CN101671035B - Method for synthesizing A-type ultrafine zeolite - Google Patents
Method for synthesizing A-type ultrafine zeolite Download PDFInfo
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- CN101671035B CN101671035B CN2009101847438A CN200910184743A CN101671035B CN 101671035 B CN101671035 B CN 101671035B CN 2009101847438 A CN2009101847438 A CN 2009101847438A CN 200910184743 A CN200910184743 A CN 200910184743A CN 101671035 B CN101671035 B CN 101671035B
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- 239000010457 zeolite Substances 0.000 title claims abstract description 74
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 73
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- 230000005514 two-phase flow Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 16
- 239000012530 fluid Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 description 36
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- -1 silicon aluminate Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 241001455445 Alfaro Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
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Abstract
The invention relates to a method for synthesizing A-type ultrafine zeolite, comprising the following concrete steps: preparing silicon source, aluminum source, sodium hydroxide and water into zeolite synthetic fluid according to a certain molar ratio; carrying out pre reaction at a certain temperature to obtain pre-reaction synthetic fluid; preparing the silicon source, aluminum source, sodium hydroxide and water into silicon-aluminum clear liquid according to a certain molar ratio; mixing the silicon-aluminum clear liquid and the pre-reaction synthetic fluid and injecting the mixture in a microreactor for crystallization reaction; and centrifuging, washing and drying the obtained suspension to obtain the A-type ultrafine zeolite. The invention can obtain the A-type ultrafine zeolite with an even size in a shorter time, and can conveniently regulate the average size and size distribution of the final products.
Description
Technical field
The present invention relates to a kind of method of synthetic A type ultrafine zeolite, relate in particular to a kind ofly under the condition of not adding organic formwork agent, utilize the microreactor method of the uniform A type of preparation size ultrafine zeolite in extremely rapid succession.
Background technology
A type zeolite is a kind of silicon aluminate crystal with special pore passage structure.Because its unique fractionation by adsorption, ion-exchange and good chemistry can be modified ability, are widely used in industries such as metallurgy, oil, chemical industry, food, medicine as sorbent material, siccative, catalyzer.Ultrafine zeolite generally refers to the zeolite crystal of particle diameter at 100-500nm, when the size of A type zeolite is decreased to ultra-fine level, its performance of aspects such as exclusive absorption and ion-exchange can significantly improve.In addition, the uniform A type of size zeolite can be used in many emerging fields, such as: matrix material of humidity sensor, drug release, multilevel hierarchy or the like.
At present, the conventional means that reduces A type zeolite is to add a large amount of organic structure directed agents (abbreviation template) in zeolite synthesis liquid, mainly is TMAOH (Tetramethylammonium hydroxide).Schoeman etc. contain TMA with utilizations such as Zhu
+A type zeolite synthesis liquid in 100 ℃ of following respectively crystallization after 2 days and 13 days, obtained the A type zeolite (Zeolites, 1994,14,110 and Chem Mater, 1998,10,1483) of 110-300 and 100-200nm.But in the process of removing template, cause the irreversible reunion of nano zeolite and the reduction of degree of crystallinity easily, and use organic formwork agent to pollute the environment.
