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CN101182004B - Method for preparing nano molecular sieve - Google Patents

Method for preparing nano molecular sieve Download PDF

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CN101182004B
CN101182004B CN2007100790382A CN200710079038A CN101182004B CN 101182004 B CN101182004 B CN 101182004B CN 2007100790382 A CN2007100790382 A CN 2007100790382A CN 200710079038 A CN200710079038 A CN 200710079038A CN 101182004 B CN101182004 B CN 101182004B
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molecular sieve
oil
silica gel
synthetic method
nano molecular
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CN101182004A (en
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王鼎聪
孙万富
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a preparation method of nanoparticle molecular sieve. The method evenly mixes hydrocarbon components with surfactant firstly and then silica gel and alumino silica gel are added to continue to stir until raw materials are mixed evenly, and a super solubilized system of oil pocket molten materials is obtained, the nanoparticle molecular sieve is acquired after crystallization, drying and calcinations. The crystallization of the molecular sieve of the invention is carried out in a super solubilized micelle system of the silica gel or the alumino silica gel melten in the oil pocket; the growth of molecular sieve crystals is limited in a nanometer micelle to avoid over growth of the molecular sieve crystals. The surfactant and the hydrocarbon components used in the invention have small quantity and low cost. The method has simple technique and can be carried out in mass industrial production.

Description

A kind of preparation method of nano molecular sieve
Technical field
The present invention relates to a kind of molecular sieve forms and the preparation method.Particularly relate to a kind of nano level molecular sieve preparation method.
Background technology
Over past ten years, synthesizing of relevant nanoscale molecular sieve seems quite active, and this mainly ascribes nanoscale molecular sieve and the distinct performance of micro-meter scale molecular sieve to.The granularity of molecular sieve crystal is reduced to nano level from micron order, and its mass transfer, heat transfer etc. and molecular sieve adsorption, the relevant performance of katalysis can change.Make the nanoscale molecular sieve catalyst in some hydro carbons catalytic conversion reactions, show better activity, selectivity and anti-carbon deposition ability.So far have with the reaction of nano molecular sieve: hydrocracking as catalyzer, fluid catalytic cracking, the alkylation of benzene, the oligomerisation reaction of alkene, preparing gasoline by methanol, methylamine synthetic etc., the result of these reactions shows that nano molecular sieve shows in reaction: reactive behavior height, to advantages such as the distinctive selectivity of product, anti-carbon deposition ability are strong.
The general synthetic method of molecular sieve is that silicon source and aluminium source are mixed in certain medium (normally alkaline aqueous solution), forms unformed alumino silica gel, under hydrothermal temperature, goes out molecular sieve crystal through the certain hour crystallization then.If the nucleus in the synthetic system is many more, the molecular sieve crystal size that then finally synthesizes is more little and the crystal grain distribution is even more.Owing in the molecular sieve crystallization process, exist running balance between the formation of molecular sieve nucleus and crystalline growth and its dissolving.With compare than small-crystalline or than the small crystal nucleus presoma, have bigger growth tendency than macrocrystal or big nucleus presoma, dissolving trend is then less.Therefore, along with the carrying out of molecular sieve crystallization process, can cause than small-crystalline or than the dissolving of small crystal nucleus presoma than the growth of macrocrystal or bigger nucleus presoma, thereby be unfavorable for the molecular sieve that composite crystals size and crystal grain are evenly distributed.
People such as Li are at document Microporous Mesoporous Mater, 2000, described among 40 (1/3) L53-L62 when synthetic Silicalite-1 zeolite, reduction along with crystallization temperature, the nano particle diameter that is synthesized is progressively reduced to about 60nm from about 90～100nm, but crystallization time extends to about 10d from 1d.Though this method is operation easily, and can effectively reduce the particle diameter of particle, crystallization time is longer, thereby has prolonged the operational cycle, is unfavorable for that industrial production is only limited to laboratory study.
