CN104556086B

CN104556086B - A kind of method utilizing organic quaternary ammonium salt synthesis silica zeolite

Info

Publication number: CN104556086B
Application number: CN201310522818.5A
Authority: CN
Inventors: 舒兴田; 夏长久; 林民; 朱斌; 彭欣欣; 郑爱国; 忻睦迪
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-10-29
Filing date: 2013-10-29
Publication date: 2016-07-06
Anticipated expiration: 2033-10-29
Also published as: CN104556086A

Abstract

A kind of method utilizing organic quaternary ammonium salt synthesis silica zeolite, including template, organosilicon source, inorganic source of ammonium and water mixed hydrolysis are caught up with alcohol, aging, mix with solid silicon source again, then crystallization in closed reactor, reclaiming silica zeolite, described template is the mixture of quaternary ammonium salt and organic amine.The silica zeolite that silica zeolite synthetic method provided by the invention obtains has higher cyclohexanone-oxime Beckmann rearrangement activity.

Description

A kind of method utilizing organic quaternary ammonium salt synthesis silica zeolite

Technical field

The present invention relates to a kind of silica zeolite and synthetic method thereof, the method specifically utilizing organic quaternary ammonium salt template synthesis silica zeolite.

Background technology

The synthesis of silica zeolite generally uses quaternary ammonium base or quaternary ammonium salt. template agent, compared with quaternary ammonium base, organic quaternary ammonium salt low price, the alkalescence in order to ensure synthetic system generally uses with organic bases such as organic amine simultaneously, but the silica zeolite activity of its synthesis at present is not high.

Disclosed silica zeolite direct hydrothermal synthesis method at present, it is common to use organosilicon source and/or inorganic silicon source.Organosilicon source such as organo-silicon ester TEOS, price comparison is expensive, and its active constituent content forming molecular sieve is relatively low, it is difficult to improve the solid content of Zeolite synthesis crystallization product, and a large amount of ethanol that volatilizees in process of producing molecular sieve, and these ethanol is difficult to collect recycling.In order to reduce cost, research worker research adopts inorganic silicon source to replace part or all of organosilicon source, but the silica zeolite crystal grain of currently used inorganic silicon source synthesis is relatively big, and activity is less high.

The method that union carbide corporation of the U.S. in 1977 reports direct hydrothermal synthesis all-silica MFI structure molecular screen in USP4061724, it is first prepared and mole consists of (0-6.5) M₂O:(13-50) SiO₂:Q₂O:(150-700) H₂The reactant mixture of O, at then this mixture being placed in 100-250 DEG C crystallization 50-150 hour, wherein M was alkali metal ion, organic formwork agent Q=R₄X⁺, R is the alkyl of 2-6 carbon atom, and X is P or N.Then they disclose again the interpolation fluorine element method to reduce total silicon S-1 Crystallization of Zeolite temperature in patent USP4073865, but environment is had severe contamination by fluorine element, and its application is restricted.Silica zeolite prepared by above method is not high for cyclohexanone-oxime Beckmann rearrangement activity.

CN97100231.2 discloses the synthetic method of a kind of crystalline silicon dioxide molecular sieve, the method is with solid silicone for raw material, with amine Organic substance (Q) for template, it is obtained by mixing mole consists of (0.02-0.3) Na with water with NaOH₂O:(0.05-0.8)SiO₂:(1-10)H₂The reactant mixture of O, then by this reactant mixture according to a conventional method in 100-200 DEG C of crystallization 8 hours to 10 days.The silica zeolite that the method obtains is very low for cyclohexanone-oxime Beckmann rearrangement activity.

Patent CN201010616382 discloses a kind of S-1 silica zeolite and preparation method and the application in preparing caprolactam, and S-1 silica zeolite is made by following method: the synthesis of (1) TPAOH template；(2) synthesis of molecular sieve: by TPAOH aqueous solution and tetraethyl orthosilicate and ethanol synthesis, filtering, with deionized water wash, reactant liquor dries, and roasting obtains molecular screen primary powder；In molecular screen primary powder, add Ludox, Macrogol 2000, strong aqua ammonia, field mountain valley with clumps of trees and bamboo powder and active carbon powder, after mediating with kneader, carry out extruded moulding；Roasting；Product after roasting is sequentially placed into NH₃-NH₄NO₃Mixed solution and hydrofluoric acid aqueous solution soak, uses deionized water wash；Dry, roasting again, namely make a kind of S-1 silica zeolite.The method uses quaternary ammonium base synthesis silica zeolite.

Summary of the invention

The technical problem to be solved in the present invention is to synthesize, for existing use organic quaternary ammonium salt, a kind of method that the deficiency of silica zeolite provides new use organic quaternary ammonium salt template synthesis silica zeolite.

