CN104556086A

CN104556086A - Method for synthesizing all-silicon molecular sieve from organic quaternary ammonium salt

Info

Publication number: CN104556086A
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: 2015-04-29
Anticipated expiration: 2033-10-29
Also published as: CN104556086B

Abstract

The invention discloses a method for synthesizing an all-silicon molecular sieve from an organic quaternary ammonium salt. The method comprises the following steps: mixing a template agent, an organic silicon source, an inorganic ammonium source and water, hydrolyzing to reduce alcohol, aging, further mixing with solid silicon, crystallizing in a sealed reaction kettle, and recycling the all-silicon molecular sieve, wherein the template is a mixture of the quaternary ammonium salt and organic amine. The all-silicon molecular sieve prepared by using the all-silicon molecular sieve synthesis method disclosed by the invention is relatively high in cyclohexanone-oxime beckmann rearrangement activity.

Description

A kind of method utilizing organic quaternary ammonium salt to synthesize silica zeolite

Technical field

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

Background technology

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

Disclosed silica zeolite direct hydrothermal synthesis method, uses organosilicon source and/or inorganic silicon source usually at present.Organosilicon source is organo-silicon ester TEOS such as, price comparison is expensive, and its active constituent content forming molecular sieve is also lower, is difficult to the solid content improving 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 costs, researchist studies and adopts inorganic silicon source to replace part or all of organosilicon source, but uses the silica zeolite crystal grain of inorganic silicon source synthesis comparatively large at present, and activity is not higher.

Within 1977, union carbide corporation of the U.S. reports the method for direct hydrothermal synthesis all-silica MFI structure molecular screen in USP4061724, and it is first prepared and mole consists of (0-6.5) M ₂o:(13-50) SiO ₂: Q ₂o:(150-700) H ₂the reaction mixture of O, crystallization 50-150 hour at then this mixture being placed in 100-250 DEG C, wherein M is alkalimetal ion, organic formwork agent Q=R ₄x ⁺, R is the alkyl of 2-6 carbon atom, and X is P or N.Then they disclose again and add fluorine element to reduce the method for total silicon S-1 Crystallization of Zeolite temperature in patent USP4073865, but fluorine element has severe contamination to environment, and its application is restricted.Silica zeolite prepared by above method is not high for cyclohexanone-oxime Beckmann rearrangement activity.

CN97100231.2 discloses a kind of synthetic method of crystalline silicon dioxide molecular sieve, the method take solid silicone as raw material, with amine organism (Q) for template, itself and NaOH and water are obtained by mixing and mole consist of (0.02-0.3) Na ₂o:(0.05-0.8) SiO ₂: (1-10) H ₂the reaction mixture of O is then little of 10 days in 100-200 DEG C of crystallization 8 according to a conventional method by this reaction mixture.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 is preparing the application in hexanolactam, and S-1 silica zeolite makes by following method: the synthesis of (1) TPAOH template; (2) synthesis of molecular sieve: by the TPAOH aqueous solution and tetraethoxy and ethanol synthesis, filters, and with deionized water wash, reaction solution is dry, and roasting, obtains molecular screen primary powder; In molecular screen primary powder, add silicon sol, Macrogol 2000, strong aqua, 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 put into NH successively ₃-NH ₄nO ₃soak in mixing solutions and hydrofluoric acid aqueous solution, with deionized water wash; Drying, again roasting, 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 a kind of method providing use organic quaternary ammonium salt template synthesis silica zeolite newly for the deficiency of existing use organic quaternary ammonium salt synthesis silica zeolite.

