CN106698461B - A kind of method that in-situ crystallization prepares nano NaY molecular sieve - Google Patents
A kind of method that in-situ crystallization prepares nano NaY molecular sieve Download PDFInfo
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Abstract
A kind of method that in-situ crystallization prepares nano NaY molecular sieve.This method comprises: deionized water, binder is added, manufactured mixed serum is spray-dried to obtain kaolin microsphere using kaolin as raw material；Kaolin atomized microball is obtained into high native microballoon in 920~1000 DEG C of roasting 2h；Above-mentioned high native microballoon is handled at 20~65 DEG C with inorganic acid solution, the high native microballoon of acid processing is mixed with silicon source, aqueous slkali, directed agents, and nonionic surfactant is added and chlorination alkaline earth, crystallization, filter cake obtain in-situ crystallization product after filtration, washing and drying.NaY molecular sieve crystallite dimension contained by prepared in-situ crystallization product is nanoscale, and the nano molecular sieve has the characteristics that easily separated, stability is preferable.
Description
Technical field
The invention belongs to oil refining catalyst fields, more particularly to catalytic cracking catalyst.
Background technique
Fluid catalytic cracking (FCC) is the important means of processing of heavy oil, and wherein FCC catalyst is even more to be used as core technology quilt
Lasting research.FCC catalyst is divided into binder-type catalyst and in-situ crystallization type catalyst two major classes, and binder-type catalyst is
The microspherical catalyst made of binder molding bonded by molecular sieve and matrix, in-situ crystallization catalyst are the height with preforming
Ridge soil microballoon is raw material, the catalyst obtained from growth in situ molecular sieve in microsphere surface and duct.Two class catalyst are closing
There are biggish differences in architectonical, raw material and method.But no matter which kind of catalytic cracking catalyst, Y type molecular sieve conduct
Most important active component, catalytic performance directly affect catalytic cracking reaction as a result, economy to catalytic cracking unit
There are vital influences for benefit.The crystallite dimension of molecular sieve directly affects the absorption and diffusion of reactants and products, in turn
Determine the superiority and inferiority of its catalytic performance.For the partial size of regular industrial NaY molecular sieve generally in 800~1000nm, crystal grain is larger, outer surface
Product is smaller, and duct is relatively long and narrow, is unfavorable for the absorption and diffusion of reactants and products, especially for heavy oil catalytic cracking reaction,
Since heavy oil molecules size is larger, it is difficult to be contacted with the activated centre of inner surface and cause catalytic activity lower.Also, due to weight
The diffusion of oil molecule limits, it is easy to carbon distribution occur and lead to catalyst inactivation.
Nano molecular sieve refers to crystallite dimension in the molecular sieve of 1~100nm.Compared with stock size Y type molecular sieve, nanometer
Molecular sieve has the advantage that (1) external surface area is big, and aperture is more, and accessible activated centre is more, and surface can be higher, appearance
Face atom is in valence link undersaturated condition, easy adsorption reaction object molecule, thus shows high catalytic activity, especially works as reactant
When molecular dimension is greater than molecular sieve bore diameter, nano molecular sieve will show bigger superiority.(2) there is short and regular duct,
Cause reactant molecule that can rapidly enter, product molecule can quickly leave, the improvement of molecular sieve pore passage diffusion, it will
Significantly influence the catalytic activity and selectivity of molecular sieve.(3) skeleton component is evenly distributed, the sky with more reasonable acid site
Between be distributed, can effectively eliminate acid site concentration gradient, improve the activity and selectivity of catalyst.(4) anti-carbon and it is anti-in
Malicious ability is strong.Since product can be spread out from nano molecular sieve duct quickly, reduces reaction depth and become coking deactivation
Slowly；Due to the polymolecularity of nano molecular sieve, keep catalyst anti-greatly heavy metal ion and sulfur-bearing, nitrogenous compound saturation
Poisoning capability enhancing.(5) content of metal with higher.Nano molecular sieve has more aperture and shorter duct, gold
Belong to component to be easier to enter duct, its dispersion degree and effective content is improved, to improve catalytic performance.But nano molecular
There is also separation difficulty and the relatively poor problems of thermal stability for sieve.