More same investigators also find not add the A type zeolite that template also can be prepared small particle size, and means commonly used comprise: optimize composition, the prolongation pre-reaction time of synthetic liquid, reduce temperature of reaction and adopt special reaction unit or the like.Comfortable field etc. (Chinese patent CN 1160600A) with the synthetic liquid of faujusite as the silicon source, with Tai-Ace S 150 or sodium aluminate is the aluminium source, the mixed synthetic liquid in silicon source and aluminium source behind 70～105 ℃ of following crystallization 1.5～10h, has been obtained the A type ultrafine zeolite particle of about 500nm.Utilize identical method, Yang Xiaoming etc. (Chinese patent CN 1078179C) further optimize composition, temperature of reaction and the time of zeolite synthesis liquid, and the size of A type ultrafine zeolite is further reduced to 200～400nm.(the optimization mol ratio is 6Na to the Si/Al of Wang Deju etc. (Chinese patent CN 1290767C) by regulating A type zeolite synthesis liquid than, water-content and basicity
2O: 2.5Al
2O
3: 1SiO
2: 128H
2O), behind 60 ℃ of following crystallization 8～12h, obtained the A type zeolite of 200～500nm.Alfaro etc. (Mater Lett., 2007,61,4655) will synthesize liquid earlier 40 ℃ of following pre-reactions 6 days, and then having obtained mean sizes behind 100 ℃ of following crystallization 24h is 500nm, is distributed as the A type zeolite of 200～1400nm.Valtchev etc. (Langmuir, 2005,21,10724 and U.S. Pat 2004/0047803 A1) with fresh synthetic liquid at room temperature crystallization obtained the A type zeolite of 100～300nm after 3 days.As seen, though above-mentioned synthetic method can be prepared the less product of size, the reaction times is generally all longer.Recently, Zhou Zhou etc. (gas chemical industry, 2001,6,4) utilize overcritical device, and having obtained median size behind reaction 30min under 270 ℃ is the A type zeolite of 50nm.Chinese patent CN1544327A also discloses a kind of employing microwave and ultrasonic coupled technology prepares A type nano zeolite.They utilize microwave and ultrasonic growth to nucleus to control, and limit it and grow up, so obtained the less product of size.In frequency is 20kHz, and power is that the ultrasonic and frequency of 100W is 880MHz, and power is under the microwave coupling technique of 300W, and having obtained median size behind the reaction 20min is the A type zeolite of 80nm.Though adopt these special devices can obtain nano level product, troublesome poeration, and cost costliness.
Above-mentioned synthesizing all carried out in batch reactor.The shortcoming of rhythmic reaction is to be difficult to control the synthetic physical parameter exactly, as stirring velocity, and temperature and time etc., thereby caused the character of every batch of product to have to a certain degree difference.Utilize microreactor can accurately control reaction parameter, and have the mode of production of serialization; Its excellent heat and mass transfer ability can shorten the needed time of reaction greatly simultaneously.For the previous period, we utilize cheap stainless steel capillary microreactor to prepare the A type zeolite (Chem.Eng.J. of median size for 400nm continuously, 2006,116,115), the result shows that generated time has dwindled an order of magnitude than popular response, size and distributing also all less than the product of conventional hydro-thermal.But average size of products distributes still big (400nm), distribution of sizes is broad (150-800nm) also.
Summary of the invention
Technical problem to be solved by this invention is: in order to overcome prior art under the situation of not adding template, be difficult to obtain that size is little, the A type zeolite of narrowly distributing by conventional synthetic method, and generally need problem such as long generated time and proposed a kind of mixed solution that adopts sial clear liquid and the synthetic liquid of pre-reaction, the method for in microreactor, synthesizing the uniform A type of size ultrafine zeolite fast.
Technical scheme of the present invention is: utilize the sial clear liquid to mix with the zeolite synthesis liquid of pre-reaction, can increase the dissolution rate of the gel in the initial pre-reaction zeolite synthesis liquid like this, cause finally the nucleus quantity in the synthetic liquid liquid phase to increase, reach and reduce A type zeolite size (＜200nm) purpose.Simultaneously, utilize the higher heating rate of microreactor, mixed solution promptly can be heated to the synthesis temperature that oil bath is controlled from room temperature.This process can be avoided the secondary nucleation phenomenon in the zeolite forming process effectively, thereby obtains the uniform A type of size zeolite in the short time (in the 50min).