The present invention provides the synthetic method of a kind of silica zeolite, comprises the steps:

(1) template, organosilicon source, inorganic source of ammonium and water are mixed, stir at least 10 minutes at 0～150 DEG C, so that organosilicon source is hydrolyzed and reduces the content of the alcohol that the hydrolysis of organosilicon source obtains in product；The mixing time of described stirring such as 10 minutes～50 hours；

(2) by aging for step (1) products therefrom, described aging be in left at room temperature 1～60 hour such as 2～50 hours or 3～30 hours by step (1) products therefrom, such as 3～15 hours further；

(3) ageing products obtained for step (2) is mixed homogeneously according to the weight ratio of 1:0.1～10 with solid silicon source, then crystallization in closed reactor, reclaim silica zeolite；In wherein said part by weight, ageing products that step (2) is obtained and solid silicon source are all with SiO₂Meter；

Wherein, the mol ratio of template, silicon source, inorganic source of ammonium and water is (0.08～0.6): 1:(0.01～0.1): (3～100), in wherein said mol ratio, silicon source (also referred to as total silicon source) is with SiO₂Meter organosilicon source and with SiO₂The total mole number of the solid silicon source of meter, inorganic source of ammonium is with NH₄ ⁺Meter, inorganic source of ammonium can be inorganic ammonium salt and/or ammonia, and water is with H₂O counts；Described template is the mixture of organic quaternary ammonium salt and organic amine, and wherein organic quaternary ammonium salt and silicon source are (with SiO₂Meter organosilicon source and with SiO₂The total mole number of solid silicon source of meter) mol ratio be 0.04～0.55:1, the mol ratio in organic amine and silicon source is 0.04～0.45:1.

Silica zeolite synthetic method provided by the invention, organic quaternary ammonium salt template is used to synthesize silica zeolite without organic quaternary amine alkali, the molecular sieve of the more existing use of obtained molecular sieve organic quaternary amine synthesis has less grain size, has higher activity.Molecular sieve prepared by the inventive method has more defective bit quantity, its Q⁴/Q³Lower than 90, for instance be 10～70:1, it is 15～50:1, wherein Q further⁴For described silica zeolite²⁹In SiNMR spectrogram, chemical shift is the peak intensity at-112 ± 2ppm place, represents with peak height, Q³For described silica zeolite²⁹In SiNMR spectrogram, chemical shift is the peak intensity at-103 ± 2ppm place, represents with peak height.In addition, silica zeolite synthetic method provided by the invention, use the relatively inexpensive solid silicon source being easy to get such as high-purity silica gel or/and white carbon, part replaces expensive organosilicon source, organic quaternary ammonium salt is used to replace quaternary ammonium base, it is possible to reduce the waste discharge of process of producing molecular sieve and the cost that economizes in raw materials.Silica zeolite synthetic method provided by the invention can obtain and the suitable silica zeolite of silica zeolite grain size being all Material synthesis with organosilicon and quaternary ammonium base.Silica zeolite synthetic method provided by the invention, can in relatively low template agent consumption and relatively low water silicon are than situation synthesis silica zeolite, the synthesis cost of silica zeolite can be substantially reduced, improve the solid content of synthesis of molecular sieve crystallization product, improve single still molecular sieve yield.

Accompanying drawing explanation

Fig. 1 is the XRD spectra of total silicon S-1 molecular sieve prepared by the present invention.

Fig. 2 is the XRD spectra of total silicon beta-molecular sieve prepared by the present invention.

Fig. 3 is the total silicon S-1 molecular sieve of prior art and present invention synthesis²⁹SiNMR spectrogram.

Fig. 4 is the SEM scanning figure of the total silicon S-1 molecular sieve of embodiment 1 synthesis.

Fig. 5 is that total silicon beta-molecular sieve (also known as the beta molecular sieve) SEM that the present invention synthesizes scans figure

Fig. 6 is the TEM figure of the total silicon S-1 molecular sieve that embodiment 1 step (4) obtains.

Detailed description of the invention

The synthetic method of silica zeolite provided by the invention, silica zeolite can be synthesized in relatively low template agent consumption situation, thus template agent consumption can reduce, such as template agent with the mol ratio in organosilicon source that silicon dioxide is counted for 0.1～0.36:1, be 0.1～0.25:1 or 0.1～0.2:1 further；In method provided by the invention, silica zeolite can be synthesized under high solids content, from can and reduce the consumption that makes of water, improve output per single reactor and namely under same synthesis reactor volume, synthesize more molecular sieve, the mol ratio of therefore described water and silicon dioxide can be 5～80:1 or be 5～50:1, is such as 6～30:1 further or is 6～20:1.