Have several reports about nano NaY preparation method, such as the clear liquid synthetic method based on organic formwork agent
(Holmberg B A,Wang H,Norbeck J M,et al.Controlling size and yield of zeolite
Y nanocrystals using tetramethylammonium bromide[J].Microporous and
Mesoporous Materials, 2003,59 (1): 13-28), (Chao Zisheng, vast stretch of wooded country is strong, Chen Guozhou, waits ultra micro for additive method
The synthesis (II) of NaY molecular sieve -- influence [J] advanced chemical journal of addition aluminum complexing agent, 2001,22 (1): 10-15),
Microwave assisting method (microwave induced quickly synthesizing nano NaY molecular sieve [J] the physical chemistry of Cheng Zhilin, Chao Zisheng, ten thousand favour continuous heavy rain
Report, 2003,19 (6): 487-491), limit space law (Tang K, Wang Y G, Song L J, et al.Carbon
nanotube templated growth of nano-crystalline ZSM-5 and NaY zeolites[J]
.Materials Letters, 2006,60 (17): 2158-2160), (Tan Juan, Chen Ying, Liu Jing wait Dynamic Water to dynamic crystallization method
Thermal crystallisation method synthesizes nano NaY type molecular sieve [J] silicate notification, 2011,30 (1): 13-18) etc..Existing report is big absolutely
Majority is all to have perhaps that synthesis condition is harsh, synthesis cost is higher or molecular sieve based on silica-alumina gel hydrothermal synthesis
It separates the problems such as difficult and stability is relatively poor and is difficult to industrial application.It is small to develop partial size, narrow particle size distribution is at low cost,
Easily separated, stability is preferable, and industrial nano Y-shaped molecular sieve is suitble to be still very big challenge.
The preparation process of in-situ crystallization synthesis NaY molecular sieve are as follows: it is first that kaolin mashing is spraying at kaolin microsphere, it will be micro-
Ball high-temperature roasting obtains required active silicon source and silicon source, then raw on the surface of microballoon and in duct through hydro-thermal in-situ crystallization
Long zeolite molecular sieve.In-situ crystallization prepares nano Y-shaped molecular sieve on kaolin microsphere, is able to solve nano molecular sieve and is difficult to point
The stability for improving molecular sieve by chemistry key connection from problem, while between molecular sieve and matrix, most promises to be reality
The breach of existing nano molecular sieve industrial application.The crystallite dimension of the NaY molecular sieve of conventional in situ crystallization method preparation 500~
600nm.The NaY molecular sieve that more little crystal grain is prepared using in-situ crystallization, the crystallization body in situ such as Liu Honghai are also attempted at present
Polyvinylpyrrolidone or polyvinyl alcohol are added in system, obtains the in-situ crystallization NaY (Liu Hong that crystallite dimension is 200~400nm
Sea, Wang Yimeng, Yan Lijun wait a kind of synthetic method [P] of the kaolin microsphere in-situ crystallization object containing small crystal grain NaY molecular sieve of
China: CN 102019197A, 2011-04-20).But report yet there are no using the molecular sieve of in-situ crystallization technology synthesis nano
Road.
Summary of the invention
The object of the present invention is to provide a kind of methods that in-situ crystallization prepares nano NaY molecular sieve, and this method is due to molecule
Sieve matrix between by chemistry key connection, prevent the reunion between nanocrystal, solve nano molecular sieve and be difficult to separate and heat
The relatively poor problem of stability.
