CN102452666A - Method for synthesizing IM-5 molecular sieve - Google Patents
Method for synthesizing IM-5 molecular sieve Download PDFInfo
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- CN102452666A CN102452666A CN2010105142049A CN201010514204A CN102452666A CN 102452666 A CN102452666 A CN 102452666A CN 2010105142049 A CN2010105142049 A CN 2010105142049A CN 201010514204 A CN201010514204 A CN 201010514204A CN 102452666 A CN102452666 A CN 102452666A
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Abstract
The invention relates to a method for synthesizing IM-5 molecular sieve, which comprises the following steps: 1) dissolving inorganic base, aluminum source and a template in deionized water, uniformly mixing; 2) adding silicon source in a mixture obtained in the step 1), adding an additive or not to prepare colloid or a solid-liquid mixture, uniformly mixing; 3) moving the colloid or the solid-liquid mixture obtained in the step 2) to a crystallization kettle, carrying out hydrothermal dynamic crystallization at the temperature of 120-200 DEG C for 1-10 days, cooling after finishing the crystallization, washing the obtained mixed liquor, filtering and drying to obtain the IM-5 molecular sieve raw powder; wherein the mole ratio of the reactant is SiO2: Al2O3:M2O: R: H2O with 60: (0.3-6): (6-20): (0.6-18): (300-1800), M2O is alkali metal oxide and R is the template. The method of the invention has the advantages that IM-5 molecular sieve crystallization time is shortened, the raw material ratio range is wide, the single kettle yield is enhanced and the industrial amplification can be achieved.
Description
Technical field
The present invention relates to a kind of compound method of molecular sieve, more particularly, relate to a kind of method of synthetic IM-5 molecular sieve.
Background technology
The effect that molecular sieve play more and more in petrochemical industry is important.Along with the development of petrochemical complex and Fine Chemical Industry, environmental requirement strictness day by day also constantly increases the new catalytic material demand in the production process.Wherein the ten-ring molecular sieve is because its distinctive pore size and pore passage structure make it have a wide range of applications in the shape selective catalysis field.The molecule that has only size and shape and molecular sieve pore passage to be complementary could get into molecular sieve pore passage, utilizes the pore size of molecular sieve and the difference on the pore passage structure, can realize " molecule screening " to a certain extent, makes it have the ability of shape selective catalysis.The IM-5 molecular sieve is a kind of, and this molecular sieve has two-dimentional ten-ring pore canal system, limited short duct on the third dimension, and its pore canal system and ZSM-5 molecular sieve are quite similar, in reactions such as aromatic disproportion, isomerizing, alkylation, have good shape selectivity.WO98/17581A1 discloses IM-5 molecular sieve and compound method thereof first; Its compound method is according to certain proportioning, and water is joined in the blended solid sample that contains silicon source, template, is stirred to obtain a kind of uniform mixture; The mixed solution of then sodium aluminate and caustic soda being dissolved into adds wherein; Keep stirring, kept 15 minutes, be transferred to one then and be equipped with in the teflon-lined autoclave; Crystallization under certain condition is through the synthetic bullion that filters, washing, oven dry obtain the IM-5 molecular sieve.
The IM-5 molecular sieve has good thermostability and hydrothermal stability; Catalytic performance is good, in catalyzed reaction, has a wide range of applications, for example the disclosed a kind of catalyzer of US5989410; Be that the hydrogenation/dehydrogenation metallic element is loaded on the IM-5 molecular sieve, this catalyzer can effectively improve the paraffin pour point.The molecular sieve that the disclosed catalytic cracking catalyst of US6007698 is comprised comprises IM-5 molecular sieve and USY molecular sieve, and this catalyzer is used for the heavy oil feedstock catalytic cracking process, can effectively improve the reaction mass transformation efficiency, simultaneously high yield propylene, butylene.
Synthetic report about the IM-5 molecular sieve is less; WO98/17581A1 discloses several kinds of compound methods of IM-5; Comprise and adopt 1; Two (N-crassitude) the pentane bromine salt or 1 of 5-, two (N-crassitude) the hexane bromine salt of 6-are as template, and crystallization synthesized pure phase IM-5 molecular sieve in 8～13 days under 160～170 ℃ of conditions.