The synthetic method of silica zeolite provided by the invention, the mol ratio of described template, silicon source (i.e. total silicon source), inorganic source of ammonium and water can be (0.1～0.55): 1:(0.01～0.1): (5～100) are such as (0.1～0.36): 1:(0.01～0.1): (5～80), further, the mol ratio of described template, silicon source, inorganic source of ammonium and water is (0.1～0.36): 1:(0.01～0.1): (5～50).Preferably, the mol ratio of described template, silicon source, inorganic source of ammonium and water is (0.1～0.25): 1:(0.01～0.07): (6～30).Under preferable case, the mol ratio in described template and silicon source is 0.1～0.25:1;The mol ratio in described water and silicon source is 6～20:1；The mol ratio in described inorganic source of ammonium and silicon source is 0.01-0.05:1.

The synthetic method of silica zeolite provided by the invention, the mixture that template agent is organic amine and organic quaternary ammonium salt described in step (1).Described organic amine is one or more in fatty amine, aromatic amine or hydramine, and described fatty amine (present invention is also referred to as fat amine compound), its formula is R³(NH₂)_n, wherein R³For having alkyl or the alkylidene of 1～4 carbon atom, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR⁴)_mNH_(3-m), wherein R⁴For having the alkyl of 1～4 carbon atom, m=1,2 or 3.One or more in described fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；One or more in described hydramine such as monoethanolamine, diethanolamine or triethanolamine.Described aromatic amine refers to the amine with an armaticity substituent group, for instance one or more in aniline, toluidines, p-phenylenediamine.

Described template agent, organic quaternary ammonium salt with SiO₂The mol ratio in the silicon source (described silicon source refers both to total silicon source) of meter is 0.05～0.3:1, for instance be 0.05～0.2:1；Organic amine with SiO₂The mol ratio in the silicon source of meter is 0.05～0.45:1, for instance is 0.05～0.35:1, or is 0.1～0.25:1.

One or more in described organic quaternary ammonium salt such as 4-propyl bromide, tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride.

A kind of embodiment, described silica zeolite is S-1 molecular sieve, and described organic quaternary ammonium salt is 4-propyl ammonium chloride and/or 4-propyl bromide.

A kind of embodiment, described silica zeolite is S-2 molecular sieve, and described organic quaternary ammonium salt is tetrabutylammonium chloride and/or tetrabutyl ammonium bromide.

A kind of embodiment, described silica zeolite is total silicon beta molecular sieve (total silicon beta-molecular sieve), and described organic quaternary ammonium salt is tetraethylammonium chloride and/or tetraethylammonium bromide.

Silica zeolite synthetic method provided by the invention, the organosilicon source described in step (1) is organic silicone grease, described organo-silicon ester, and its formula is Si (OR¹)₄, R¹Selected from the alkyl such as R with 1～6 carbon atom¹For C₁-C₄Alkyl, described alkyl can be branched alkyl or straight chained alkyl.One or more in described organic silicone grease such as silicic acid four formicester, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl estersil；Wherein one or more in preferred quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil.Solid silicon source described in the present invention is highly purified silica solid or powder, for instance can be white carbon and/or high-purity silica gel.Under preferable case, with butt weight for solid silicon source SiO described in benchmark₂Content is not less than 99.99 weight %, and the mass content of Fe, Al and Na impurity (in element) is less than 10ppm；Such as SiO₂Content is 99.99～100 weight %, is typically greater than 99.99 and less than 100 weight %.Described solid silicon source can be high silica gel and/or white carbon, it is preferable that white carbon, SiO in wherein said silica gel₂It is such as more than 99.99 weight % and less than 100 weight % that content is preferably greater than or equal to 99.99 weight %, and the total content of Fe, Al and Na impurity is less than 10ppm(mass).The specific surface area of described white carbon is preferably between 50-400m²Between/g, with the butt weight of white carbon for benchmark, SiO in described white carbon₂Content be preferably greater than or equal to 99.99 weight % be such as 99.99～100 weight % such as more than 99.99 weight % and less than 100 weight %, in described white carbon, the gross mass content of Fe, Al and Na impurity is less than 10ppm.Described white carbon can be purchased, or prepares according to existing method, for instance prepares according to the patent CN200910227646.2 method provided.A kind of preparation method is to be obtained with hydrogen and oxygen generation combustion reaction by Silicon chloride..

Silica zeolite synthetic method provided by the invention, the inorganic source of ammonium described in step (1) is inorganic ammonium salt and/or ammonia, obtains one or more in described inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate.Described inorganic source of ammonium is preferably ammonia, with NH₄ ⁺Meter ammonia with SiO₂The mol ratio in the silicon source (with described organosilicon source and described solid silicon source total amount) of meter is for 0.01～0.1:1, for instance be 0.01～0.07:1 or 0.01～0.05:1.