The concrete technical scheme of the present invention is: a kind of method of synthetic A type ultrafine zeolite, its concrete steps are: with silicon source, aluminium source, sodium hydroxide and water according to SiO
2: Al
2O
3: Na
2O: H
2The mol ratio of O is 1.0: 0.3～0.8: 3～8: 80～200 to be made into zeolite synthesis liquid, at 10～50 ℃ of following pre-reaction 5～35h, obtains the synthetic liquid of pre-reaction; With silicon source, aluminium source, sodium hydroxide and water according to Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O is 8.6: 0.2～0.5: 0.5～2: 150 preparation sial clear liquids; With the synthetic liquid of sial clear liquid and pre-reaction according to volume ratio 0.5～8: 1 mix after, by peristaltic pump mixed solution is injected in the microreactor that internal diameter is 0.3～2mm and carries out crystallization; Control crystallization temperature is 60～120 ℃, and the control crystallization time of mixed solution in microreactor is 5～50min; At last the suspension of gained is carried out centrifugal, wash and be drying to obtain A type ultrafine zeolite.
Described aluminium source is preferably sodium aluminate, aluminium hydroxide or aluminum isopropylate; The silicon source is water glass or tetraethoxy.In addition, described microreactor is kapillary microreactor and flat microreactor, and the material of microreactor can be tetrafluoroethylene, glass, synthetic glass or stainless steel.The mode that mixed solution injects is divided into single-phase flow or two phase flow, and two phase flow is solution-air or liquid-liquid two-phase.Internal diameter 0.3～the 1mm of refin tubule microreactor wherein.Effective channel size of preferred flat microreactor is 0.5～1mm.When adopting liquid-liquid two-phase, the oil phase immiscible with mixed solution is whiteruss or normal hexane; When adopting gas-liquid two-phase flow, gas is air or nitrogen.
Among the present invention, A type zeolite synthetic depended on multiple factor, temperature and time as pre-reaction, the synthetic liquid of sial clear liquid and pre-reaction separately composition and both blending ratios, the channel size of microreactor and type, the injection mode of mixed solution, crystallization temperature and crystallization time or the like.In general, when liquid was synthesized in the preparation pre-reaction, preferred pre-reaction temperature was 20～40 ℃, and pre-reaction time is 10～30h; The mixed volume ratio of preferred sial clear liquid and the synthetic liquid of pre-reaction is 0.5～4: 1; Preferred crystallization temperature is 60～100 ℃, and the crystallization time is preferably 5～30min, generally microreactor is immersed in control crystallization temperature in the oil bath.The reaction product of collecting is washed with deionized water through after centrifugal at last.Preferably in 80～100 ℃ baking oven, dry by the fire and promptly obtain the uniform A type of size zeolite after 12～24 hours.
Beneficial effect:
The present invention utilizes the sial clear liquid to mix with the zeolite synthesis liquid of process pre-reaction earlier, impel and produce more nucleus, then utilize microreactor apace with these nucleus crystallization, avoid the secondary nucleation phenomenon, but obtain the uniform median size of size within a short period of time at the A of 150～300nm type ultrafine zeolite crystal.In addition, by change sial clear liquid and pre-reaction synthesize liquid separately composition and both blending ratios, the temperature and time of pre-reaction, both mixed volume ratios, the channel size of microreactor and the injection mode of mixed solution can be regulated the mean sizes and the size distribution of final product easily.
Description of drawings
Fig. 1 is the stereoscan photograph (SEM) of sample A1.
Fig. 2 is the XRD figure spectrum of sample A1, A4, A5 and A6.
Fig. 3 is the stereoscan photograph (SEM) of sample A3.
Fig. 4 is the XRD figure spectrum of sample B1, B2, B3 and B4.
Fig. 5 is the stereoscan photograph (SEM) of sample B1.
Embodiment
Embodiment 1
9.141g sodium hydroxide is dissolved in the 60ml deionized water, and the back that stirs is divided in two plastic beakers by equal volume.Then the 3g sodium aluminate is added in one of them beaker, stirring and dissolving is designated as A solution to vitreous state; The 6.438g water glass is added in the another one beaker, stir to clarify vitreous state equally, be designated as B solution; B solution is poured into rapidly in the A solution, obtained fresh zeolite synthesis liquid, mol ratio is 6.2Na
2O: 0.6Al
2O
3: 1.0SiO
2: 150H
2O.Should behind 30 ℃ of following pre-reaction 20h, obtain the synthetic liquid of pre-reaction by fresh synthetic liquid.
