~ 30, cell parameter is 2.425 ~ 2.445nm, middle strong acid ratio
Example 50% ~ 90%, boron oxide content≤4.0wt%.
2. method according to claim 1 it is characterised in that：The specific surface area of described molecular sieve is 600 ~ 800m2/ g, silicon
Al mole ratio 10 ~ 20, boron oxide content≤2.5wt%.
3. method according to claim 1 it is characterised in that：Step（1）Ammonium fluoroborate solution process for preparation is as follows：Take suitable
Amount ammonium fluoroborate is dissolved in the distilled water of stirring, and temperature is 30 ~ 60 DEG C, through filtering, makes the stable concentration of clear
Ammonium fluoroborate solution for 0.2 ~ 4.0mol/L.
4. method according to claim 1 it is characterised in that：Step（2）Industrial production Y molecular sieve is low sodium Y molecular sieve,
Na2O content is 0.4wt% ~ 2.0wt%.
5. method according to claim 1 it is characterised in that：Step（2）Middle making beating liquid-solid ratio 3:1~10:1, temperature of pulling an oar
80 ~ 100 DEG C, beating time 30 ~ 240Min.
6. method according to claim 5 it is characterised in that：Pulping process is carried out in the presence of ultrasonic wave, ultrasonic wave
Frequency is 40～100kHz, and power is calculated as 2～40W/mL by liquor capacity.
7. method according to claim 1 it is characterised in that：Step（2）60 ~ 180 DEG C of middle baking temperature, drying time 3 ~
8h.
8. method according to claim 1 it is characterised in that：Step（3）Middle macromolecular organosilicon includes methyl-silicone oil, second
Base silicone oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, silicon ether, one or more of siloxanes.
9. method according to claim 1 it is characterised in that：Spray the amount of organosilicon according to silicon-containing compound quality/point
Son sieve quality is 1:20~1:100 meters.
10. method according to claim 1 it is characterised in that：Step（3）Baking temperature be 60 ~ 100 DEG C, time 3 ~
8h.
11. methods according to claim 1 it is characterised in that：Step（3）After drying, hydro-thermal process is entered in tube furnace
OK, temperature be 400 DEG C ~ 750 DEG C, hydro-thermal process 30 ~ 300min under the conditions of water vapour pressure 0.05 ~ 1.0MPa.
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| CN107344116B (en) * | 2016-05-05 | 2019-11-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method and application |
| CN111686784B (en) * | 2019-03-12 | 2023-05-26 | 中国石油天然气股份有限公司 | Preparation method of modified Y-type molecular sieve |
| CN110465331A (en) * | 2019-07-05 | 2019-11-19 | 江苏大学 | The preparation method and application of B-SBA-16 load silico-tungstic acid type ionic liquid composite catalyst |
| CN112758952B (en) * | 2020-12-31 | 2022-12-30 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-ratio Y molecular sieve with hierarchical pore structure and preparation method thereof |
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| CN1033446A (en) * | 1987-12-11 | 1989-06-21 | 中国石油化工总公司石油化工科学研究院 | The preparation method of rich silicon molecular sieve by crystal skeleton |
| CN1178193A (en) * | 1996-09-27 | 1998-04-08 | 中国石油化工总公司 | Modified zeolite and manufacture thereof |
| CN103073024A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1033446A (en) * | 1987-12-11 | 1989-06-21 | 中国石油化工总公司石油化工科学研究院 | The preparation method of rich silicon molecular sieve by crystal skeleton |
| CN1178193A (en) * | 1996-09-27 | 1998-04-08 | 中国石油化工总公司 | Modified zeolite and manufacture thereof |
| CN103073024A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
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