In silica zeolite synthetic method provided by the invention, by template, organosilicon source, inorganic source of ammonium and water by mixing in step (1), at least 10 minutes are stirred at 0～150 DEG C such as 10～100 DEG C, so that the hydrolysis of organosilicon source, and reduce the monohydric alcohol content in gained mixture, namely it is hydrolyzed and catches up with alcohol.Usual mixing time is 10～3000 minutes, for instance be 2～30 hours.Catch up with alcohol by being hydrolyzed, obtain the organosilicon hydrolyzation liquid of clear.In the mixture that usual step (1) obtains, the mass content of the monohydric alcohol that the hydrolysis of organosilicon source produces is not higher than 10ppm.In the product of preferred steps 1, the mass content of monohydric alcohol is less than 10ppm.

Silica zeolite synthetic method provided by the invention, in step (2), by aging for step (1) products therefrom, described aging be at room temperature by step (1) products therefrom stand 1～60 hour.Described room temperature is 15～40 DEG C；Ageing time is 1～60 hour is such as 2～50 hours, it is preferable that 3～30 hours such as 3～15 hours, be not stirred in ageing process, described material and step (1) products therefrom is stood.

Silica zeolite synthetic method provided by the invention, mixes the ageing products that step (2) obtains with solid silicon source in step (3), with SiO₂The mol ratio of meter, the product that step (2) obtains and solid silicon source is 1:0.1～10, for instance can be 0.2:1～9, it is possible to be 1:2～8, it is possible to be that 1:1～7 are further for 1:3～6.Method provided by the invention, it is possible to use the solid silicon source synthesis silica zeolite of higher proportion, it is possible to improve the solid content of synthetic product, thus improving the yield of single synthesis when synthesis reaction vessel is constant.Obtain the production die that the synthetic method of product more existing use solid silicon source obtains less, it is possible to reach all to use the crystal grain level in organosilicon source, even less.

Silica zeolite synthetic method provided by the invention, step (3) described crystallization, the temperature of crystallization is 110～200 DEG C, crystallization pressure is self-generated pressure, the time of crystallization is 2 hours～20 days, and the time of usual described crystallization is 0.5～20 day, for instance crystallization time is 0.5～10 day, the temperature of the crystallization described in further step (3) is 140～180 DEG C and is such as 160～180 DEG C, and crystallization time is 0.5～6 day is such as 1～3 day.Crystallization pressure is self-generated pressure.Described crystallization can carry out in rustless steel stirred tank.Crystallization heat up can one section of intensification can also multistage heating mode.Heating rate can carry out according to existing crystallization temperature-rising method, for instance for 0.5-1 DEG C/min.Described crystallization can carry out in rustless steel stirred tank.A kind of embodiment, the crystallization temperature of described crystallization is 160～180 DEG C, and crystallization time is 0.5～6 day such as 0.5～3 day, and crystallization pressure is self-generated pressure.A kind of embodiment, the crystallization described in step (3) is: crystallization 0.5～1.5 day at 100～130 DEG C such as 110～130 DEG C, then crystallization 1～3 day at 160～180 DEG C, crystallization pressure is self-generated pressure.

Silica zeolite synthetic method provided by the invention, reclaiming silica zeolite described in step (3) is existing method, including by crystallization product filtration, washing and roasting or by crystallization product filtration, washing, dry then roasting.The purpose filtered is that silica zeolite crystallization obtained separates with crystallization mother liquor, the purpose of washing is the siliceous template solution washing away and being adsorbed on sieve particle surface, can be such as room temperature～50 DEG C in temperature, the weight ratio 1:1～20 such as 1:(1-15 of molecular sieve and water) under carry out mixing, washing or drip washing.Dry purpose is to remove the most of moisture in molecular sieve, and to reduce water evaporation quantity when roasting, dry temperature can be 100～200 DEG C.The purpose of roasting is to remove the template in molecular sieve, for instance the temperature of described roasting is 350～650 DEG C, and roasting time is 2-10 hour.Silica zeolite product provided by the present invention is obtained by reclaiming.

In silica zeolite synthetic method provided by the invention, step (3) reclaims the silica zeolite obtained and is also may pass through further process, i.e. silica zeolite synthetic method provided by the invention, it is also possible to include step (4):