Adopt above-mentioned identical compound method, with 34.2g NaOH, the deionized water of 200ml, 3.34g sodium aluminate and 11.5g water glass mix, and (mol ratio is: 8.6Na to be mixed with the sial solution of clear
2O: 0.18Al
2O
3: 1.5SiO
2: 150H
2O), do not need to wear out.
With the synthetic liquid of sial clear liquid and pre-reaction according to volume ratio be mix at 0.5: 1 after, stir 30min under the room temperature.Adopt the feeding manner of single-phase flow, utilize peristaltic pump mixed solution to be injected in 80 ℃ the polytetrafluoroethylene capillary microreactor of internal diameter for 1mm, the control crystallization time is 10min, has obtained product.Through after centrifugal, after washing with deionized water, baking is after 24 hours in 80 ℃ baking oven with reaction product, and having obtained median size is 155nm, is distributed as the A type zeolite of 80～260nm, is designated as sample A1 (Fig. 1).Characterize the characteristic diffraction peak that show sample A1 has A type zeolite by X-ray diffraction, and degree of crystallinity higher (Fig. 2).
Embodiment 2
Adopt the method identical to test, synthesize liquid and sial clear liquid but adopt different silicon sources and aluminium source to prepare pre-reaction with example 1.Silicon source and aluminium source in the synthetic liquid of pre-reaction are respectively tetraethoxy and aluminium hydroxide.And silicon source in the sial clear liquid and aluminium source are respectively water glass and aluminum isopropylate.The product that reaction obtains is designated as sample A2.Characterize the characteristic diffraction peak that these products of demonstration all have A type zeolite by X-ray diffraction.The mean sizes of product is 200nm, and distribution of sizes is 120～330nm.As seen under identical reaction conditions, the kind that changes reactant feed can cause the mean sizes and the distribution of sizes of final A type zeolite to change.
Embodiment 3
Experimentize with the method identical, but adopt the composition of synthetic liquid of different pre-reactions and sial clear liquid, consist of 4.5Na with example 1
2O: 0.43Al
2O
3: 1SiO
2: 150H
2O.And the silicon source of sial clear liquid and aluminium source are respectively tetraethoxy and sodium aluminate; Consist of 8.6Na
2O: 0.5Al
2O
3: 2SiO
2: 150H
2O.Both blending ratios still are 0.5: 1, behind the reaction 10min, have obtained sample A3 in the microreactor of 80 ℃ 1mm.X-ray diffraction characterizes and shows that product is an A type zeolite, and has very high degree of crystallinity.SEM characterizes and shows that also the mean sizes of product is 188nm, and distribution of sizes is 80～360nm (Fig. 3).As seen under identical reaction conditions, the composition that changes synthetic liquid can cause the mean sizes and the distribution of sizes of final A type zeolite to change.
Embodiment 4-6
Experimentize with the method identical, synthesize liquid blended volume ratio with pre-reaction, be respectively 2: 1 and 4: 11: 1 but change the sial clear liquid with example 1.With the reaction product of collecting, obtained sample A4, A5 and A6 after washing and the drying.The degree of crystallinity that characterize to show A4 by X-ray diffraction obviously descends, and A5 and A6 are amorphous fully (Fig. 2).As seen, when volume ratio surpasses 0.5: 1, increase both blended volume ratios and can cause the degree of crystallinity of final product to reduce, until amorphous.