It realizes the technical solution of the present invention is as follows: a kind of method that in-situ crystallization prepares nano NaY molecular sieve, this method packet
Include: by high native microballoon at 20~65 DEG C, preferably 30~50 DEG C are handled with inorganic acid solution, the high native microballoon of acid processing and silicon source, alkali
Solution, directed agents mixing, are added nonionic surfactant and chlorination alkaline earth, crystallization, and filter cake obtains after filtration, washing and drying
To in-situ crystallization product, wherein the mass ratio that feeds intake of nonionic surfactant and high native microballoon is 0.01~0.2, preferably 0.03
~0.15, more preferable 0.03~0.09, the mass ratio that feeds intake of chlorination alkaline earth and high native microballoon is 0.01~0.2, preferably 0.04~
0.12。
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the described native microballoon of height 20~
55 DEG C with 2~8h of mineral acid treatment, and by filtering, washing, it is dry after obtain the high native microballoon of acid processing.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the native microballoon of the height is ability
Well known to field technique personnel, detailed narration has been carried out to high native microballoon and preparation method thereof in patent CN102019197A；
The described native microballoon of height, refer to kaolin atomized microball through 920~1000 DEG C of roastings it is obtained mainly comprising Spinel and
The soil ball of active silica phase.Currently preferred high native microballoon the preparation method comprises the following steps: by kaolin, binder, water it is mixed
It closes slurries and is prepared into kaolin atomized microball, in 920~1000 DEG C, preferably 920~950 DEG C, roast 1~3h.The bonding
Agent be selected from one of sodium metasilicate, silica solution, Aluminum sol, boehmite or a variety of, additional amount be kaolin quality 2%~
10%, preferably 2~8%, the main function of binder is the wear-resisting property as dispersing agent and improvement catalyst.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the native microspherulite diameter of the height are
20~110 μm, preferably 40~90 μm.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve includes crystalline substance in the kaolin
Body kaolinite mass content 80%~100%, iron oxide mass content 0~1.7%, the sum of sodium oxide molybdena and potassium oxide mass content
0~0.5%；More specifically, the kaolin comes from one of soft kaolin, hard kaoline, Coaseries kaolin
Or it is a variety of.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the native microballoon inorganic acid of the height
Processing, acid are inorganic acid solution.The inorganic acid is selected from one of hydrochloric acid, sulfuric acid, nitric acid or a variety of.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, preferably inorganic acid solution concentration are 6
The mass ratio that feeds intake of~12mol/L, inorganic acid solution and high native microballoon is 1~5.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the non-ionic surface are living
Property agent be a kind of surfactant for not generating ion in aqueous solution, do not dissociated when the substance is due to being dissolved in water, institute
It is high with its stability, it does not influence vulnerable to existing for strong electrolyte, can be stabilized in alkali, acid solution, and have excellent
Emulsification, dispersion performance.Common nonionic surfactant has alkyl phenol polyoxyethylene ether (APEO) series, fatty alcohol polyoxy
Vinethene (AEO) series, tween (Tween) series.Wherein, alkyl phenol polyoxyethylene ether series non-ionic surfactants are typical
Substance have nonylphenol polyoxyethylene ether (TX), octyl phenol polyoxyethylene ether (OP), such as TX-10, OP-20；Fatty alcohol polyoxy
The typical substance of vinethene nonionic surfactant has AEO-9, AEO-25；TWEEN Series nonionic surfactant is typical
Substance has Tween-20, Tween-40, Tween-60, Tween-80.Method of the present invention, nonionic surfactant are selected from upper
State one of one or more series/nonionic surfactant types or a variety of specific substances.The preferred tween system of the present invention
Column, one of more preferable Tween-20, Tween-40, Tween-60, Tween-80 or a variety of.Nonionic surfactant and height soil
The mass ratio that feeds intake of microballoon is 0.01~0.2, preferably 0.03~0.15, more preferable 0.03~0.09.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the chlorination alkaline earth are selected from chlorine
Change one of magnesium, calcium chloride, strontium chloride, barium chloride or a variety of；The mass ratio that feeds intake of chlorination alkaline earth and high native microballoon is 0.01
~0.2, preferably 0.04~0.12.
The method that a kind of in-situ crystallization disclosed by the invention prepares nano NaY molecular sieve, the silicon source, are led at aqueous slkali
It is known to those skilled in the art to the type of agent and its additional amount, in patent CN102372281A and CN103240113A
Disclose its type and additional amount.The present invention recommends silicon source to be selected from one of waterglass, silica solution, white carbon black or a variety of,
It is preferred that waterglass；Aqueous slkali is sodium hydroxide solution；Mole group of directed agents becomes (14~16) Na2O:(0.7~1.3)
Al2O3: (14~16) SiO2: (300~330) H2O。
The method that a kind of in-situ crystallization disclosed in this invention prepares nano NaY molecular sieve, the acid processing Gao Tuwei
Ball is mixed with silicon source, aqueous slkali, directed agents, when mixing various materials mass ratio are as follows: at the acid of (1.0~1.2) in terms of butt
The high native microballoon of reason: (0.05~0.5) is with SiO2The silicon source of meter: the aqueous slkali of (0.15~0.6) in terms of MOH: (0.05~0.5) is led
To agent: (0.01~0.2) nonionic surfactant: (0.01~0.2) chlorination alkaline earth；M therein is alkali metal.