(4) the silica zeolite Crystallizing treatment in organic alkali solution step (3) obtained, then reclaims silica zeolite.This process makes obtained silica zeolite have hollow-core construction or claim grain surface to have empty male and fomale(M&F), and the present invention is referred to as molecular sieve and resets.Wherein molecular sieve is (with SiO₂Meter) with the molar ratio of organic base be 1:0.02～0.5 such as 1:0.02～0.2, with SiO₂The molecular sieve of meter and the mol ratio of water are 1:2～50 is such as 1:5～10 for 1:2～20, crystallization temperature is 120～200 DEG C, time is 0.5～10 day such as 0.5～8 day, crystallization pressure is self-generated pressure, preferably, crystallization temperature described in step (4) is 150-200 DEG C, and crystallization time is 0.5～6 day.Recovery method is existing method, generally includes crystallization product filtration, washing, dry and roasting, can refer to the recovery method described in step (3).Described organic base is one or more in organic quaternary ammonium salt, organic amine.One or more mixture in described quaternary ammonium base such as TPAOH, TBAH or tetraethyl ammonium hydroxide.Described organic amine is one or more in fatty amine, aromatic amine and hydramine, and described fatty amine (present invention is also referred to as fat amine compound), its formula is R³(NH₂)_n, wherein R³For having alkyl or the alkylidene of 1～4 carbon atom, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR⁴)_mNH_(3-m), wherein R⁴For having the alkyl of 1～4 carbon atom, m=1,2 or 3.One or more in described fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；Described aromatic amine refers to the amine with an armaticity substituent group, for instance one or more in aniline, toluidines, p-phenylenediamine；One or more in described hydramine such as monoethanolamine, diethanolamine or triethanolamine.A kind of embodiment, described silica zeolite is S-1 molecular sieve, and the quaternary ammonium base described in step (4) is TPAOH.A kind of embodiment, described silica zeolite is S-2 molecular sieve, and the quaternary ammonium base described in step (4) is TBAH.A kind of embodiment, described silica zeolite is total silicon beta molecular sieve (total silicon beta-molecular sieve), and the quaternary ammonium base described in step (4) is tetraethyl ammonium hydroxide.

Step (4) present invention is referred to as molecular sieve and resets, and this process can carry out once, it is also possible to be repeated once or repeatedly, described repetition, the silica zeolite obtained by process replaces the molecular sieve that step (3) obtains to process according to the method for step (4).Processed by rearrangement, it is possible to obtaining the silica zeolite with secondary pore structure, the crystal grain of gained silica zeolite is hollow-core construction, and the radical length of the chamber portion of this hollow crystal grain is 5～300nm, at 25 DEG C, P/P₀=0.10, the benzene adsorbance recorded when adsorption time 1 hour is at least 70 milligrams per gram, there is hysteresis loop between adsorption isotherm and the desorption isotherm of the nitrogen absorption under low temperature of this molecular sieve.There is higher pore volume and specific surface area..

Silica zeolite prepared by the method utilizing organic quaternary ammonium salt synthesis silica zeolite provided by the invention, its Q⁴/Q³It is 10～90:1, wherein Q⁴For described silica zeolite²⁹In SiNMR spectrogram, chemical shift is the peak intensity at-112 ± 2ppm place, represents with peak height, Q³For described silica zeolite²⁹In SiNMR spectrogram, chemical shift is the peak intensity at-103 ± 2ppm place, represents with peak height.Described Q⁴/Q³It is preferably 15～50:1.The grain size (short-axis direction) of described silica zeolite is such as 200nm～2 μm, 140nm～2 μm, is such as 200nm～700nm further.The granule of described silica zeolite is that single crystal grain or multiple crystal grain are assembled and formed.Described silica zeolite is preferably S-1 molecular sieve, S-2 molecular sieve or beta-molecular sieve.

In silica zeolite, a silicon atom is connected by oxygen with four additional silicon atom, is represented by Si (OSi)₄, its²⁹In SiNMR spectrogram, having peak in chemical shift for-112 ± 2ppm place, its peak intensity (represents with peak height value) and is expressed as Q⁴；One silicon atom and the other three silicon atom are connected by oxygen and (are represented by SiOH (OSi)₃), its²⁹In SiNMR spectrogram, chemical shift has peak for-103 ± 2ppm place, and its peak intensity (represents with peak height value) and is expressed as Q³；Q⁴/Q³Reflecting the quantity of defective bit contained by silica zeolite to a certain extent, this ratio is more big, represents that defective bit is more few.This ratio of silica zeolite prepared by prior art is more than 95.

Silica zeolite provided by the invention, has the more defect silicon position connecting 3 silicon atoms in lattice, have higher catalysis activity for cyclohexanone-oxime Beckmann rearrangement.

The present invention is further illustrated for the following examples, but and is not so limited the present invention.What reagent used in embodiment did not further illustrate is commercially available analytical reagent.Silica zeolite used in comparative example 1 is the S-1 sieve sample prepared by the method described in the method for prior art CN1338427A.

Q in embodiment⁴/Q³Measuring method adopt²⁹SiMASNMR method.Use VarianINOVA300 type nuclear magnetic resonance chemical analyser to measure, adopt solid double resonance probe, Φ 6mmZrO₂Rotor.²⁹It is 59.588MHz that Si detects the resonance spectrum of core, and evil spirit angle rotating speed is 3kHz, sampling time 0.02s, pulsewidth 1.5 μ s, circulation delay time 3s, scanning times 3000 times.