Embodiment 7-8
Experimentize with the method identical, but change the temperature and time (20 ℃ of following pre-reaction 30h and 40 ℃ of following pre-reaction 10h) of pre-reaction with embodiment 1.Reaction product through after centrifugal, is washed with deionized water, and baking was designated as A7 respectively, A8 after 12 hours in 100 ℃ baking oven.X-ray diffraction characterizes and shows that product all has the characteristic diffraction peak of A type zeolite, and degree of crystallinity is 100%.The SEM picture shows that the mean sizes of product is respectively 130 and 175nm, and distribution of sizes is 80～230nm and 120～370nm.As seen, the pre-reaction under lesser temps and long period can reduce the mean sizes of product.
Embodiment 9-11
Experimentize with the method identical, but change the material of kapillary microreactor and size (0.3 and 0.6mm) with embodiment 1.Utilize the stainless steel capillary microreactor of internal diameter for 1mm, the prepared A type zeolite of the glass capillary microreactor of 0.6mm is designated as sample A9, A10 and A11 successively.The X-ray diffraction of gained characterizes and shows that product all has the characteristic diffraction peak of A type zeolite, and degree of crystallinity is higher.The SEM picture shows that average size of products is respectively 160,135 and 110nm, and distribution of sizes is 80～275nm, 80～230nm and 60～200nm.As seen, the material of kapillary microreactor is less for the size impact of final zeolite, but the internal diameter that reduces microreactor but can obtain the less A type zeolite of size.
Embodiment 12
Experimentize with the method identical, but the injection mode that changes mixed solution is liquid-liquid two-phase that wherein oil phase is a whiteruss with embodiment 1.The making processes of microreactor is: the stainless steel capillary that is 0.5mm with one section internal diameter is the polytetrafluoroethylene capillary of 1mm from axially being inserted into another root internal diameter, and the distance of insertion is 5cm.
After the synthetic liquid of sial clear liquid and pre-reaction mixed according to 0.5: 1 volume ratio, utilize peristaltic pump that mixed solution is driven in the interior pipe.Utilize peristaltic pump whiteruss to be driven in the outer tube of 1mm, mixed solution and whiteruss have formed uniform liquid-liquid two-phase blocking fluid in outer tube.Outer tube is immersed in 80 ℃ the oil bath, the control crystallization time of mixed solution in outer tube is 10min, and resulting product is designated as B1.Characterize the characteristic diffraction peak (Fig. 4) that the demonstration product has A type zeolite by X-ray diffraction.SEM picture (Fig. 5) shows that average size of products is 162nm, and distribution of sizes is 95～230nm.
Embodiment 13
Experimentize with the method identical, but changing oil phase is normal hexane that prepared A type zeolite is designated as sample B2 with embodiment 12.Characterize the characteristic diffraction peak (Fig. 4) that the demonstration product has A type zeolite by X-ray diffraction.The SEM picture shows that average size of products is 159nm, and distribution of sizes is 90～235nm.As seen the kind of oil phase is little for the size impact of A type zeolite.
Embodiment 14-15
Experimentize with the method identical, but the kind that changes flow pattern is a gas-liquid two-phase flow that wherein gas phase is air and nitrogen with embodiment 12.The A type zeolite that reacts prepared is designated as sample B3 and B4 successively.Characterize the characteristic diffraction peak (Fig. 4) that the demonstration product has A type zeolite by X-ray diffraction.The SEM picture shows that average size of products is 158 and 161nm, and distribution of sizes is 92～230nm and 90～235nm.As seen the kind of two phase flow is also little for the size impact of A type zeolite.
Embodiment 16
Experimentize with the method identical, but the type that changes microreactor is flat microreactor that material is a synthetic glass with embodiment 12.This flat microreactor has two inlets, and one is advanced mixed solution, a feed liquor paraffin body; And two inlets form the T type with the position that crosses.Effective channel size of microreactor is 0.5mm.Flat microreactor is soaked in 80 ℃ the oil bath, and the resulting product of reaction 10min is designated as sample B5.Characterize to show that by X-ray diffraction product has the characteristic diffraction peak of A type zeolite, and the SEM picture shows that average size of products is 140nm, distribution of sizes is 80～180nm.