The method that a kind of in-situ crystallization disclosed in this invention prepares nano NaY molecular sieve, preferred crystallization process condition
Are as follows: 60~100 DEG C of temperature, crystallization time is 8~36h.
The method that a kind of in-situ crystallization disclosed in this invention prepares nano NaY molecular sieve, by being carried out to high native microballoon
Acid processing, and its process conditions is controlled, leach the part Al in high native microballoon2O3, improve the SiO of high native microballoon2/Al2O3It rubs
Your ratio can effectively slow down dissolution rate of the silicon source in situ in crystallization process, to reduce crystal growth rate.Pass through addition
Nonionic surfactant, changes the property of crystal growing surface, reduces the presence of plane of crystal hydroxyl, reduce little crystal grain it
Between reunion, improve the dispersibility of material.By the way that alkali salt is added, adsorb alkaline-earth metal ions in particle surface, energy
The absolute value for improving particle surface current potential, to generate strong electric double layer electrostatic repulsion；Meanwhile electrolyte can also enhance
Grain surface is to the wetness degree of water, to be effectively prevented the reunion of little crystal grain in water.Compared to 800 traditional~1000nm's
Gel method synthesizes NaY molecular sieve, and the in-situ crystallization method of even 500~600nm synthesizes NaY molecular sieve, prepared by the present invention
The crystallite dimension of in-situ crystallization type NaY molecular sieve is nanoscale (1~100nm), and average grain size is 70~100nm.The party
Method between molecular sieve and matrix by chemistry due to being keyed, so that nano NaY molecular sieve passes through conventional filtering in crystallization product
It can be easily separated, solve the problems, such as that nano molecular sieve is difficult to separate；Chemical bond between molecular sieve and matrix simultaneously
Effect prevents the reunion between nanocrystal, solves the problems, such as that nano molecular sieve thermal stability is relatively poor.
Average grain size of the present invention is to use Nano based on the stereoscan photograph of in-situ crystallization product
Measure software, which is counted, to be obtained.
The method that a kind of in-situ crystallization disclosed in this invention prepares nano NaY molecular sieve, the molecular sieve of preparation, which has, to be received
The crystallite dimension and thermal stability of meter level are relatively preferable, are applicable to heavy oil catalytic cracking.
Detailed description of the invention
The XRD diagram of Fig. 1 embodiment 1, embodiment 1 prepare in-situ crystallization product in crystal phase be NaY molecular sieve.
The SEM of Fig. 2 embodiment 1 schemes, and NaY molecular sieve average grain size prepared by embodiment 1 is 80nm.
The particle diameter distribution of Fig. 3 embodiment 1 finds after being counted by the crystallite dimension to Fig. 2, the crystal grain of 70~90nm
Account for the 95% of all crystal grains.
The SEM of Fig. 4 comparative example 1 schemes, and NaY molecular sieve average grain size prepared by comparative example 1 is 540nm.
The particle diameter distribution of Fig. 5 comparative example 1 finds after being counted by the crystallite dimension to Fig. 4, the crystalline substance of 450~650nm
Grain accounts for the 81% of all crystal grains.
Specific embodiment
The present invention is further illustrated below with reference to embodiment and comparative example, but the present invention is not by the limit of following specific embodiments
System.
1, primary raw material source:
Kaolin: Kaolin of Suzhou, China Kaolin Clay Co., Ltd.'s production, middle partial size is 3.2 μm, and kaolinite content is
82%, iron oxide content 0.74%, the sum of potassium oxide and sodium oxide content are 0.35%.
Waterglass: SiO2250g/L, Na2O 88g/L, Lanzhou Petrochemical Company production.
Aqueous slkali: NaOH 150g/L, Lanzhou Petrochemical Company production.