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

(1) by template, organosilicon source, Inorganic Ammonium source and water mixing, stir at least 10 minutes at 0 ~ 150 DEG C, be hydrolyzed to make organosilicon source and reduce organosilicon source in product and be hydrolyzed the content of the alcohol obtained; The churning time of described stirring such as 10 minutes ~ 50 hours;

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

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

Wherein, the mol ratio of template, silicon source, Inorganic Ammonium source and water is (0.08 ~ 0.6): 1:(0.01 ~ 0.1): (3 ~ 100), in wherein said mol ratio, silicon source (also claiming total silicon source) is for SiO ₂meter organosilicon source and with SiO ₂the total mole number of the solid silicon source of meter, Inorganic Ammonium source is with NH ₄ ⁺meter, Inorganic Ammonium source can be inorganic ammonium salt and/or ammoniacal liquor, and water is with H ₂o 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 SiO ₂meter organosilicon source and with SiO ₂the 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, use organic quaternary ammonium salt template and silica zeolite need not be synthesized by organic quaternary amine alkali, the molecular sieve of the more existing use of the molecular sieve obtained organic quaternary amine synthesis has less grain size, has higher activity.Molecular sieve prepared by the inventive method has more defective bit quantity, its Q ⁴/ Q ³lower than 90, such as, being 10 ~ 70:1, is 15 ~ 50:1, wherein Q further ⁴for described silica zeolite ²⁹in SiNMR spectrogram, chemical shift is the peak intensity at-112 ± 2ppm place, represents, Q with peak height ³for described silica zeolite ²⁹in 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 be easy to get such as high-purity silica gel or/and white carbon black, part replaces expensive organosilicon source, use organic quaternary ammonium salt to replace quaternary ammonium base, the waste discharge of process of producing molecular sieve and the cost that economizes in raw materials can be reduced.Silica zeolite synthetic method provided by the invention can obtain with all with the silica zeolite that organosilicon and the quaternary ammonium base silica zeolite grain size that is Material synthesis is suitable.Silica zeolite synthetic method provided by the invention, silica zeolite can be synthesized than in situation at lower template agent consumption and lower water silicon, greatly can reduce the synthesis cost of silica zeolite, improve the solid content of synthesis of molecular sieve crystallization product, improve single still molecular sieve output.

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 that prior art and the present invention synthesize ²⁹si NMR spectrogram.

Fig. 4 is the SEM scintigram of the total silicon S-1 molecular sieve that embodiment 1 is synthesized.

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

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

Embodiment

The synthetic method of silica zeolite provided by the invention, silica zeolite can be synthesized in lower template agent consumption situation, thus template agent consumption can reduce, such as template agent with in the mol ratio in the organosilicon source of silicon-dioxide 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 usage quantity of water, improve output per single reactor and namely under same synthesis reactor volume, synthesize more molecular sieve, therefore described water and the mol ratio of silicon-dioxide can be 5 ~ 80:1 or be 5 ~ 50:1, are such as 6 ~ 30:1 further or are 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 Ammonium source 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 Ammonium source and water is (0.1 ~ 0.36): 1:(0.01 ~ 0.1): (5 ~ 50).Preferably, the mol ratio of described template, silicon source, Inorganic Ammonium source 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; Described Inorganic Ammonium source and the mol ratio in silicon source are 0.01-0.05:1.

The synthetic method of silica zeolite provided by the invention, the template agent described in step (1) is the mixture of organic amine and organic quaternary ammonium salt.Described organic amine is one or more in aliphatic amide, aromatic amine or hydramine, and described aliphatic amide (the present invention also claims fat amine compound), its general formula is R ³(NH ₂) _n, wherein R ³for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Described hydramine (the present invention also claims alcamine compound) its general formula is (HOR ⁴) _mnH _(3-m), wherein R ⁴for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3.One or more in described aliphatic amide such as ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; One or more in described hydramine such as monoethanolamine, diethanolamine or trolamine.Described aromatic amine refers to have the substituent amine of aromaticity, such as, in aniline, Tolylamine, Ursol D one or more.