The measuring method of grain size: adopt SEM Electronic Speculum characterizing method, the Quanta200F type scanning electron microscope that FEI Co. produces: after sample drying processes, vacuum evaporation metal spraying, to increase electric conductivity and contrast effect；Analytic electron microscope accelerating potential is 20.0kV, amplification 1～30k.

TEM method: electron microscope experiment carries out on FEI Co. TecnaiF20G2S-TWIN type transmission electron microscope, is furnished with the energy filter system GIF2001 of Gatan company, adnexa is equipped with X-ray energy spectrometer.Electron microscopic sample adopts the method for suspended dispersed to prepare on micro-grid of diameter 3mm.

XRD measuring method: X-ray diffraction (XRD) the crystalline phase figure carrying out sample on SiemensD5005 type x-ray diffractometer measures, and radiographic source is CuK αTube voltage 40kV, tube current 40mA, 0.5 °/min of scanning speed, sweep limits 2 θ=4 °～40 °.

The method of testing of BET specific surface area and pore volume adopts N2 adsorption volumetric method, according to BJH computational methods.(can referring to Petrochemical Engineering Analysis method (RIPP test method), RIPP151-90)

In embodiment and comparative example, raw materials used character is as follows:

4-propyl bromide, commercial goods, concentration is 20.05 weight %,

4-propyl ammonium chloride, commercial goods, concentration is 20.05 weight %,

Tetraethyl orthosilicate, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.

Ammonia, analytical pure, concentration 20 weight %.

White carbon, Zhejiang Ju Hua group product, model AS-150；Solid content is more than 95 weight %;In butt, dioxide-containing silica is more than 99.99 weight %, and the gross mass content of ferrum, sodium and Al is less than 10ppm, and specific surface area is 195m²/g。

Embodiment 1

(1) by 4-propyl bromide (TPABr) aqueous solution that 17.9g concentration is 20.05 weight %, it is added sequentially in the beaker of 500ml with the ammonia that 1.62 grams of ethylenediamines, 20.8g tetraethyl orthosilicate, 0.26g concentration are 20 weight % and 13.5g deionized water, put into the magnetic stirring apparatus with heating and agitating function, stir 4 hours at 80 DEG C, supplement the moisture of evaporation at any time, obtain the organic base hydrolyzed solution of silicon；Wherein the content of monohydric alcohol is less than 10ppm；

(2) the organic base hydrolyzed solution of gained silicon being under agitation cooled to room temperature, then at room temperature standing 12 is hours aging, obtains ageing products；

(3) under stirring, described ageing products adds 12g white carbon powder (in butt), stir 2 hours, be transferred in rustless steel closed reactor, in 165 DEG C of thermostatic crystallizations 12 hours, total silicon S-1 Crystallization of Zeolite product, the S-1 Crystallization of Zeolite product obtained is filtered, uses the deionized water wash decupling molecular sieve, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, obtain S-1 sample S-1-Y1；Its XRD analysis spectrogram is as shown in Figure 1；²⁹SiMASNMR characterization result as it is shown on figure 3, SEM as shown in Figure 4.Its BET specific surface area is 420m².g^-1, mesopore volume is 0.082mL.g^-1, micro pore volume is 0.171mL.g^-1。

(4) by the TPAOH aqueous solution Homogeneous phase mixing of 6gS-1-Y1 sample and 10 mass %, wherein the consumption of aqueous solution is 25.2g, in airtight reactor, 150 DEG C of crystallization 3 days, filter, wash, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, obtain sample S-1-Y1P.Its XRD analysis spectrogram is as it is shown in figure 1, its BET specific surface area is 437m²/ g, micro pore volume is 0.155mL.g^-1, mesopore volume is 0.158mL.g^-1, in transmission electron microscope photo, it is hollow-core construction (shown in Fig. 6).

The preparation condition of embodiment 1 and the characterization result of obtained molecular sieve are in Table 1.

Embodiment 2～6

Preparing molecular sieve according to the method for embodiment 1, the difference is that adjusting proportioning and preparation condition, the wherein condition inconvenience of step (4), its proportioning and characterization result are in Table 1.

Embodiment 7

Template is 4-propyl ammonium chloride (TPACl) and ethamine, TPACl: the mol ratio=0.1:0.15 of ethamine, preparation method reference example 1, preparation condition and characterization result are in Table 1.

Embodiment 8

Changing template, synthesize total silicon S-2 molecular sieve, preparation condition and characterization result are in Table 1.

Embodiment 9

Changing template, synthesize total silicon beta-molecular sieve, preparation condition and characterization result in Table 1, XRD spectra is as in figure 2 it is shown, SEM schemes as shown in Figure 5.

Comparative example 1

This comparative example illustrates to prepare conventional silica zeolite S-1 according to the method for CN1338427A.

