CN104549417A - 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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- CN104549417A CN104549417A CN201310499214.3A CN201310499214A CN104549417A CN 104549417 A CN104549417 A CN 104549417A CN 201310499214 A CN201310499214 A CN 201310499214A CN 104549417 A CN104549417 A CN 104549417A
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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, particularly relate to and adopt boron-containing compound and organo-silicon compound to carry out the method for modification to Y zeolite, prepare the Modified Zeolite Y of high silica alumina ratio, skeleton boracic.
Background technology
The features such as hydrocracking technology has that adaptability to raw material is strong, production operation and products scheme flexibility is large, good product quality, various heavy inferior charging can be converted into the high-quality jet fuel of market in urgent need, diesel oil, lube basestocks and chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, become one of modern oil refining and petro chemical industry most important heavy oil deep processing technique, obtain increasingly extensive application at home and abroad.But because crude quality is deteriorated year by year, the sour crude of import increases considerably, and refinery is for increasing economic efficiency, start generally to adopt crude oil deep vacuum distillation technology, doing of vacuum distillate is made to have brought up to about 600 DEG C by original 520 DEG C, the impurity contents such as its density is increasing, boiling range is more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, structure also becomes increasingly complex, sulphur nitrogen also get more and more, greatly increase the difficulty of hydrocracked, treated, these are proposed higher requirement to hydrocracking technology and hydrocracking catalyst.
In catalytic field, how to prepare and have high activity, fine selectivity and long-life effective catalyst are the problems that people pay close attention to and pay attention to always.For with the catalyst of carrier loaded active component, use the carrier of high-specific surface area, the loaded catalyst of high dispersive can be prepared, thus improve the reactivity worth of catalyst; There is in catalyst larger pore volume, then can improve its anti-coking or coking resistivity, and then the service life of extending catalyst, also help catalyst regeneration simultaneously.Improve pore volume and the specific area of carrier, to giving full play to active constituent catalyst activity, improving catalyst performance, having positive meaning.
According to carbonium ion reaction mechanism, in feedstock oil, the speed of all kinds of hydrocarbon molecule generation hydrocracking reaction increases with the increase of molecular weight, after reaching a maximum, reaction speed starts to decline, this is due to microporous catalyst, especially be the catalyst of main acid function with zeolite, be subject to the impact of spreading the effect controlled, namely when the hydrocarbon molecule diameter of reactant is greater than the orifice diameter of catalyst micropore, reactant molecule directly cannot contact with the activated centre in micropore, and at this moment diffusion will become the rate-determining steps of reaction.Along with the increase of Hydrocracking Raw Oil hydrocarbon molecule, and its structure is also more complicated, the impact that the hydrocracking catalyst of use typical cell structure is subject to spreading control is more and more obvious, the hydrocarbon molecule of larger molecular weight, especially condensed-nuclei aromatics, because volume is comparatively large, inside, catalyst duct can not be entered into and contact with the activated centre in duct.But hydrocracking catalyst inner surface occupies more than 90% of effect active surface area, the catalytic active center overwhelming majority is distributed on the inner surfaces of pores of catalyst, so those height do many rings heavy constituent, and hydrogenation, cracking reaction can not occur, and be retained in hydrocracking tail oil.This just causes hydrocracking to be that to transform the BMCI value of oil higher, and T90, T95 are with to do compared with feedstock oil reduction not obvious, and sometimes even raise, the product quality of the hydrocracking tail oil product obtained is poor; In addition, because condensed-nuclei aromatics ring-opening reaction can not occur, and easily cause condensed-nuclei aromatics to assemble, cause green coke, carbon distribution, affect catalyst service life.At present, the hydrocracking tail oil that the device that industrial part enters heavy hydrogenated cracked stock oil is produced is done and is not reduced compared with feedstock oil, what have even also increases, device does not reach expection service cycle, study carefully its main cause, cause because used catalyst pore structure is not suitable for the Hydrocracking Raw Oil processed containing macromolecule hydrocarbon.Molecular sieve is the main acidic cracking components of hydrocracking catalyst, and its pore structure affects the most key factor of catalyst performance.Therefore, how research improves the pore structure of Y zeolite, improves pore volume and the average pore size of molecular sieve, increases secondary pore ratio, have very positive meaning.