Directed agents: using preparation method described in CN1081425A, proportion are as follows: 16SiO2: A12O3: 16Na2O:320H2O
(molar ratio).
Hydrochloric acid: pure, density 1.19g/L, mass concentration 36.5% are analyzed.
Sulfuric acid: pure, density 1.84g/L, mass concentration 98.3% are analyzed.
Nitric acid: pure, density 1.42g/L, mass concentration 69.2% are analyzed.
Tween-20, Tween-40, Tween-60, Tween-80, OP-20, AEO-25: chemistry is pure, buys in Chinese medicines group
Learn reagent Co., Ltd.
Magnesium chloride, calcium chloride, strontium chloride, barium chloride: analysis is pure, buys in Sinopharm Chemical Reagent Co., Ltd..
2, main analysis method used in embodiment:
Kaolin testing graininess uses laser particle analyzer method, method standard Q/SYLS0519-2002；Kaolin microsphere changes
Property front and back sample element composition use XRF method；The test of NaY molecular sieve crystallinity uses x-ray powder diffraction, method mark
Standard is Q/SYLS0596-2002；NaY molecular sieve grain size uses SEM method, based on the SEM photograph of in-situ crystallization product, uses
Nano Measure software, which is counted, obtains average grain size.
Embodiment 1
By kaolin 2000g (bright base), sodium metasilicate 4%, it is 42% that deionized water, which is added, and is prepared into kaolin solid content
Mixed serum, spray drying obtain the kaolin atomized microball that 1840g average grain diameter is 70 μm；Kaolin atomized microball is existed
950 DEG C of roasting 2h obtain roasting high native microballoon；Soil microballoon high after roasting is immersed in 12mol/L hydrochloric acid and reacts 5h at 45 DEG C,
The high native microballoon of acid processing is obtained after filtering, washing, drying；By the hydroxide of 50g acid processing high native microballoon and 40mL silicon source, 95mL
Sodium solution, the mixing of 3mL directed agents, addition 2.5g Tween-20,2g calcium chloride, 80 DEG C of crystallization 12h, filter cake are filtered, washed, are done
In-situ crystallization product is obtained after dry.
Through X-ray diffraction measure, relative crystallinity 12%, XRD spectra, SEM photograph and particle diameter distribution are respectively as schemed
1, shown in Fig. 2 and Fig. 3, gained molecular sieve average grain diameter is 80nm, and epigranular.
Embodiment 2
Using the high native microballoon of gained roasting in embodiment 1, it is immersed in 6mol/L hydrochloric acid and reacts 5h, mistake at 40 DEG C
The high native microballoon of acid processing is obtained after filter, washing, drying；By the sodium hydroxide of 50g acid modified high native microballoon and 35mL silicon source, 90mL
Solution, the mixing of 3.5mL directed agents, addition 2g Tween-40,1.5g strontium chloride, 85 DEG C of crystallization 10h, filter cake are filtered, washed, are done
In-situ crystallization product is obtained after dry.
Through X-ray diffraction measure, relative crystallinity 10%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter is 85nm.
Embodiment 3
Using the high native microballoon of gained acid processing in embodiment 1, by the modified high native microballoon of 50g acid and 30mL silicon source, 85mL
Sodium hydroxide solution, 4mL directed agents mixing, be added 1.5g Tween-60,2.5g magnesium chloride, 80 DEG C of crystallization 14h, filter cake through filtering,
In-situ crystallization product is obtained after washing, drying.
Through X-ray diffraction measure, relative crystallinity 11%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter is 87nm.
Embodiment 4
Using the high native microballoon of gained acid processing in embodiment 1, by the modified high native microballoon of 50g acid and 25mL silicon source, 80mL
Sodium hydroxide solution, the mixing of 4.5mL directed agents, addition 3g Tween-80,3g barium chloride, 80 DEG C of crystallization 16h, filter cake are filtered, are washed
Wash, dry after obtain in-situ crystallization product.
Through X-ray diffraction measure, relative crystallinity 10%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter is 83nm.