People such as Van Grieken are at document Micreporous Mesoporous Mater, 2000,39 (1/2): described among the L135-L147, become hydro-thermal under the glue conditions of mixture ratios (443K) to synthesize the nano-ZSM-5 zeolite of 10～100nm (TEM) in supersaturation, and carry out systematic study to influencing the synthetic factor, Gu propose this method is to become the viewpoint of zeolite by the initial amorphous solid that forms by solid-reformulations crystallization, discovery is the aluminium source with the aluminum isopropylate, long digestion time, higher basicity and lower sodium content help the formation of nano zeolite, the existence of sodium ion has then reduced the crystallization velocity of ZSM-5 zeolite, causes crystal grain obviously to increase.Present method has been investigated the multiple factor that influences size of particles, though size of particles has obtained better controlled, the aluminium source of adopting is an aluminum isopropylate, improves greatly than other inorganic aluminium costs.
People such as Myatt are at Zeolite, 1994,14 (3): described in the 190-197 document, by systematically investigation table surface-active agent and solubility polymer to forming the influence of NaA nucleus.Find to add cats product, help the formation of a large amount of less crystal seeds, thereby the grain fineness number of final molecular sieve reduces; And the adding anion surfactant has suppressed nucleation, has reduced nucleation rate.Therefore form the crystal seed that number is less and radius is bigger, this makes zeolite crystal bigger.A bigger shortcoming of this method is exactly that water-content is higher, the template consumption is increased, thereby raise the cost.
USP 3516786 has described a kind of method of synthesis of molecular sieve, when the synthesizing octahedral zeolite-type molecular sieves, before synthetic system intensification crystallization, to wherein adding a spot of organic solvent, as dimethyl sulfone, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol and acetone etc., the zeolite crystal that synthesizes is of a size of 10～100nm.Change the hydro-thermal synthetic system into water-organic solvent system from water solution system, can on certain Cheng Du, reduce the granularity of molecular sieve,, thereby reduce the granularity of molecular sieve because the organic solvent that adds can promote cationic solvation degree in the solution.Though this method can be improved the particle diameter of molecular sieve effectively, same higher owing to water-content, cause the template large usage quantity, improved cost.
A kind of synthetic method of beta zeolite in small crystal grain has been described among the CN1108213A.When synthetic β zeolite, with 200-300 purpose silica gel is the silicon source, mix with it with working solution that aluminium source, sodium source, tetraethylammonium cation source and water are made into, make the silica gel surface just wetting by working solution institute, the β zeolite of being prepared by this system is the 0.1-10 micron.This method has overcome the existing shortcoming of above method, has reduced water-content, has reduced the template consumption largely simultaneously, provides cost savings, but fails to synthesize the nano beta zeolite, is only limited to the synthetic of small crystal grain molecular sieve.
Summary of the invention
Purpose of the present invention aims to provide a kind of nano molecular sieve synthetic method.The particle diameter that the inventive method can effectively be controlled particle and presents very monodisperse status uniformly in nanometer range, used tensio-active agent and hydrocarbon component consumption are little, and the usage quantity of template and mineralizer is also less, thereby greatly reduces cost.
The contriver finds through a large amount of experiments, melts can be solubilized in hydrocarbon component and the water-in-oil-type surfactant mixtures, form super solubilising nanometer micelle, carry out the control reaction of restricted in-situ nano micelle with the nanometer micelle, reaction, the weathering process of melts are all carried out in the nanometer micelle, limit growing up of micelle, after roasting, can form nano molecular sieve.
The synthetic method step of the said nano molecular sieve of the present invention is as follows:
(1) preparation of reaction alumino silica gel: under 10-40 ℃ and agitation condition, by (0-0.1) Al 2O 3: 1.0SiO 2: (2.0-10.0) H 2O: (0.2-2.0) organic solvent: (0.01-1.0) mineralizer: (0.05-0.1) the mole proportioning of template, with silicon source, aluminium source, mineralizer, organic solvent, template and water thorough mixing, continue to be stirred to raw material and mix, make the reaction alumino silica gel.
(2) preparation of the stable super solubilising self-assembly system of oil bag melting salt: at first the cosurfactant that hydrocarbon component, tensio-active agent and selectivity are added mixes under 70-130 ℃ and agitation condition, splashes into the alumino silica gel of gained in the step (1) then; Continue to be stirred to raw material and mix, obtain the super solubilising self-assembly system of oil bag melts.