Synthesis NaY and HY can not meet the instructions for use of catalyst, so must carry out modification to it due to active, pore structure and stability aspect.Aluminium atom content in Y zeolite catalysis performance and zeolite and state are the closest, and therefore, molecular sieve dealuminzation is the topmost modified method of Y zeolite, and the dealuminzation mode of Y zeolite is a lot, but is summed up nothing more than hydrothermal dealumination and chemical dealuminization two kinds.Patent US3293192 and US3449070 provide be NaY zeolite is exchanged through ammonium, high-temperature roasting and the standby USY zeolite of secondary ammonium exchange system, it is simple that this zeolite has preparation method, there is certain resistant to ammonia stability and certain secondary pore, the once extensive use of this zeolite is with the hydrocracking catalyst of combining oily company, show good catalytic performance, but this molecular sieve nitrogen resistance is poor, pore volume and aperture are little and its structural stability is inadequate, gradually substitute by hydrophobic zeolite.US4503023 and US5013699 describes hydrophobic molecule sieve prepared by two kinds of method routes respectively, the former adopts NaY zeolite ammonium fluosilicate to carry out the dealumination complement silicon mode of liquid phase, prepare molecular sieve crystallinity high, silica alumina ratio is high, there is the ability that certain resistance to organic nitrogen is poisoning, but because its structure is too complete, almost do not have secondary pore, pore volume and aperture are also relatively little; The latter adopts hydrothermal treatment consists to combine with strong acid dealuminzation, prepare the Modified Zeolite Y having and enrich secondary apertures, high-crystallinity, high silica alumina ratio, but Y zeolite prepared by the method is owing to being subject to the action face structural deterioration of strong acid more serious, cause the inhomogeneities of zeolite the Nomenclature Composition and Structure of Complexes, catalytic performance is had a certain impact.Patent CN96119840.0 improves further to patent US5013699, change its strong acid into certain cushioning liquid, reduce the severity of process, improve the performance of molecular sieve, prepared one and had and enrich secondary pore, high-crystallinity, high-ratio surface sum high silica alumina ratio, and structure and the good Modified Zeolite Y of composition homogeneity, its aperture is generally at 1.7nm ~ 2.0nm, secondary pore ratio is 46.0% ~ 50%, pore volume 0.40mL/g ~ 0.50mL/g, specific area 800m
2/ g ~ 850m
2/ g, relative crystallinity 90% ~ 96%, silica alumina ratio 8 ~ 12, adopts this molecular sieve in patent CN03133815.1, process do the Hydrocracking Raw Oil being less than 530 DEG C time show very high activity, in selective and open-loop performance.But process high do feedstock oil after, especially after adopting the heavy decompressed wax oil of deep vacuum distillation isolation technics, because the ratio of strong acid, B acid in Cracking Component in catalyst is not high, not enough to the conversion capability of super large hydrocarbon molecules, indifferent to the selective opening of many rings heavy constituent, device real-world operation effect is undesirable.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of Modified Zeolite Y and preparation method thereof.The method adopts boron-containing compound and organo-silicon compound to carry out to Y zeolite the boracic modified Y zeolite that modification prepares senior middle school's strong acid content.
The character of Modified Zeolite Y of the present invention is as follows: specific surface 500m
2/ g ~ 900m
2/ g, is preferably 600 ~ 800m
2/ 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, preferably 10 ~ 20, cell parameter is 2.425 ~ 2.445nm, middle strong acid ratio 50% ~ 90%, boron oxide content≤4.0wt%, is preferably≤2.5wt%.