Embodiment 5
Using the high native microballoon of gained acid processing in embodiment 1, by the high native microballoon of 50g acid processing and 40mL silicon source, 95mL
Sodium hydroxide solution, 3mL directed agents mixing, be added 3.5g OP-20,2.5g calcium chloride, 85 DEG C of crystallization 12h, filter cake through filtering,
In-situ crystallization product is obtained after washing, drying.
Through X-ray diffraction measure, relative crystallinity 11%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter is 98nm.
Embodiment 6
Using the high native microballoon of gained acid processing in embodiment 1, by the high native microballoon of 50g acid processing and 40mL silicon source, 95mL
Sodium hydroxide solution, the mixing of 3mL directed agents, addition 4g AEO-25,1.5g calcium chloride, 80 DEG C of crystallization 14h, filter cake are filtered, are washed
Wash, dry after obtain in-situ crystallization product.
Through X-ray diffraction measure, relative crystallinity 9%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter is 95nm.
Comparative example 1
Use the high native microballoon of gained roasting in embodiment 1, without peracid treatment, high soil microballoon and 40mL after 50g is roasted
Silicon source, the sodium hydroxide solution of 95mL, the mixing of 3mL directed agents, for 24 hours, filter cake obtains 96 DEG C of crystallization after filtration, washing and drying
In-situ crystallization product.
Through X-ray diffraction measure, relative crystallinity 16%, stereoscan photograph and particle diameter distribution respectively such as Fig. 4 and
Shown in Fig. 5, gained molecular sieve average grain diameter about 540nm.
Comparative example 2
Using the high native microballoon of gained roasting in embodiment 1,50g is roasted to the hydrogen-oxygen of high native microballoon and 40mL silicon source, 95mL
Change sodium solution, the mixing of 3mL directed agents, 2.5g Tween-20,94 DEG C of crystallization 22h is added, filter cake obtains after filtration, washing and drying
In-situ crystallization product.
Through X-ray diffraction measure, relative crystallinity 17%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter about 205nm.
Comparative example 3
Using the high native microballoon of gained roasting in embodiment 1,50g is roasted to the hydrogen-oxygen of high native microballoon and 40mL silicon source, 95mL
Change sodium solution, the mixing of 3mL directed agents, 2g calcium chloride, 92 DEG C of crystallization 20h is added, filter cake obtains original after filtration, washing and drying
Position crystallization product.
Through X-ray diffraction measure, relative crystallinity 16%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter about 290nm.
Comparative example 4
Using the high native microballoon of gained acid processing in embodiment 1, by the high native microballoon of 50g acid processing and 40mL silicon source, 95mL
Sodium hydroxide solution, the mixing of 3mL directed agents, 90 DEG C of crystallization 26h, filter cake obtain in-situ crystallization production after filtration, washing and drying
Object.
Through X-ray diffraction measure, relative crystallinity 24%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter about 180nm.
Comparative example 5
Using gained kaolin atomized microball in embodiment 1, part kaolin atomized microball is obtained in 600 DEG C of roasting 2h
Partially native microballoon；Part kaolin atomized microball obtains high native microballoon in 950 DEG C of roasting 2h；It will partially native microballoon, high native microballoon difference
It is immersed in 12mol/L hydrochloric acid and reacts 5h at 45 DEG C, the partially native microballoon of acid processing is obtained after filtering, washing, drying, acid handles high soil
Microballoon；The partially native microballoon of 25g acid processing, the high native microballoon of 25g acid processing are led with 40mL silicon source, the sodium hydroxide solution of 95mL, 3mL
It is mixed to agent, for 24 hours, filter cake obtains in-situ crystallization product to 96 DEG C of crystallization after filtration, washing and drying.
Through X-ray diffraction measure, relative crystallinity 29%, stereoscan photograph and particle diameter distribution show gained molecule
Sieve average grain diameter about 625nm.
From embodiment as can be seen that using the high native microballoon of acid processing for raw material, while a certain amount of non-ionic surface is added
Activating agent and chlorination alkaline earth, and in-situ crystallization condition is controlled, the in-situ crystallization product comprising nano NaY molecular sieve can be made.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (16)
1. a kind of method that in-situ crystallization prepares nano NaY molecular sieve, it is characterised in that this method comprises: by high native microballoon 20
~65 DEG C are handled with inorganic acid solution, and the high native microballoon of acid processing is mixed with silicon source, aqueous slkali, directed agents, and non-ionic surface is added
Activating agent and chlorination alkaline earth, crystallization obtain in-situ crystallization product after filtration, washing and drying；Wherein nonionic surfactant
It is 0.01~0.2 with high native microspheres quality ratio, chlorination alkaline earth and high native microspheres quality ratio are 0.01~0.2.