Described template agent, organic quaternary ammonium salt with SiO ₂the mol ratio in the silicon source (described silicon source all refers to total silicon source) of meter is 0.05 ~ 0.3:1, such as, be 0.05 ~ 0.2:1; Organic amine with SiO ₂the mol ratio in the silicon source of meter is 0.05 ~ 0.45:1, such as, be 0.05 ~ 0.35:1, or be 0.1 ~ 0.25:1.

One or more in described organic quaternary ammonium salt such as 4-propyl bromide, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon 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 amonium 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 etamon 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 general formula is Si (OR ¹) ₄, R ¹be selected from the alkyl such as R with 1 ~ 6 carbon atom ¹for C ₁-C ₄alkyl, described alkyl can be branched-chain 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; One or more wherein preferably in quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil.The said solid silicon source of the present invention is highly purified silica solid or powder, such as, can be white carbon black and/or high-purity silica gel.Under preferable case, with butt weight for solid silicon source SiO described in benchmark ₂content is not less than 99.99 % by weight, and the mass content of Fe, Al and Na impurity (in element) is less than 10ppm; Such as SiO ₂content is 99.99 ~ 100 % by weight, is generally and is greater than 99.99 and is less than 100 % by weight.Described solid silicon source can be high silica gel and/or white carbon black, preferred white carbon black, SiO in wherein said silica gel ₂content is preferably greater than or equal to 99.99 % by weight such as being greater than 99.99 % by weight and being less than 100 % by weight, and the total content of Fe, Al and Na impurity is less than 10ppm(quality).The specific surface area of described white carbon black is preferably between 50-400m ²between/g, with the butt weight of white carbon black for benchmark, SiO in described white carbon black ₂it is such as 99.99 ~ 100 % by weight such as being greater than 99.99 % by weight and being less than 100 % by weight that content is preferably greater than or equal to 99.99 % by weight, and in described white carbon black, the total mass content of Fe, Al and Na impurity is less than 10ppm.Described white carbon black can be purchased, or prepares according to existing method, such as, according to the method preparation that patent CN200910227646.2 provides.Silicon tetrachloride and hydrogen and oxygen generation combustion reactions obtain by a kind of preparation method.

Silica zeolite synthetic method provided by the invention, the Inorganic Ammonium source described in step (1) is inorganic ammonium salt and/or ammoniacal liquor, obtains one or more in described inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate.Described Inorganic Ammonium source is preferably ammoniacal liquor, with NH ₄ ⁺meter ammoniacal liquor with SiO ₂the mol ratio in the silicon source (with described organosilicon source and described solid silicon source total amount) of meter for 0.01 ~ 0.1:1, such as, is 0.01 ~ 0.07:1 or 0.01 ~ 0.05:1.

In silica zeolite synthetic method provided by the invention, in step (1), template, organosilicon source, Inorganic Ammonium source and water are pressed mixing, at least 10 minutes are stirred at 0 ~ 150 DEG C such as 10 ~ 100 DEG C, be hydrolyzed to make organosilicon source, and the monohydroxy-alcohol content reduced in gained mixture, be namely hydrolyzed and catch up with alcohol.Usual churning time is 10 ~ 3000 minutes, such as, be 2 ~ 30 hours.Catch up with alcohol by hydrolysis, obtain the organosilicon hydrolyzation liquid of clear.In the mixture that usual step (1) obtains, the mass content of the monohydroxy-alcohol that the hydrolysis of organosilicon source produces is not higher than 10ppm.In the product of preferred steps 1, the mass content of monohydroxy-alcohol is no more 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 leave standstill 1 ~ 60 hour.Described room temperature is 15 ~ 40 DEG C; Digestion time is 1 ~ 60 hour is such as 2 ~ 50 hours, preferably 3 ~ 30 hours such as 3 ~ 15 hours, does not stir in weathering process, described material and step (1) products therefrom is left standstill.