The preparation method of Modified Zeolite Y of the present invention, comprises the steps:
(1) fluoboric acid ammonia solution is prepared;
(2) get the fluoboric acid ammonia solution that industrial production Y molecular sieve puts into step (1), there is following dealuminzation and mend boron reaction in slurry system: NH
4bF
4+ Al
3++ Na
+=NaAlF
4(bulky grain precipitation)+B
3++ NH
4 +, after terminating, carry out Separation of Solid and Liquid, drying;
(3) in step (2) dried material, spray the ethanolic solution of large molecule organo-silicon compound, after drying, hydrothermal treatment consists, prepare Modified Zeolite Y of the present invention.
The inventive method, step (1) fluoboric acid ammonia solution process for preparation is as follows: get appropriate fluoboric acid ammonia and be dissolved in the distilled water of stirring, temperature is 30 ~ 60 DEG C, 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, Na
2o content is 0.4wt% ~ 2.0wt%, optimum 0.8wt% ~ 1.5wt%.
The inventive method, making beating solid-to-liquid ratio 3:1 ~ 10:1 in step (2), making beating temperature 80 ~ 100 DEG C, beating time 30 ~ 240Min.Pulping process can carry out under hyperacoustic effect, and ultrasonic frequency is 40 ~ 100kHz, and power counts 2 ~ 40W/mL by liquor capacity, adopts ultrasonic wave making beating can improve the performance of Modified Zeolite Y further.
The inventive method, baking temperature 60 ~ 180 DEG C in step (2), preferably 100 ~ 150 DEG C, time 3 ~ 8h.
The inventive method, in step (3), large molecule organosilicon can be methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, silicon ether, one or more in the organosilicons such as siloxanes.Organosilicon adopts ethanol as solvent, and spraying organosilyl amount according to silicon-containing compound quality/molecular sieve quality is 1:20 ~ 1:100 meter.The baking temperature of step (3) is 60 ~ 100 DEG C, time 3 ~ 8h.
The inventive method, after step (3) is dry, hydrothermal treatment consists is carried out in tube furnace, is 400 DEG C ~ 750 DEG C, water vapour pressure 0.05 ~ 1.0Mpa Water Under heat treatment 30 ~ 300min in temperature.
The present invention utilizes the feature that aluminium congeners boron chemical property is close, adopts boron-containing compound to process Y zeolite, by the boron element substitution of Al element on framework of molecular sieve, makes the acidity of Y zeolite and hole structural property obtain obvious improvement.
The present invention utilizes the aluminium atom on boron atom replacement molecular sieve in the undersaturated aluminum-oxygen tetrahedron of topmost acid centre coordination, form the same undersaturated boron oxygen tetrahedron of coordination on framework of molecular sieve, because boron atomic weight is less, chemical property is more active, therefore molecular sieve surface formed more in, 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 evenly replaces part framework aluminum in the structure of molecular sieve, is conducive to the middle strong acid ratio improving molecular sieve, improves molecular sieve pore passage structure, give full play to the catalytic performance of molecular screen material.
In the molecular sieve modified procedure of the present invention, mend in the process of boron at dealuminzation, there is no supplementing of boron atom after still having part framework aluminum to remove, can cause a large amount of holes, form secondary pore, therefore the pore passage structure of molecular sieve can obtain obvious improvement.
Large molecule organo-silicon compound are flooded in the present invention in molecular sieve pore passage, compound decomposition under hydrothermal high-temperature environment, for molecular sieve dealumination complement silicon process provides silicon source, framework of molecular sieve structure is made to keep complete, after structure cell shrinks, still can keep higher degree of crystallinity and stability, total acid content reduces simultaneously, and acid enhancing.
Larger molecular organics in molecular sieve pore passage of the present invention, in hydrothermal treatment process, expanded by heating decomposes, good reaming effect is had to the microcellular structure of molecular sieve, the silicon post that organosilicon is residual after Roasting Decomposition simultaneously supports or partial destruction microcellular structure, substantially increase the ratio of macroporous structure, the average pore size of modified molecular screen is obviously increased.
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 and make full use of, and whole modifying process technological process is short, and operating procedure is simple.