(3) crystallization of molecular sieve: oil is wrapped melts change in the autoclave pressure, under autogenous pressure, seal 80-180 ℃ of following static crystallization 9-50 hour;
(4) with the product of step (3) gained through separate, washing, dry again with roasting after, obtain sieve sample;
Weight with the mixture of step (2) gained is benchmark, the consumption of reaction alumino silica gel is 60wt%～95wt%, better is 80wt%～95wt%, and the consumption of tensio-active agent is 0.1wt%-8wt%, better be 0.5wt%-4wt%, preferably 0.8wt%-2wt%; The consumption of hydrocarbon component is 3wt%～30wt%, better is 3wt%～15wt%, preferably 4wt%～8wt%; The consumption of cosurfactant is 0～3wt%.
The used VB value of the present invention is the water-in-oil-type tensio-active agent less than 1 tensio-active agent.Relevant VB value notion please refer to " A Study of Identifying Emulsion Type of Surfactant--Volume BalanceValue " paper that this patent people is published in the Journal of colloid and interface science fourth phase in 2002.The VB value is a kind of constant of hydrophilic and oleophilic performance of more effective judgement tensio-active agent than the HLB value, both have following difference: 1) the VB value of HLB value 3-6 water-in-oil-type tensio-active agent is less than 1, but the HLB to many tensio-active agents is difficult for measuring, many tensio-active agents do not have the HLB value, and any tensio-active agent all can directly calculate the VB value according to the chemical structure of tensio-active agent; 2) some HLB value can form water-in-oil emulsion about 10, and the VB value is 1 to be boundary, determines its oleophylic or wetting ability.The VB value is an oil soluble surfactant less than 1; The VB value is the water soluble surfactant active greater than 1.The used tensio-active agent of the present invention is selected from SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride, two sweet esters, ethylene glycol monostearate, the glycol ether monostearate, propyleneglycoles list dodecyl ester, polyisobutenyl toxilic acid glycol ether ester, polyisobutenyl toxilic acid triethyleneglycol ester, polyisobutenyl toxilic acid triethanolamine ester, polyisobutenyl toxilic acid glycol ether ester and succimide class (the two succimides of hanging of T-152, the two succimides of hanging of T-154, the single succimide of hanging of T-151, T-153 hangs succimide more, T-155 hangs succimide more) in one or more, be preferably: polyisobutenyl toxilic acid glycol ether ester, SP-80, the succimide class, in polyisobutenyl toxilic acid triethanolamine ester and the two sweet esters one or more.
The used hydrocarbon component of the present invention can be selected petroleum component for use, the not volatile heavy distillate of the general selection of petroleum hydrocarbon components, also can select animal-plant oil, be one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetables oil, animal oil.Wherein vacuum distillate is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more mixture of the dewaxing of four line distillates or wax-containing distillate, can come from paraffinic base, intermediate base or naphthenic base crude; The decompression slack wax is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more slack waxs that obtain in the four line distillates, as being the second line of distillation slack wax, subtracting three-way slack wax, subtracting four line slack waxs and composition thereof; The residual oil slack wax is frivolous asphalt oil and/or heavy deasphalting slack wax; Deasphalted oil is frivolous asphalt oil and/or heavy deasphalted oil.Vegetables oil is one or more in soya-bean oil, peanut oil, rape seed oil, Viscotrol C, Oleum Helianthi, Oleum Cocois and the plam oil; Animal oil is one or more in butter, sheep oil, lard and the fish oil.
Also can be in tensio-active agent with cosurfactant, the effect of cosurfactant can reduce the consumption of tensio-active agent, can form more stable complexed surfactant film, helps the stability of tensio-active agent film.Cosurfactant comes from one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate and the dodecyl alcohol acyl phosphoric acid ester.
The used silicon source of the present invention is ultra micro SiO 2, in the white carbon black, water glass, tetraethoxy, methyl silicate, water glass, silicon sol, silica gel, atlapulgite, sodium-potassium silicate, silicic acid one or more.