Synthetic, the sign of IM-5 and NU-88 molecular sieve and catalysis characteristics (Synthesis; Characterization; And catalytic properties of zeolites IM-5 and NU-88.Journal of Catalysis 2003:215 151～170) and IM-5: the shape slective cracking molecular sieve of a kind of high thermal stability and hydrothermal stability (IM-5:A Highly Thermal and Hydrothermal Shape-Selective Cracking Zeolite. (Journal of Catalysis 2002:206; 125～133) also reported the compound method of IM-5 molecular sieve in respectively and comparatively at large set forth its synthesising law: in the compound method of having reported; Have only employing WHITE CARBON BLACK (Aerosil 130/200) can successfully synthesize the IM-5 molecular sieve of pure phase as the silicon source; And synthesis cycle is longer, needs 10 to 14 days mostly.Proportion of raw materials narrow range, particularly sodium-silicon-rate only can synthesize pure IM-5 molecular sieve when the IM-5 molecular sieve was synthetic near 0.73, changed will generate stray crystals such as MOR, ZSM-12 and ANA mutually a little, and synthetic narrow range is unfavorable for the industry amplification.IM-5 molecular sieve synthetic system water-content is too high, and water silicon ratio is not less than 40, causes single still yield low, and only in little reaction kettle (about 50ml), can synthesize, and amplifies difficulty.
Since less to the study on the synthesis of IM-5 molecular sieve, the relevant report solution to the problems described above do not had so far.Therefore explore effective synthesizing mean, widen the proportioning raw materials scope, shorten generated time, improve single still yield, it is significant to seek suitable amplification method.
Summary of the invention
The technical problem that the present invention will solve is on the basis of existing technology, the IM-5 molecular sieve compound method that provide a kind of proportioning raw materials broad, crystallization time to lack, single still yield is high, is easy to amplify production.
A kind of method of synthetic IM-5 molecular sieve may further comprise the steps:
(1) mineral alkali, aluminium source, template are dissolved in the deionized water, mix;
(2) in the mixing solutions of step (1), add the silicon source, add or do not add additive, mix, process colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in the crystallizing kettle, the hydro-thermal dynamic crystallization is 1～10 day under 120～200 ℃ temperature, and crystallization cools after finishing, and the gained mixed solution promptly obtains the IM-5 molecular screen primary powder through washing, filtration, oven dry;
The mole of said reactant consists of SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.3～6): (6～20): (0.6～18): (300～1800), M
2O is an alkalimetal oxide, and R is a template.
Preferred reactant mole consists of: SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.5～4): (6～19.5): (3～12): (600～1200).
The beneficial effect of method provided by the invention is:
The method of a kind of synthetic IM-5 molecular sieve provided by the invention can shorten the crystallization time of IM-5 molecular sieve effectively, widens the proportion of raw materials scope, improves single still yield.Present method in the water-content, has added different additives in reducing building-up process, make generated time obtain further shortening.The compound method of IM-5 molecular sieve provided by the invention is easier to amplify and produces, and it is synthetic to be implemented in 2 liters of crystallization in the reaction kettle.
Description of drawings
Fig. 1 is the IM-5 molecular sieve X-ray diffractogram (XRD) of report in the Comparative Examples 1.
Fig. 2 is the X-ray diffractogram (XRD) of embodiment 11 synthetic IM-5 molecular sieves.
Fig. 3 is the ESEM shape appearance figure (SEM) of embodiment 11 synthetic IM-5 molecular sieves.
Fig. 4 is the transmission electron microscope shape appearance figure (TEM) of embodiment 11 synthetic IM-5 molecular sieves.
Embodiment
Compound method provided by the present invention can adopt different silicon sources and aluminium source to synthesize, and template is 1, and the salt of two (N-crassitude) pentanes of 5-also can add an amount of other additive or crystal seed, according to the synthetic IM-5 molecular sieve of the method for conventional hydrothermal crystallizing.
The method of synthetic IM-5 molecular sieve provided by the invention may further comprise the steps:
(1) mineral alkali, aluminium source, template are dissolved in the deionized water, mix;
(2) in the mixing solutions of step (1), add the silicon source, add or do not add additive, mix, process colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in the crystallizing kettle, the hydro-thermal dynamic crystallization is 1～10 day under 140～200 ℃ temperature, and crystallization cools after finishing, and the gained mixed solution promptly obtains the IM-5 molecular screen primary powder through washing, filtration, oven dry;
Wherein, the mole of said reactant consists of SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.3～6): (6～20): (0.6～18): (300～1800), M
2O is an alkalimetal oxide, and R is a template.
Preferred reactant mole consists of: SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.5～4): (6～19.5): (3～12): (600～1200).
In the method provided by the invention; Step (1) can be at room temperature be dissolved in mineral alkali, aluminium source, the template of certain proportioning in the deionized water together; Mix with stirring method, also can mineral alkali, aluminium source, the template of certain proportioning be dissolved in respectively in the deionized water, be prepared into solution respectively; Then the solution for preparing is mixed, the present invention is not limited in this respect.Formulations prepared from solutions well after, preferably leave standstill for some time, more preferably leave standstill more than 30 minutes.
In the step (1), described silicon source is selected from one or more in soft silica, water glass, silicon sol, solid oxidation silicon, solid silicone, zeyssatite, WHITE CARBON BLACK and the tetraethoxy, is preferably silicon sol and/or solid silicone.