It is that 22.05 weight % TPAOH solution mix by 208g tetraethyl orthosilicate and 180g concentration, adds 64.5g deionized water Homogeneous phase mixing；Then at 60-80 DEG C, it is hydrolyzed 5-9h, obtains containing tetraethyl orthosilicate hydrating solution;Under the effect being stirred vigorously, this mixture is continued at 75 DEG C stirring 7h, obtain colloid, then this colloid is moved in rustless steel closed reactor, thermostatic crystallization 2 days at 170 DEG C, conventional S-1 molecular sieve can be obtained；

By the S-1 sample filtering obtained, washing, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours.By the TPAOH aqueous solution Homogeneous phase mixing that the S-1 sample after 6g roasting and 22 grams of concentration are 22.05 weight %, 150 DEG C of crystallization 1 day in airtight reactor, filter, washing, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, product described in this patent.

Preparation condition and characterization result are in Table 1.

Comparative example 2

Prepare silica zeolite according to the method for comparative example 1, the difference is that with the white carbon of equivalent (with SiO₂Meter) replace the tetraethyl orthosilicate described in comparative example 1 (with SiO₂Meter).Preparation condition and characterization result are in Table 1.

Comparative example 3

According to the method for embodiment 1, the difference is that not introducing ammonia, do not carry out aging.Preparation condition and characterization result are in Table 1.

Comparative example 4

According to the method for embodiment 1, the difference is that, by solid silicon source, organosilicon source, template, water mixing, after stirring hydrolysis, direct crystallization, it is added without ammonia.Preparation condition and characterization result are in Table 1.

Comparative example 5

According to the method for embodiment 1, aging the difference is that not carrying out.Preparation condition and characterization result are in Table 1.

Evaluation operation example

Molecular sieve after the silica zeolite do not reset provide above-described embodiment and comparative example and rearrangement is evaluated.Cyclohexanone-oxime Beckmann rearrangement is adopted to evaluate the catalytic performance of gained silica zeolite.Silica zeolite tabletting, then crushes, and takes the granule of 20-60 order as catalyst.Evaluation result is in Table 1.Appreciation condition is as follows:

Reaction unit is that normal pressure flows fixing bed continuously, and reactor inside diameter is 5 millimeters, and catalyst (silica zeolite) loadings is 0.5g, and the grain graininess of catalyst is 20-60 order.

Catalyst loads after reaction tube, pretreatment 2 hours in normal pressure, the nitrogen atmosphere of 350 DEG C.

The concentration of cyclohexanone-oxime is 35.7 weight %, and weight space velocity (WHSV) is 7.5h^-1, solvent is methanol, and reaction temperature is 350 DEG C, and the flow velocity of nitrogen is 1.8 ls/h, 3 hours response time.

Product is by collecting after water circulating condensing, and hydrogen flame detector, gas chromatography records its composition.

It should be noted that can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims

1. a synthetic method for silica zeolite, comprises the following steps:

(1) template, organosilicon source, inorganic source of ammonium and water are mixed, stir at least 10 minutes at 0～150 DEG C；

(2) by aging for step (1) products therefrom, described aging be in left at room temperature 1～60 hour by step (1) products therefrom；

(3) by mixed in molar ratio according to 1:0.1～10 of ageing products obtained for step (2) and solid silicon source, then crystallization in closed reactor, silica zeolite is reclaimed；In wherein said part by weight, the obtained ageing products of described step (2) is with SiO₂Meter, solid silicon source is with SiO₂Meter；The mol ratio of template, silicon source, inorganic source of ammonium and water is (0.08～0.6): 1:(0.01～0.1): (3～100)；In wherein said mol ratio, silicon source is with SiO₂Meter, for SiO₂Meter organosilicon source and with SiO₂The summation of the solid silicon source of meter, inorganic source of ammonium is with NH₄ ⁺Meter；Described inorganic source of ammonium is inorganic ammonium salt and/or ammonia；Described template is the mixture of organic quaternary ammonium salt and organic amine, and wherein organic quaternary ammonium salt is 0.04～0.55:1 with the mol ratio in silicon source, and the mol ratio in organic amine and silicon source is 0.04～0.45:1.

2. in accordance with the method for claim 1, it is characterised in that described organic amine with SiO₂The mol ratio in silicon source of meter is 0.05～0.35:1, organic quaternary ammonium salt with SiO₂The mol ratio in the silicon source of meter is 0.05～0.3:1.

3. the method described in claim 1 or 2, it is characterized in that, the mol ratio of described template, silicon source, inorganic source of ammonium and water is (0.1～0.36): 1:(0.01～0.1): (5～80) or (0.1～0.36): 1:(0.01～0.1): (5～50).