The used aluminium source of the present invention is one or more in sodium aluminate, (plan) boehmite, gibbsite, aluminum isopropylate, metallic aluminium, nine water aluminum nitrates, aluminum chloride, potassium aluminium alum, 18 water Tai-Ace S 150, aluminum fluoride, aluminum bromide, the aluminum iodide.
The used mineralizer of the present invention is fluorine source (F -) or alkali source (OH -), wherein the fluorine source is NH 4F, HF, CaF 2, KHF 2, NH 4HF 2, SiF 4, CsF, NaF, AgF, (NH 4) 2SiF 6, AlF 3H 2O, NH 4BF 4In one or more, alkali source is sodium hydroxide, magnesium hydroxide, hydrated barta, calcium hydroxide, potassium hydroxide, urea, yellow soda ash, volatile salt, one or more in lime carbonate, salt of wormwood, bicarbonate of ammonia, carbonated aqueous ammonia, liquefied ammonia, the ammoniacal liquor.
The used organic solvent of the present invention is ethylene glycol, glycerol, ethanol, glycol ether, triethylene glycol, one or more in propyl carbinol, poly(oxyethylene glycol) 400, the Macrogol 2000.
The used template of the present invention is TPAOH, TMAOH, TEAOH, TPABr, Pr 3N, Et 3N, (C 2H 5) 3N, (C 3H 7) 3N, (CH 3) 2NCH 2C 6H 5, (C 2H 5) 2NCH 2CH 2OH, CH 3N (CH 2CH 2OH) 2One or more.
Described oven dry and roasting condition are as follows: 80-110 ℃ of oven dry down, 250～300 ℃ of roastings 1～3 hour, be warming up to 350～650 ℃ of roastings 5～24 hours then.Described roasting can be carried out under the atmosphere of air or inert gas (preferred nitrogen).
Stirring described in step (1) and the step (3) can be adopted conventional mechanical stirring device, and its stirring velocity is 500-4000r/min.But the separation ordinary method of described product is separated, such as centrifugation; Described washing can be washed till neutrality with product by conventional washing methods and washings, and used washings can be ethanol, sherwood oil, water etc.
The present invention if institute's raw material water content that adopts is higher, can carry out processed in advance in the synthesis of molecular sieve process, meeting the requirement of proportioning raw materials of the present invention, such as the silicon sol of employing among the embodiment 1.
Nano molecular sieve specific surface area by gained of the present invention is big, pore volume is big, and its specific nature is as follows: specific surface is 200～600m 2/ g is preferably 300～500m 2/ g, pore volume 0.1～0.3ml/g, mean pore size is 1～4nm, median size is 10～100nm, is preferably 20～50nm.Surface-area among the present invention and pore structure are with U.S. ASAP2400 type low temperature liquid nitrogen absorption instrument, calculate by the BET method.Median size wherein obtains with TEM (transmission electron microscope) analysis.
The crystallization of molecular sieve is carried out in oil bag fused silica gel or alumino silica gel system among the present invention, super solubilising micelle is formed each homogeny, transparent and thermodynamically stable dispersion system by hydrocarbon component, tensio-active agent, cosurfactant, the particle diameter of micelle is about 10-100nm, micelle is oil bag fused silica gel or alumino silica gel system, because the crystal growth of molecular sieve is limited by the finite space of nanometer micelle, can avoid excessively growing up of molecular sieve crystal; Simultaneously, the effect of mass transmitting between the nanometer micelle is restricted, and also can reduce and avoid the dissolving than the small crystal nucleus presoma that growth caused than macrocrystal or big nucleus presoma.Therefore can effectively synthesize nanometer particle size and the narrower molecular sieve of particle size distribution range.Sieve sample adopts X-ray diffraction (XRD), transmission electron microscope technology such as (TEM) that crystalline phase and crystalline size are characterized, and the average grain size size of the molecular sieve that is synthesized is less than 100nm, and narrower size distribution is arranged.
The nano molecular sieve of the inventive method gained can be used for that hydrofining, hydrocracking, isomerization, alkylation, catalytic cracking, alkene are saturated, alkene oligomerization, catalytic reforming, hydrogenation dearomatization, Aromatizatian catalytic agent carrier, be especially suitable for use as hydrofining catalyst carrier, especially the carrier of Hydrobon catalyst.