Detailed description of the invention
The preparation method of modified Y molecular sieve of the present invention, specifically comprises the steps:
(1) get appropriate fluoboric acid ammonia crystal, adding temperature is gradually in 30 ~ 60 DEG C of distilled water stirred, and filters out the impurity in solution, makes the fluoboric acid ammonia solution that clear is stable.
(2) the low sodium Y molecular sieve of industrial production is got, sodium oxide content 0.5 ~ 2.0wt%, insert the fluoboric acid ammonia solution under stirring, solid-to-liquid ratio 3:1 ~ 10:1, solution temperature rises to 80 ~ 100 DEG C, can open Ultrasound Instrument, under mixed serum is placed in ultrasonic irradiation, ultrasonic frequency is 40 ~ 100kHz, and power counts 2 ~ 40W/m by liquor capacity.There is following dealuminzation in slurry system and mend boron reaction:
NH
4bF
4+ Al
3++ Na
+=NaAlF
4(bulky grain precipitation)+B
3++ NH
4 +
Reaction time 30 ~ 240Min, slurries are filtered, solid-liquor separation by slurries and solid particle precipitate and separate simultaneously, filter cake are carried out drying process, temperature 60 ~ 180 DEG C, time 3 ~ 8h.
(3) prepare the ethanolic solution of organosilicon wet goods compound, organic silicone oil is dropped in the ethanol of stirring at normal temperature state, treat solution clear.Get step (2) and prepare molecular sieve, insert and spray in tank, spray the ethanolic solution of the organo-silicon compound of metering, after organic solvent homogeneous immersion molecular sieve, spray end.Drying process is carried out 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, and temperature programming is to treatment temperature, and treatment temperature is 400 DEG C ~ 750 DEG C, water vapour pressure 0.05 ~ 1.0Mpa, and process 30 ~ 300min, prepares this modified molecular screen.
Analytical method of the present invention: specific surface and pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, meleic acid amount, B acid amount and L acid amount adopt Pyridine adsorption IR spectra method, wherein the summation of B acid amount and L acid amount is meleic acid amount, and middle strong acid is the total acid content of desorption between 250 ~ 350 DEG C.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiments.
Embodiment 1
Measuring 219.0g fluoboric acid ammonia adds in the 2000mL distilled water of 50 DEG C of stirrings gradually, preparation fluoboric acid ammonia spirit.Get 500g industrial production low sodium ammonium Y molecular sieve (Na
2o content is 1.1%, degree of crystallinity 102%, and lattice constant is 2.475nm), joined by molecular sieve in the fluoboric acid ammonia spirit of stirring gradually, slurry temperature is increased to 95 DEG C, process 60min; First slurries are separated with solid particle (cryolite), then carrying out Separation of Solid and Liquid, filter cake is carried out drying at 120 DEG C, time 6h; Get above-mentioned 500g molecular sieve, by 200mL organic silicone oil ethanolic solution (concentration 18.4gSiO
2/ 100mL) spray uniformly on molecular sieve.Drying process is carried out to molecular sieve after dipping, temperature 80 DEG C, time 3h; Molecular sieve containing organo-silicon compound is carried out hydrothermal treatment consists, treatment temperature 550 DEG C, pressure 0.05MPa, and process 90min, namely prepares modified molecular screen of the present invention, is numbered BCY-1.
Embodiment 2
Change sodium ammonium Y low in example 1 into SSY molecular sieve, fluoboric acid ammonia solution concentration is adjusted to 15.2g/100mL, and making beating solid-to-liquid ratio is 1:5, and making beating temperature 70 C, beating time is 2h, and organosilicon becomes siloxanes, and other, with example 1, is numbered BCY-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, making beating temperature 90 DEG C, beating time is 4h, and organosilicon becomes phenyl silicone oil, and hydrothermal conditions is adjusted to treatment temperature 650 DEG C, pressure 0.1MPa, process 120min, other is with example 1, numbering BCY-3.