Described aluminium source is selected from one or more in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, phosphagel phosphaljel, aluminum chloride, aluminum nitrate, white lake, aluminum oxide and the pseudo-boehmite, is preferably in sodium metaaluminate, aluminum nitrate and the aluminum chloride one or more.
Described mineral alkali is NaOH or KOH, is preferably NaOH.
Described template is 1, and the salt of two (N-crassitude) pentanes of 5-is preferably 1, two (N-crassitude) the pentane bromine salt of 5-.
In the method provided by the invention, add the silicon source in the solution that in step (1), makes in the step (2), the preferred silicon source solution that slowly drips of the process of adding can be reacted into glue after making silicon source solution add solution with very slow speed.Can add or not add additive in the method provided by the invention, more preferably add additive, additive adds the solid state additive after can or becoming glue with the common dissolving of other materials, with the SiO that adds
2Weight be benchmark, the add-on of additive is SiO
2The 1-20wt% of weight.
Described additive is selected from crystal seed, the synthetic precursor of IM-5, NaBr, NaNO
3And NaClO
4In one or more, one or more among synthetic precursor of crystal seed, IM-5 and the NaBr more preferably.
Wherein, said crystal seed is the IM-5 molecular sieve after the roasting.The synthetic precursor of said IM-5 is the extract of IM-5 colloid crystallization pilot process.
In the method provided by the invention, in the step (3) colloid of step (2) gained or solidliquid mixture moved to and carry out hydrothermal crystallizing in the crystallizing kettle, said hydrothermal crystallizing is the usual manner of hydrothermal crystallizing in the prior art, comprises static hydrothermal crystallization or dynamic hydrothermal crystallizing.Hydrothermal crystallizing in the method provided by the invention be meant under 120～200 ℃ the temperature with autogenous pressure under hydrothermal crystallizing 1～10 day, preferably under 140～180 ℃ the temperature with autogenous pressure under hydrothermal crystallizing 3～5 days.Crystallization cools after finishing, and the gained mixed solution is promptly obtained the IM-5 molecular screen primary powder through washing, filtration, oven dry.Wherein, washing, filtration, oven dry are the mode of various routines in this area, and the present invention is not limited in this respect.Preferably dry down and spend the night, obtain the IM-5 molecular screen primary powder at 80 ℃.
The beneficial effect of the compound method of IM-5 molecular sieve provided by the invention is:
Method provided by the invention has solved problems such as the crystallization time length, proportioning raw materials narrow range, the single still yield that exist when prior art is synthesized the IM-5 molecular sieve are low, amplification difficulty.Because present method has reduced the system water-content, has improved material concentration, thereby has shortened the crystallization time of IM-5 molecular sieve widely, single still yield also is improved thereupon.Adopt this method can suppress the generation of stray crystal phase effectively simultaneously, can access the pure IM-5 molecular sieve that gets mutually in the proportioning raw materials scope of broad, help industry and amplify.Adopt present method in 2 liters of stainless steel cauldrons, to successfully synthesize pure IM-5 molecular sieve.
Pass through example in detail the present invention below, but therefore the present invention does not receive any restriction.
In embodiment and the Comparative Examples, the specification of used all ingredients with the source as follows:
NaOH, NaBr, AlCl
3And Al (NO
3)
39H
2O is analytical pure, is produced by the Beijing Chemical Plant;
1, two (N-crassitude) the pentane bromine salt brine solutions of 5-, solid content is 43.79wt%, has much Fine Chemical Works production by Guangzhou;
1, two (N-crassitude) the pentane villaumite salt brine solutions of 5-, solid content 45.28wt% has much Fine Chemical Works production by Guangzhou;
Alkaline silica sol, SiO
2Solid content 30wt% is produced by Beijing flying dragon equine trade ltd;
Solids crude piece silica gel, SiO
2Solid content 92.5wt% is produced by Qingdao Marine Chemical Co., Ltd.;
Silica gel microball, SiO
2Solid content 90.13wt% is produced by Qingdao Marine Chemical Co., Ltd.;
Pseudo-boehmite, solid content 66.3wt% is produced by Chang Ling catalyzer branch office of limited-liability company of China Petrochemical Industry.
Comparative Examples 1
Comparative Examples 1 explanation documents 1 (the synthesizing of IM-5 and NU-88 molecular sieve, sign and catalysis characteristics; Synthesis, characterization, and catalytic properties of zeolites IM-5 and NU-88.Journal of Catalysis 2003:215 151～170) in the compound method of disclosed IM-5 molecular sieve.