The prepared nano molecular sieve of the inventive method has the following advantages:
1, the inventive method is to utilize oil bag melts can form the character of disperseing super solubilising micelle in the height mutually.Utilize the nanometer character of micelle, melts carries out original position in micelle synthetic, avoided the increase of crystal grain, and particle diameter is monodisperse status.
2, the inventive method makes template agent reduce by reducing water-content in the solution significantly, and the consumption of mineralizer also reduces thereupon simultaneously, thereby reduces the synthetic cost of nano molecular sieve.
3, used tensio-active agent and the hydrocarbon component consumption of the inventive method is little, and cost is low, and molecular sieve presents monodisperse status very uniformly, and crystal formation is grown also more perfect, and nano-scale is little, and catalytic performance is good.
4, the inventive method technology is simple, can carry out industrial production in enormous quantities.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1, and Fig. 2 is the TEM spectrogram (magnification is 105000) of embodiment 1 gained molecular sieve.
Embodiment
The present invention will be further described below by embodiment.
Embodiment 1
According to 0.02Al 2O 3: 1.0SiO 2: 0.08NH 4HF 2: 0.06TMAOH: 3H 2O: 0.3C 2H 5The mol ratio of OH is with silicon sol (with the silicon sol deep dehydration 200g of 408g 28wt%), the 9.1g NH after the 208g processing 4HF 2, 6.6gNaAlO 2, 11gTMAOH, 15gH 2O and 28gC 2H 5OH at room temperature and under the mechanical stirring (4000r/min) mixes, and after continuing to be stirred to the raw material uniform mixing, obtains the alumino silica gel of leucosol shape.13.9g second line of distillation distillate, 0.5g polyisobutene toxilic acid triethanolamine ester are mixed under the mechanical stirring of 90 ℃ and 4000r/min rotating speed, splash into the 277.7g alumino silica gel then, and be stirred to raw material and mix, can obtain stable super solubilising micelle system.Change in the autoclave pressure, seal 140 ℃ of following static crystallization 30 hours.Product is extremely neutral through centrifugation, washing, and after oven dry under 110 ℃, 250 ℃ of bubbling air roastings 2 hours, is warming up to 350 ℃ of bubbling air roastings 5 hours then, obtains sieve sample.Characterize with XRD, BET and TEM technology.X-ray analysis shows that the sample that above-mentioned synthetic method makes is the ZSM-5 molecular sieve.The BET specific surface of gained molecular sieve: 368m 2/ g, pore volume: 0.15ml/g, mean pore size: 1.9nm, median size: 60nm.
Embodiment 2
According to 1.0SiO 2: 0.02NH 4F: 0.07 (C 2H 5) 3N: 5H 2O: the mol ratio of 0.5 ethylene glycol, 208g tetraethoxy, 0.8g Neutral ammonium fluoride, 6.1g triethylamine, 54g water and 31g ethylene glycol at room temperature with under the mechanical stirring of 800rpm rotating speed are mixed, and after continuing to be stirred to the raw material uniform mixing, obtain the alumino silica gel of leucosol shape.21.4g is subtracted three-way distillate, 4.3g polyisobutenyl toxilic acid glycol ether ester and 4.3g lauryl alcohol Soxylat A 25-7 (10), under the mechanical stirring of 90 ℃ and 800rpm rotating speed, mix, slowly add the 300g alumino silica gel then, and be stirred to raw material and mix, can obtain stable super solubilising micelle system.Change in the autoclave pressure, seal 140 ℃ of following static crystallization 30 hours.After handling, product such as embodiment 1 carry out XRD, BET and TEM sign.Characterization result shows that product S ilicalite-1 is a molecular sieve, BET specific surface: 320m 2/ g, pore volume: 0.21ml/g, mean pore size: 2.5nm, median size: 50nm.