Embodiment 4
Carry out under pulping process in example 1 being placed in hyperacoustic effect, ultrasonic frequency is 40kHz, and power counts 10W/mL by liquor capacity, and all the other, with embodiment 1, are numbered BCY-4.
Comparative example 1
Ammonium fluoroborate in example 1 is changed into the ammonium fluosilicate of same molar ratio, other obtains molecular sieve numbering BJY-1 with example 1.
Comparative example 2
Organosilicon in example 1 is sprayed processing procedure to cancel, other obtains molecular sieve numbering BJY-2 with example 1.
The molecular sieve character of embodiment and comparative example gained is in table 1.
the character of table 1 embodiment and comparative example gained molecular sieve
Claims (12)
1. a Modified Zeolite Y, is characterized in that: the specific area 500m of this molecular sieve
2/ g ~ 900m
2/ 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 50% ~ 90%, boron oxide content≤4.0wt%.
2. molecular sieve according to claim 1, is characterized in that: the specific surface of this molecular sieve is long-pending 600 ~ 800m
2/ g, silica alumina ratio 10 ~ 20, boron oxide content≤2.5wt%.
3. the preparation method of molecular sieve described in claim 1 or 2, is characterized in that comprising the steps:
(1) fluoboric acid ammonia solution is prepared;
(2) get the fluoboric acid ammonia solution that industrial production Y molecular sieve puts into step (1), there is following dealuminzation and mend boron reaction in slurry system: NH
4bF
4+ Al
3++ Na
+=NaAlF
4(bulky grain precipitation)+B
3++ NH
4 +, after terminating, carry out Separation of Solid and Liquid, drying;
(3) in step (2) dried material, spray the ethanolic solution of large molecule organo-silicon compound, after drying, hydrothermal treatment consists, prepare Modified Zeolite Y of the present invention.
4. method according to claim 2, it is characterized in that: step (1) fluoboric acid ammonia solution process for preparation is as follows: get appropriate fluoboric acid ammonia and be dissolved in the distilled water of stirring, temperature is 30 ~ 60 DEG C, 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.
5. method according to claim 2, is characterized in that: step (2) industrial production Y molecular sieve is low sodium Y molecular sieve, Na
2o content is 0.4wt% ~ 2.0wt%, optimum 0.8wt% ~ 1.5wt%.
6. method according to claim 2, is characterized in that: making beating solid-to-liquid ratio 3:1 ~ 10:1 in step (2), making beating temperature 80 ~ 100 DEG C, beating time 30 ~ 240Min.
7. the method according to claim 2 or 6, is characterized in that: pulping process carries out under hyperacoustic effect, and ultrasonic frequency is 40 ~ 100kHz, and power counts 2 ~ 40W/mL by liquor capacity.
8. method according to claim 2, is characterized in that: baking temperature 60 ~ 180 DEG C in step (2), preferably 100 ~ 150 DEG C, drying time 3 ~ 8h.
9. method according to claim 2, is characterized in that: in step (3), large molecule organosilicon comprises methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, silicon ether, one or more in siloxanes.
10. method according to claim 2, is characterized in that: spraying organosilyl amount according to silicon-containing compound quality/molecular sieve quality is 1:20 ~ 1:100 meter.
11. methods according to claim 2, is characterized in that: the baking temperature of step (3) is 60 ~ 100 DEG C, time 3 ~ 8h.
12. methods according to claim 2, is characterized in that: after step (3) is dry, hydrothermal treatment consists is carried out in tube furnace, is 400 DEG C ~ 750 DEG C, water vapour pressure 0.05 ~ 1.0Mpa Water Under heat treatment 30 ~ 300min in temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107344116A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method and application |
| 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 |
| CN111686784A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Preparation method of modified Y-type molecular sieve |
| CN112758952A (en) * | 2020-12-31 | 2021-05-07 | 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344116A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method and application |
| 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 |
| CN111686784A (en) * | 2019-03-12 | 2020-09-22 | 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 |
| CN112758952A (en) * | 2020-12-31 | 2021-05-07 | 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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