Embodiment 17
Experimentize with the method identical, but change the Y type that is shaped as at two inlets and the position that crosses with embodiment 16.React resulting product and be designated as sample B6.X-ray diffraction characterize to show that product has the characteristic diffraction peak of A type zeolite, and the SEM picture shows that average size of products is 138nm, and distribution of sizes is 75～180nm.As seen, the hybrid mode of two-phase inlet is little to the size impact of A type zeolite.
Embodiment 18
Experimentize with the method identical, but the effective channel size that changes microreactor is 1mm, reacts resulting product and is designated as sample B7 with embodiment 16.X-ray diffraction characterize to show that product has the characteristic diffraction peak of A type zeolite, and the SEM picture shows that average size of products is 160nm, and distribution of sizes is 85～230nm.As seen, in flat microreactor, the size that increases passage also can increase the size of A type zeolite.
Embodiment 19-20
Experimentize with the method identical, but change temperature and the reaction times that flat microreactor soaks with embodiment 16.Microreactor is immersed in 60 and 100 ℃ respectively, the reaction times be respectively 30 and the A type zeolite of 5min gained be designated as sample B8 and B9.X-ray diffraction characterizes and shows that two products all have the characteristic diffraction peak of A type zeolite, and degree of crystallinity is very high.The SEM picture characterizes and shows that average size of products is respectively 125,290nm, and distribution of sizes is 60～145nm, 125～450nm.As seen, the rising temperature of reaction can increase the mean sizes of product, but can shorten the reaction times.
Claims (7)
1. a synthetic median size is in the method for the A of 150～300nm type ultrafine zeolite, and its concrete steps are: with silicon source, aluminium source, sodium hydroxide and water according to SiO
2: Al
2O
3: Na
2O: H
2The mol ratio of O is 1.0: 0.3～0.8: 3～8: 80～200 to be made into zeolite synthesis liquid, at 10～50 ℃ of following pre-reaction 5～35h, obtains the synthetic liquid of pre-reaction; With silicon source, aluminium source, sodium hydroxide and water according to Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O is 8.6: 0.2～0.5: 0.5～2: 150 preparation sial clear liquids; With the synthetic liquid of sial clear liquid and pre-reaction according to volume ratio 0.5～8: 1 mix after, by peristaltic pump mixed solution is injected in the microreactor that internal diameter is 0.3～2mm and carries out crystallization; Control crystallization temperature is 60～120 ℃, and the control crystallization time of mixed solution in microreactor is 5～50min; At last the suspension of gained is carried out centrifugal, wash and be drying to obtain median size at the A of 150～300nm type ultrafine zeolite.
2. in accordance with the method for claim 1, it is characterized in that described aluminium source is sodium aluminate, aluminium hydroxide or aluminum isopropylate; The silicon source is water glass or tetraethoxy.
3. in accordance with the method for claim 1, it is characterized in that described pre-reaction temperature is 20～40 ℃, pre-reaction time is 10～30h.
4. in accordance with the method for claim 1, it is characterized in that the synthetic liquid blended volume ratio of sial clear liquid and pre-reaction is 0.5～4: 1.
5. in accordance with the method for claim 1, it is characterized in that described crystallization temperature is that the crystallization time of described control mixed solution in micro passage reaction is 5～30min in 60～100 ℃ the oil bath.
6. in accordance with the method for claim 1, it is characterized in that described microreactor kind is kapillary microreactor or flat microreactor, material is tetrafluoroethylene, glass, synthetic glass or stainless steel; The mode that mixed solution injects is divided into single-phase flow, or solution-air or liquid-liquid two-phase.
7. in accordance with the method for claim 6, the internal diameter that it is characterized in that described kapillary microreactor is 0.3～1mm; When adopting liquid-liquid two-phase, the oil phase immiscible with mixed solution is whiteruss or normal hexane; When adopting gas-liquid two-phase flow, gas is air or nitrogen.
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