Embodiment 3
According to 0.04Al 2O 3: 1SiO 2: 0.04KOH: 0.05TPABr: 2H 2O: the mol ratio of 0.3 glycol ether, with 120g white carbon black, 7.8g pseudo-boehmite, 2.7gTPABr, 4.5gKOH, 72gH 2O and 63g glycol ether at room temperature and under the mechanical stirring (rotating speed 1500rpm) mix, and after continuing to be stirred to the raw material uniform mixing, obtain the alumino silica gel of leucosol shape.33.8g is subtracted four line distillates, 13.5gSP-80 and 6.75g Yelkin TTS, under the mechanical stirring of 90 ℃ and 1000rpm rotating speed, mix, slowly add the 270g alumino silica gel then, and be stirred to raw material and mix, can obtain stable super solubilising micelle system.Change in the autoclave pressure, seal 120 ℃ of following static crystallization 30 hours, feed nitrogen roasting 3 hours, be warming up to 350 ℃ then and feed nitrogen roasting 7 hours, obtain sieve sample at 250 ℃.Carrying out XRD, BET and TEM characterizes.Characterization result shows that product is a beta-molecular sieve, BET specific surface: 350m 2/ g, pore volume: 0.3ml/g, mean pore size: 3.5nm, median size: 45nm.
Embodiment 4
This example preparation feedback alumino silica gel is identical with embodiment 1 with consumption with the raw material of the super solubilising micelle of melts system, but prepared reaction alumino silica gel and super solubilising micelle system respectively under 40 ℃ and 100 ℃, the super solubilising micelle system of gained was 150 ℃ of following crystallization 24 hours.After product such as embodiment 1 handle, characterize with XRD, BET and TEM, the result shows that product is the ZSM-5 molecular sieve, BET specific surface: 360m 2/ g, pore volume: 0.27ml/g, mean pore size: 1.3nm, median size: 40nm.
Embodiment 5
According to 1SiO 2: 1HF: 0.1TMAOH: 10H 2O: the mol ratio of 2 triethylene glycols, with 284gNa 2SiO 39H 2O, 14gHF, 9.1gTMAOH and 150g triethylene glycol mix down in room temperature and mechanical stirring (rotating speed 1000rpm), and after continuing to be stirred to the raw material uniform mixing, obtain the alumino silica gel of leucosol shape.101.6g is subtracted four line slack waxs, 25.4g two sweet esters and 15.2g sodium stearate, under the mechanical stirring of 90 ℃ and 1000rpm rotating speed, mix, slowly add the 457.1g alumino silica gel then, and be stirred to raw material and mix, can obtain stable super solubilising micelle system.Change in the autoclave pressure, seal 140 ℃ of following static crystallization 40 hours.After handling, product such as embodiment 2 carry out XRD, BET and TEM sign.Characterization result shows that product S ilicalite-1 is a molecular sieve, BET specific surface: 379m 2/ g, pore volume: 0.22ml/g, mean pore size: 1.9nm, median size: 35nm.
Embodiment 6
Press 0.02Al 2O 3: 1.0SiO 2: 0.01NaOH: 0.06TEAOH: 2H 2O: the mol ratio of 0.2 glycol ether, 180g white carbon black, 22.5g nine water aluminum nitrates, 1.2gNaOH, 26.5gTEAOH, 90g water and 63.6g glycol ether at room temperature and under the mechanical stirring (rotating speed 1000rpm) are mixed, and after continuing to be stirred to the raw material uniform mixing, obtain the alumino silica gel of leucosol shape.With 121.2g lard, 28.3g polyisobutene toxilic acid triethanolamine ester and 10.1g Yatall MA acid amides, under the mechanical stirring of 90 ℃ and 1000rpm rotating speed, mix, slowly add the 384g alumino silica gel then, and be stirred to raw material and mix, can obtain the super solubilising micelle of stable fused salt system.Change in the autoclave pressure, seal 120 ℃ of following static crystallization 50 hours.After handling, product such as embodiment 3 carry out XRD, BET and TEM sign.Characterization result shows that product is a beta-molecular sieve, BET specific surface: 320m 2/ g, pore volume: 0.26ml/g, mean pore size: 2.3nm, median size: 46nm.