Silica zeolite synthetic method provided by the invention, mixes the ageing products that step (2) obtains with solid silicon source, with SiO in step (3) ₂meter, the mol ratio of the product that step (2) obtains and solid silicon source is 1:0.1 ~ 10, such as, can be 0.2:1 ~ 9, can be 1:2 ~ 8, can be 1:1 ~ 7 be further 1:3 ~ 6.Method provided by the invention, can use the solid silicon source synthesis silica zeolite of higher proportion, can improve the solid content of synthetic product, thus improve the output of single synthesis when synthesis reaction vessel is constant.The production die that the synthetic method obtaining product more existing use solid silicon source obtains is less, can reach the crystal grain level all using 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 autogenous pressure, the time of crystallization is 2 hours ~ 20 days, and the time of usual described crystallization is 0.5 ~ 20 day, and such as 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 autogenous pressure.Described crystallization can be carried out in stainless steel stirring tank.Crystallization heat up can one section heat up also can multistage heating mode.Temperature rise rate can carry out according to existing crystallization temperature-rising method, such as, be 0.5-1 DEG C/min.Described crystallization can be carried out in stainless steel stirring 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 autogenous 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, and crystallization pressure is autogenous pressure.

Silica zeolite synthetic method provided by the invention, reclaiming silica zeolite described in step (3) is existing method, comprises by crystallization product filtration, washing and roasting or by crystallization product filtration, washing, drying then roasting.The object of filtering is that silica zeolite crystallization obtained is separated with crystallization mother liquor, the object of washing washes away the siliceous template solution 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 object is the most of moisture in removing molecular sieve, and to reduce water evaporation quantity when roasting, dry temperature can be 100 ~ 200 DEG C.The object of roasting is the template in removing molecular sieve, and the temperature of such as 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 also can be passed through further process, i.e. silica zeolite synthetic method provided by the invention, can also comprise 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 structure or claims 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 SiO ₂meter) be 1:0.02 ~ 0.5 with the molar ratio of organic bases be such as 1:0.02 ~ 0.2, with SiO ₂the mol ratio of molecular sieve and the water of meter is 1:2 ~ 50 for 1:2 ~ 20 are such as 1:5 ~ 10, crystallization temperature is 120 ~ 200 DEG C, time is 0.5 ~ 10 day such as 0.5 ~ 8 day, crystallization pressure is autogenous 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 bases 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 aliphatic amide, aromatic amine and hydramine, and described aliphatic amide (the present invention also claims fat amine compound), its general formula is R ³(NH ₂) _n, wherein R ³for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Described hydramine (the present invention also claims alcamine compound) its general formula is (HOR ⁴) _mnH _(3-m), wherein R ⁴for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3.One or more in described aliphatic amide such as ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; Described aromatic amine refers to have the substituent amine of aromaticity, such as, in aniline, Tolylamine, Ursol D one or more; One or more in described hydramine such as monoethanolamine, diethanolamine or trolamine.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) the present invention is referred to as molecular sieve and resets, and this process can be carried out once, also can repeat one or many, described repetition, is about to process the method process according to step (4) of molecular sieve that the silica zeolite that obtains replaces step (3) to obtain.By resetting process, can obtain the silica zeolite with secondary pore structure, the crystal grain of gained silica zeolite is hollow structure, and the radical length of the chamber portion of this hollow crystal grain is 5 ~ 300nm, at 25 DEG C, and P/P ₀=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.There is higher pore volume and specific surface area.。

Silica zeolite prepared by the method utilizing organic quaternary ammonium salt to synthesize silica zeolite provided by the invention, its Q ⁴/ Q ³be 10 ~ 90:1, wherein Q ⁴for described silica zeolite ²⁹in Si NMR spectrogram, chemical shift is the peak intensity at-112 ± 2ppm place, represents, Q with peak height ³for described silica zeolite ²⁹in Si NMR spectrogram, chemical shift is the peak intensity at-103 ± 2ppm place, represents with peak height.Described Q ⁴/ Q ³be preferably 15 ~ 50:1.The grain size (short-axis direction) of described silica zeolite is μm such as 200nm ~ 2 μm, 140nm ~ 2, is such as 200nm ~ 700nm further.The particle of described silica zeolite is that single crystal grain or the gathering of multiple crystal grain form.Described silica zeolite is preferably S-1 molecular sieve, S-2 molecular sieve or beta-molecular sieve.