2. according to the method described in claim 1, it is characterized in that high soil microballoon is handled at 30~50 DEG C with inorganic acid solution.
3. according to the method described in claim 1, it is characterized in that nonionic surfactant is with high native microspheres quality ratio
0.03~0.15.
4. according to the method described in claim 3, it is characterized in that nonionic surfactant is with high native microspheres quality ratio
0.03~0.09.
5. according to the method described in claim 1, it is characterized in that the mass ratio that feeds intake of chlorination alkaline earth and high native microballoon is 0.04
~0.12.
6. method described in any claim according to claim 1~5, it is characterised in that the preparation method of high soil microballoon is,
The mixed serum of kaolin, binder, water is prepared into kaolin atomized microball, in 920~1000 DEG C of 1~3h of roasting.
7. according to the method described in claim 6, it is characterized in that kaolin atomized microball partial size is 20~110 μm.
8. method described in any claim according to claim 1~5, it is characterised in that at high soil microballoon inorganic acid solution
Reason, inorganic acid solution concentration are 1~12mol/L, and the mass ratio that feeds intake of inorganic acid solution and high native microballoon is 1~5.
9. method described in any claim according to claim 1~5, it is characterised in that high soil microballoon is at 20~65 DEG C with nothing
Machine acid handles 2~8h, and the high native microballoon of acid processing is obtained after filtering, washing, drying.
10. method described in any claim according to claim 1~5, it is characterised in that nonionic surfactant is selected from
TWEEN Series nonionic surfactant, alkyl phenol polyoxyethylene ether series non-ionic surfactants, aliphatic alcohol polyethenoxy
One of ether series non-ionic surfactants are a variety of.
11. according to the method described in claim 10, it is characterized in that nonionic surfactant is TWEEN Series nonionic table
One of face activating agent is a variety of.
12. according to the method described in claim 10, it is characterized in that nonionic surfactant is selected from Tween-20, tween-
40, one of Tween-60, Tween-80, OP-20, AEO-25 or a variety of.
13. method described in any claim according to claim 1~5, it is characterised in that chlorination alkaline earth is selected from magnesium chloride, chlorine
Change one of calcium, strontium chloride, barium chloride or a variety of.
14. method described in any claim according to claim 1~5, it is characterised in that it is molten that silicon source is selected from waterglass, silicon
One of glue, white carbon black are a variety of；Aqueous slkali is sodium hydroxide solution；Mole group of directed agents becomes (14~16) Na2O:
(0.7~1.3) Al2O3: (14~16) SiO2: (300~330) H2O。
15. method described in any claim according to claim 1~5, it is characterised in that the high native microballoon of acid processing and silicon source,
Aqueous slkali, directed agents, nonionic surfactant and chlorination alkaline earth the mass ratio that feeds intake are as follows: the acid of (1.0~1.2) in terms of butt
The high native microballoon of processing: (0.05~0.5) is with SiO2The silicon source of meter: the aqueous slkali of (0.15~0.6) in terms of MOH: (0.05~0.5)
Directed agents: (0.01~0.2) nonionic surfactant: (0.01~0.2) chlorination alkaline earth, M are alkali metal.
16. method described in any claim according to claim 1~5, it is characterised in that the process conditions of crystallization are as follows: temperature
60~100 DEG C, crystallization time is 8~36h.
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| CN101462741A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite by in situ crystallization |
| CN102464333A (en) * | 2010-11-04 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve by in-situ crystallization |
| CN103447069A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst containing Y-type molecular sieve and preparation method thereof |
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| CN101462741A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite by in situ crystallization |
| CN102464333A (en) * | 2010-11-04 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve by in-situ crystallization |
| CN103447069A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst containing Y-type molecular sieve and preparation method thereof |
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