4. in accordance with the method for claim 3, it is characterised in that the mol ratio of described template, silicon source, inorganic source of ammonium and water is (0.1～0.25): 1:(0.01～0.07): (6～30).

5. in accordance with the method for claim 1, it is characterised in that the mol ratio in described template and silicon source is 0.1～0.20:1；The mol ratio in water and silicon source is 6～20:1, and the mol ratio in inorganic source of ammonium and silicon source is 0.01-0.07:1；Described silicon source is with SiO₂Meter organosilicon source and with SiO₂The summation of the solid silicon source of meter.

6. in accordance with the method for claim 1, it is characterised in that described organosilicon source is organic silicone grease, described organo-silicon ester, its formula is Si (OR¹)₄, R¹Selected from the alkyl with 1～6 carbon atom, described alkyl is branched-chain or straight-chain alkyl；Described solid silicon source is high-purity silicon dioxide granule or SiO 2 powder, with butt weight for benchmark, and the SiO of described solid silicon source₂Content more than 99.99 weight %, in the Fe of atom, Al and Na total content less than 10ppm.

7. in accordance with the method for claim 6, it is characterised in that described organic silicone grease is one or more in silicic acid four formicester, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl silicone grease；Described solid silicon source is white carbon, and the specific surface area of described white carbon is 50～400m²/ g, described organic amine is one or more in fatty amine, aromatic amine and hydramine.

8. in accordance with the method for claim 7, it is characterised in that the formula of described fatty amine is R³(NH₂)_n, wherein R³For having alkyl or the alkylidene of 1～4 carbon atom, n=1 or 2；Its formula of described hydramine is (HOR⁴)_mNH_(3-m), wherein R⁴For having the alkyl of 1～4 carbon atom, m=1,2 or 3；Described aromatic amine is the amine comprising an armaticity substituent group.

9. in accordance with the method for claim 8, it is characterised in that described fatty amine is one or more in ethamine, n-butylamine, butanediamine or hexamethylene diamine；Described hydramine is one or more in monoethanolamine, diethanolamine or triethanolamine；Described aromatic amine is one or more in aniline, toluidines, p-phenylenediamine.

10. in accordance with the method for claim 1, it is characterised in that described silica zeolite is S-1 molecular sieve, described organic quaternary ammonium salt is 4-propyl ammonium chloride and/or 4-propyl bromide；Or, described silica zeolite is S-2 molecular sieve, and described organic quaternary ammonium salt is tetrabutylammonium chloride and/or tetrabutyl ammonium bromide；Or, described silica zeolite is total silicon beta molecular sieve, and described organic quaternary ammonium salt is tetraethylammonium chloride and/or tetraethylammonium bromide.

11. in accordance with the method for claim 1, it is characterised in that step (3) described crystallization, the temperature of crystallization is 110～200 DEG C, crystallization pressure is self-generated pressure, and the time of crystallization is 2 hours～20 days or 0.5～10 day.

12. in accordance with the method for claim 11, it is characterised in that the crystallization temperature of crystallization described in step (3) is 140～180 DEG C or 160～180 DEG C.

13. in accordance with the method for claim 1, it is characterised in that the crystallization described in step (3) is: crystallization 0.5～1.5 day at 100～130 DEG C, then crystallization 1～3 day at 160～180 DEG C, and crystallization pressure is self-generated pressure.

14. in accordance with the method for claim 1, it is characterised in that the temperature of step (1) described stirring is 50～90 DEG C, mixing time is 2～30 hours.

15. the method described in claim 1 or 14, it is characterised in that in the product that step (1) obtains, the mass content of the alcohol that the hydrolysis of organosilicon source produces is less than 10ppm.

16. in accordance with the method for claim 1, it is characterised in that the described aging ageing time of step (2) is 2～50 hours or is 3～30 hours or is 3～15 hours.

17. in accordance with the method for claim 1, it is characterised in that with SiO₂Meter solid silicon source and with SiO₂The mol ratio in organosilicon source of meter is 1～9:1 or is 2～8:1 or is 3～7:1.

18. according to claim 1～2,4～14 or 16～17 methods described in any one, it is characterized in that, described method also includes step (4): silica zeolite crystallization 0.5～10 day in organic base aqueous solution step (3) obtained, the temperature of crystallization is 110～200 DEG C；Wherein with SiO₂Silica zeolite and the mol ratio of described organic base that meter is described are 1:0.02-0.5, with SiO₂Silica zeolite and the mol ratio of water that meter is described are 1:2～50.

19. in accordance with the method for claim 18, it is characterised in that the temperature of step (4) described crystallization is 150～200 DEG C, with SiO₂Silica zeolite and the mol ratio of described organic base that meter is described are 1:0.02-0.2, with SiO₂Silica zeolite and the mol ratio of water that meter is described are 1:2～20, and pressure is self-generated pressure.