In silica zeolite, a Siliciumatom is connected by oxygen with other four Siliciumatoms, can be expressed as Si (OSi) ₄, its ²⁹in SiNMR spectrogram, be that-112 ± 2ppm place has peak in chemical shift, its peak intensity (representing with peak height value) is expressed as Q ⁴; Siliciumatom and other three Siliciumatoms are connected by oxygen (can be expressed as SiOH (OSi) ₃), its ²⁹in Si NMR spectrogram, chemical shift is that-103 ± 2ppm place has peak, and its peak intensity (representing with peak height value) is expressed as Q ³; Q ⁴/ Q ³reflect the quantity of defective bit contained by silica zeolite to a certain extent, this ratio is larger, represents that defective bit is fewer.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 Siliciumatoms, has higher catalytic activity for cyclohexanone-oxime Beckmann rearrangement in lattice.

The present invention is further illustrated for the following examples, but therefore do not limit 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 embodiment ⁴/ Q ³measuring method adopt ²⁹si MAS NMR method.Use Varian INOVA300 type nuclear magnetic resonance spectrometer to measure, adopt solid double resonance probe, Φ 6mm ZrO ₂rotor. ²⁹the resonance spectrum that Si detects core is 59.588MHz, and magic 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 Quanta 200F type scanning electron microscope that FEI Co. produces: after sample drying process, vacuum-evaporation metal spraying, to increase electroconductibility and contrast effect; Analytic electron microscope acceleration voltage is 20.0kV, magnification 1 ~ 30k.

TEM method: electron microscope experiment carries out on FEI Co. Tecnai F20 G2 S-TWIN type transmission electron microscope, is furnished with the energy filter system GIF2001 of Gatan company, annex is equipped with X-ray energy spectrometer.Electron microscopic sample adopts the method for suspended dispersed to be prepared on micro-grid of diameter 3mm.

XRD measuring method: X-ray diffraction (XRD) the crystalline phase figure carrying out sample on Siemens D5005 type x-ray diffractometer measures, and gamma ray source is CuK α tube voltage 40kV, tube current 40mA, sweep velocity 0.5 °/min, sweep limit 2 θ=4 ° ~ 40 °.

The testing method of BET specific surface area and pore volume adopts N2 adsorption volumetry, according to BJH method of calculation.(can see 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 % by weight,

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

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

Ammoniacal liquor, analytical pure, concentration 20 % by weight.

White carbon black, Zhejiang Ju Hua group product, model AS-150; Solid content is greater than 95 % by weight; In butt, dioxide-containing silica is greater than 99.99 % by weight, and the total mass content of iron, sodium and Al is less than 10ppm, and specific surface area is 195m ²/ g.

Embodiment 1

(1) by 17.9g concentration be 20.05 % by weight 4-propyl bromide (TPABr) aqueous solution, with 1.62 grams of quadrols, 20.8g tetraethyl orthosilicate, 0.26g concentration be 20 % by weight ammoniacal liquor and 13.5g deionized water join successively in the beaker of 500ml, 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 bases hydrolyzed solution of silicon; Wherein the content of monohydroxy-alcohol is no more than 10ppm;

(2) the organic bases hydrolyzed solution of gained silicon is under agitation cooled to room temperature, then at room temperature leaves standstill 12 hours aging, obtain ageing products;

(3) under stirring, 12g white carbon black powder (in butt) is added in described ageing products, stir 2 hours, transferred in stainless 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 that obtains is filtered, with the deionized water wash decupling molecular sieve, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, obtained S-1 sample S-1-Y1; Its XRD analysis spectrogram as shown in Figure 1; ²⁹as shown in Figure 3, SEM as shown in Figure 4 for Si MAS NMR characterization result.Its BET specific surface area is 420m ².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 6g S-1-Y1 sample and 10 quality %, wherein the consumption of the 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, obtained sample S-1-Y1P.As shown in Figure 1, its BET specific surface area is 437m to its XRD analysis spectrogram ²/ g, micro pore volume is 0.155mL.g ^-1, mesopore volume is 0.158mL.g ^-1, in transmission electron microscope photo, it is hollow structure (shown in Fig. 6).