Embodiment 7
Press 0.1Al 2O 3: 1.0SiO 2: 1.0NaF: 0.1TPAOH: 10H 2O: the mol ratio of 2 poly(oxyethylene glycol) 400, with 180g water glass (29.49wt%SiO 2), 24g aluminum chloride, 37.8gNaF, 9.4gTPAOH, 90g water and 63.6g poly(oxyethylene glycol) 400 at room temperature and mechanical stirring (rotating speed 1000rpm) mix down, and after continuing to be stirred to the raw material uniform mixing, obtain the alumino silica gel of leucosol shape.With 130.3g second line of distillation slack wax, 34.7g succimide class and 13g phosphoric acid fat, under the mechanical stirring of 90 ℃ and 1000rpm rotating speed, mix, slowly add the 412.5g alumino silica gel then, and be stirred to raw material and mix, can obtain the super solubilising micelle of stable fused salt system.Change in the autoclave pressure, seal 120 ℃ of following static crystallization 50 hours.After handling, product such as embodiment 3 carry out XRD, BET and TEM sign.Characterization result shows that product is a beta-molecular sieve, BET specific surface: 325m 2/ g, pore volume: 0.28ml/g, mean pore size: 2.4nm, median size: 49nm.
Embodiment 8
Press 1.0SiO 2: 0.01NH 4BF 4: 0.05 (C 3H 7) 3N: 2H 2O: the mol ratio of 0.2 Macrogol 2000, with 78g silicic acid, 1gNH 4BF 4, 7.2g (C 3H 7) 3N, 36g water and 300g Macrogol 2000 at room temperature and under the mechanical stirring (rotating speed 1000rpm) mix, and after continuing to be stirred to the raw material uniform mixing, obtain the alumino silica gel of leucosol shape.With 24g soya-bean oil, 6.0g SP-60 and 2g calcium mahogany sulfonate, under the mechanical stirring of 90 ℃ and 1000rpm rotating speed, mix, slowly add the 422.2g alumino silica gel then, and be stirred to raw material and mix, can obtain the super solubilising micelle of stable fused salt system.Change in the autoclave pressure, seal 120 ℃ of following static crystallization 50 hours.After handling, product such as embodiment 3 carry out XRD, BET and TEM sign.Characterization result shows that product is the Silicalite-1 molecular sieve, BET specific surface: 352m 2/ g, pore volume: 0.26ml/g, mean pore size: 3.2nm, median size: 59nm.

Claims (13)

1. the synthetic method of a nano molecular sieve comprises the steps:
(1) preparation of reaction alumino silica gel: under 10-40 ℃ and agitation condition, by (0-0.1) Al 2O 3: 1.0SiO 2: (2.0-10.0) H 2O: (0.2-2.0) organic solvent: (0.01-1.0) mineralizer: (0.05-0.1) the mole proportioning of template, with silicon source, aluminium source, mineralizer, organic solvent, template and water thorough mixing, continue to be stirred to raw material and mix, make the reaction alumino silica gel;
(2) preparation of the stable super solubilising self-assembly system of oil bag melting salt: at first the cosurfactant that hydrocarbon component, tensio-active agent and selectivity are added mixes under 70 ℃-130 ℃ and agitation condition, splashes into the alumino silica gel of gained in the step (1) then; Continue to be stirred to raw material and mix, obtain the super solubilising self-assembly system of oil bag melts; Wherein used tensio-active agent is that the VB value is less than 1 tensio-active agent;
(3) crystallization of molecular sieve: oil is wrapped melts change in the autoclave pressure, under autogenous pressure, seal 80-180 ℃ of following static crystallization 9-50 hour;
(4) with the product of step (3) gained through washing, separate, after oven dry and the roasting, obtain sieve sample then;
Weight with the mixture of step (2) gained is benchmark, and the consumption of reaction alumino silica gel is 60wt%～95wt%, and the consumption of tensio-active agent is 0.1wt%-8wt%; The consumption of hydrocarbon component is 3wt%～30wt%; The consumption of cosurfactant is 0～3wt%.
2. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that the weight with the mixture of step (2) gained is benchmark, the consumption of reaction alumino silica gel is 80wt%～95wt%, the consumption of tensio-active agent is 0.5wt%-4wt%; The consumption of hydrocarbon component is 3wt%～15wt%.
3. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that the weight with the mixture of step (2) gained is benchmark, the consumption of reaction alumino silica gel is 80wt%～95wt%, the consumption of tensio-active agent is 0.8wt%-2wt%; The consumption of hydrocarbon component is 4wt%～8wt%.
4. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that described oven dry and roasting condition are as follows: 80-110 ℃ of oven dry down, 250～300 ℃ of roastings 1～3 hour, then 350～650 ℃ of roastings 5～24 hours.
5. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that used VB value is selected from SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride, two sweet esters, ethylene glycol monostearate, glycol ether monostearate, propyleneglycoles list dodecyl ester, polyisobutenyl toxilic acid glycol ether ester, polyisobutenyl toxilic acid triethyleneglycol ester, polyisobutenyl toxilic acid triethanolamine ester, polyisobutenyl toxilic acid glycol ether ester and the succimide class one or more less than 1 tensio-active agent.
6. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that used hydrocarbon component is one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetables oil, animal oil.
7. according to the synthetic method of the described nano molecular sieve of claim 6, it is characterized in that described vacuum distillate is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more mixture of the dewaxing of four line distillates or wax-containing distillate; The decompression slack wax is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more slack waxs that obtain in the four line distillates; The residual oil slack wax is frivolous asphalt oil and/or heavy deasphalting slack wax; Deasphalted oil is frivolous asphalt oil and/or heavy deasphalted oil; Vegetables oil is one or more in soya-bean oil, peanut oil, rape seed oil, Viscotrol C, Oleum Helianthi, Oleum Cocois and the plam oil; Animal oil is one or more in butter, sheep oil, lard and the fish oil.
8. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that described cosurfactant is one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, aliphatic alcohol polyethenoxy (10) ether, aliphatic acid polyethenoxy (15) ether, alkylphenol-polyethenoxy (7) ether, aliphatic amine polyoxyethylene (15) ether, poly(oxyethylene glycol) 400, Yatall MA acid amides, sodium laurylsulfonate and the dodecyl alcohol acyl phosphoric acid ester.
9. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that used silicon source is one or more in white carbon black, water glass, tetraethoxy, methyl silicate, water glass, silicon sol, silica gel, atlapulgite, sodium-potassium silicate, the silicic acid; Used aluminium source is one or more in sodium aluminate, boehmite, gibbsite, aluminum isopropylate, metallic aluminium, nine water aluminum nitrates, aluminum chloride, potassium aluminium alum, 18 water Tai-Ace S 150, aluminum fluoride, aluminum bromide, the aluminum iodide; Used mineralizer is fluorine source or alkali source.
10. according to the synthetic method of the described nano molecular sieve of claim 9, it is characterized in that described fluorine source is NH 4F, HF, CaF 2, KHF 2, NH 4HF 2, SiF 4, CsF, NaF, AgF, (NH 4) 2SiF 6, AlF 3H 2O and NH 4BF 4In one or more, alkali source is sodium hydroxide, magnesium hydroxide, hydrated barta, calcium hydroxide, potassium hydroxide, urea, yellow soda ash, volatile salt, one or more in lime carbonate, salt of wormwood, bicarbonate of ammonia, carbonated aqueous ammonia, liquefied ammonia, the ammoniacal liquor.
11., it is characterized in that used organic solvent is ethylene glycol, glycerol, ethanol, glycol ether, triethylene glycol, one or more of propyl carbinol, polyoxyethylene glycol according to the synthetic method of the described nano molecular sieve of claim 1; Used template is TPAOH, TMAOH, TEAOH, TPABr, Pr 3N, Et 3N, (C 2H 5) 3N, (C 3H 7) 3N, (CH 3) 2NCH 2C 6H 5, (C 2H 5) 2NCH 2CH 2OH, CH 3N (CH 2CH 2OH) 2One or more.
12. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that the stirring described in the step (1) is a mechanical stirring, its stirring velocity is 500-4000r/min.
13. according to the synthetic method of the described nano molecular sieve of claim 1, it is characterized in that the character of nano molecular sieve of gained is as follows: specific surface is 200～600m 2/ g, pore volume 0.1～0.4ml/g, mean pore size is 1～4nm, median size is 10～100nm.
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