The preparation condition of embodiment 1 and obtain the characterization result of molecular sieve in table 1.

Embodiment 2 ~ 6

Prepare molecular sieve according to the method for embodiment 1, unlike adjustment 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, and preparation method's reference example 1, preparation condition and characterization result are in table 1.

Embodiment 8

Change template, synthesis total silicon S-2 molecular sieve, preparation condition and characterization result are in table 1.

Embodiment 9

Change template, synthesis total silicon beta-molecular sieve, preparation condition and characterization result are in table 1, and as shown in Figure 2, SEM figure as shown in Figure 5 for XRD spectra.

Comparative example 1

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

Be that 22.05 % by weight TPAOH solution mix by 208g tetraethyl orthosilicate and 180g concentration, add 64.5g deionized water Homogeneous phase mixing; Then at 60-80 DEG C, be hydrolyzed 5-9h, obtain containing tetraethyl orthosilicate hydrating solution; Under the effect of vigorous stirring, continued by this mixture to stir 7h at 75 DEG C, obtain colloid, then moved in stainless steel closed reactor by this colloid, thermostatic crystallization 2 days at 170 DEG C, can obtain conventional S-1 molecular sieve;

By obtain S-1 sample filtering, 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 % by 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, the 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, unlike with the white carbon black of equivalent (with SiO ₂meter) replace tetraethyl orthosilicate described in comparative example 1 (with SiO ₂meter).Preparation condition and characterization result are in table 1.

Comparative example 3

According to the method for embodiment 1, unlike not introducing ammoniacal liquor, do not carry out aging.Preparation condition and characterization result are in table 1.

Comparative example 4

According to the method for embodiment 1, unlike, by solid silicon source, organosilicon source, template, water mixing, after stirring hydrolysis, direct crystallization, does not add ammoniacal liquor.Preparation condition and characterization result are in table 1.

Comparative example 5

According to the method for embodiment 1, aging unlike not carrying out.Preparation condition and characterization result are in table 1.

Evaluation operation example

The silica zeolite do not reset provide above-described embodiment and comparative example and the molecular sieve after resetting are evaluated.Cyclohexanone-oxime Beckmann rearrangement is adopted to evaluate the catalytic performance of gained silica zeolite.Silica zeolite compressing tablet, then broken, get 20-60 object particle as catalyzer.Evaluation result is in table 1.Appreciation condition is as follows:

Reaction unit is normal pressure continuous flow fixed bed, and reactor inside diameter is 5 millimeters, and catalyzer (silica zeolite) loadings is 0.5g, and the grain graininess of catalyzer is 20-60 order.

Catalyzer loads after reaction tubes, pre-treatment 2 hours in normal pressure, the nitrogen atmosphere of 350 DEG C.

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

Reaction product is by collecting after water cycle condensation, and hydrogen flame detector, vapor-phase chromatography records its composition.

It should be noted that, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to 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) by template, organosilicon source, Inorganic Ammonium source and water mixing, 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) ageing products step (2) obtained and solid silicon source are according to the mixed in molar ratio of 1:0.1 ~ 10, and then crystallization in closed reactor, reclaims silica zeolite; In wherein said part by weight, the ageing products that described step (2) obtains is with SiO ₂meter, solid silicon source is with SiO ₂meter; The mol ratio of template, silicon source, Inorganic Ammonium source and water is (0.08 ~ 0.6): 1:(0.01 ~ 0.1): (3 ~ 100); In wherein said mol ratio, silicon source is with SiO ₂meter, for SiO ₂meter organosilicon source and with SiO ₂the summation of the solid silicon source of meter, Inorganic Ammonium source is with NH ₄ ⁺meter; Described Inorganic Ammonium source is inorganic ammonium salt and/or ammoniacal liquor; Described template is the mixture of organic quaternary ammonium salt and organic amine, and wherein the mol ratio in organic quaternary ammonium salt and silicon source is 0.04 ~ 0.55:1, 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 characterized in that, described organic amine with SiO ₂the mol ratio in silicon source of meter is 0.05 ~ 0.35:1, organic quaternary ammonium salt with SiO ₂the mol ratio in the silicon source of meter is 0.05 ~ 0.3:1.

3. according to the method described in claim 1 or 2, it is characterized in that, the mol ratio of described template, silicon source, Inorganic Ammonium source 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 characterized in that, the mol ratio of described template, silicon source, Inorganic Ammonium source 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 characterized 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 Ammonium source and silicon source is 0.01-0.07:1; Described silicon source is with SiO ₂meter organosilicon source and with SiO ₂the summation of the solid silicon source of meter.

6. in accordance with the method for claim 1, it is characterized in that, described organosilicon source is organic silicone grease, described organo-silicon ester, and its general formula is Si (OR ¹) ₄, R ¹be selected 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 source ₂content is greater than 99.99 % by weight, is less than 10ppm in the total content of Fe, Al and Na of atom.

7. in accordance with the method for claim 6, it is characterized 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 black, and the specific surface area of described white carbon black is 50 ~ 400m ²/ g, described organic amine is one or more in aliphatic amide, aromatic amine and hydramine.

8. in accordance with the method for claim 7, it is characterized in that, the general formula of described aliphatic amide is R ³(NH ₂) _n, wherein R ³for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Its general formula of described hydramine is (HOR ⁴) _mnH _(3-m), wherein R ⁴for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3; Described aromatic amine is for comprising the substituent amine of aromaticity.

9. in accordance with the method for claim 8, it is characterized in that, described aliphatic amide is one or more in ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; Described hydramine is one or more in monoethanolamine, diethanolamine or trolamine; Described aromatic amine is one or more in aniline, Tolylamine, Ursol D.

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

11. in accordance with the method for claim 1, it is characterized in that, step (3) described crystallization, and the temperature of crystallization is 110 ~ 200 DEG C, and crystallization pressure is autogenous 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 characterized 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 characterized 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 autogenous pressure.

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

15., according to the method described in claim 1 or 14, is characterized in that, in the product that step (1) obtains, the mass content of the alcohol that the hydrolysis of organosilicon source produces is no more than 10ppm.

16. in accordance with the method for claim 1, it is characterized in that, the described aging digestion 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 characterized in that, with SiO ₂meter solid silicon source and with SiO ₂the mol ratio in organosilicon source of meter is 1 ~ 9:1 or is 2 ~ 8:1 or is 3 ~ 7:1.

18., according to the method described in any one of claim 1 ~ 17, is characterized in that, described method also comprises step (4): silica zeolite step (3) obtained crystallization 0.5 ~ 10 day in the organic bases aqueous solution, and the temperature of crystallization is 110 ~ 200 DEG C; Wherein said silica zeolite is (with SiO ₂meter) be 1:0.02-0.5 with the mol ratio of described organic bases, described silica zeolite is (with SiO ₂meter) be 1:2 ~ 50 with the mol ratio of water.

19. in accordance with the method for claim 18, it is characterized in that, the temperature of step (4) described crystallization is 150 ~ 200 DEG C, and described silica zeolite is (with SiO ₂meter) be 1:0.02-0.2 with the mol ratio of described organic bases, described silica zeolite is (with SiO ₂meter) be 1:2 ~ 20 with the mol ratio of water, pressure is autogenous pressure.