With 1, salt of two (N-crassitude) pentanes of 5-and NaOH, Al (NO
3)
39H
2(98%, Junsei), (Aerosil 200, Degussa) are mixed and made into colloid with deionized water, and the mole of reaction mixture consists of: SiO for WHITE CARBON BLACK for O
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 21.9: 9: 2400.Gained mixture stirring at room 24 hours is transferred to the colloid that makes in the 45ml teflon-lined crystallizing kettle, and the rotation crystallization is after 14 days down in 160 ℃, and rotating speed is 100rpm.Stop crystallization, product promptly obtains the IM-5 molecular sieve after washing, filtration, oven dry.
The X-ray diffractogram (XRD) of gained IM-5 molecular sieve is seen accompanying drawing 1
Comparative Examples 2
Comparative Examples 2 explanation documents 2 (IM-5: the shape slective cracking molecular sieve of a kind of high thermal stability and hydrothermal stability; IM-5:A Highly Thermal and Hydrothermal Shape-Selective Cracking Zeolite.Journal of Catalysis 2002:206,125～133) disclosed IM-5 molecular sieve compound method in.
(Aerosil 200, Degussa) under stirring condition, join 1, in the aqueous solution of two (N-crassitude) the pentane bromine salt of 5-, and then add sodium aluminate (CarloErba, 56%Al respectively with the WHITE CARBON BLACK of aequum
2O
3), the aqueous solution of NaOH (Prolabo, 98%), NaBr (Scharlau, 99%), process colloid, the mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 1.5: 17: 6: 10: 2400.Gained mixture stirring at room 30 minutes was transferred to the colloid that makes in the teflon-lined crystallizing kettle, in 175 ℃ of following crystallization 10 days.Stop crystallization, product promptly obtains the IM-5 molecular sieve after washing, filtration, oven dry.
Embodiment 1
The compound method of embodiment 1 explanation IM-5 molecular sieve provided by the invention.
(1) sodium metaaluminate (NaAlO
2) preparation of solution
Take by weighing 194g NaOH and be dissolved in about 500ml deionized water, add 153g pseudo-boehmite (solid content 66.3%), boiling 30min obtains clear solution.Gained liquid is made into 1L solution while hot, cools off subsequent use.
(2) 2.95g NaOH is dissolved in the 25.57g deionized water, adds the NaAlO of preparation in the 4.01g step (1) then
2The aqueous solution and 27.40g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under stirring condition, slowly drip the 40g alkaline silica sol, process colloid, continue to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 13.5: 9: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in the 50ml teflon-lined autoclave, under 160 ℃, rotates crystallization after 6 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
The compound method of embodiment 2 explanations IM-5 molecular sieve provided by the invention.
1.65g NaOH is dissolved in the 24.66g deionized water, adds the NaAlO of preparation in 12.04g embodiment 1 step (1) then
2The aqueous solution and 18.27g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under stirring condition, slowly drip the 40g alkaline silica sol, add SiO again
2IM-5 molecular sieve after the roasting of the 5wt% of weight is processed colloid as crystal seed (seed), continues to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H2O=60: 3: 13.5: 6: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in the 50ml teflon-lined autoclave, under 160 ℃, rotates crystallization after 5 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 3
The compound method of embodiment 3 explanations IM-5 molecular sieve provided by the invention.
2.88g NaOH and 2.06g NaBr are dissolved in the 21.95g deionized water, add the 2.01g NaAlO of preparation in embodiment 1 step (1) then
2The aqueous solution, 36.54g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under stirring condition, slowly drip the 40g alkaline silica sol, process colloid, continue to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 0.5: 12: 6: 12: 1200, water silicon ratio was 20: 1.The colloid that makes is transferred in the 50ml teflon-lined autoclave, under 160 ℃, rotates crystallization after 4 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 4
The compound method of embodiment 4 explanations IM-5 molecular sieve provided by the invention.
1.99g NaOH is dissolved in the 21.74g deionized water, adds the NaAlO of preparation in 4.01g embodiment 1 step (1) then
2The aqueous solution and 27.40g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and in mixing solutions, add 12.97g solids crude piece silica gel, process solidliquid mixture.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 9.9: 6: 600, water silicon ratio is 10: 1.The solidliquid mixture that makes is transferred in the 50ml teflon-lined autoclave, under 160 ℃, rotates crystallization after 8 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
The compound method of embodiment 5 explanations IM-5 molecular sieve provided by the invention.
With 4.00g NaOH and 0.45g AlCl
3Be dissolved in the 32.72g deionized water, add 20.61g1 then, two (N-crassitude) the pentane villaumite salt brine solutions of 5-mix, and under stirring condition, slowly drip the 40g alkaline silica sol, process colloid, continue to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 0.5: 15: 9: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in the 50ml teflon-lined autoclave, under 140 ℃, rotates crystallization after 10 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 6
The compound method of embodiment 6 explanations IM-5 molecular sieve provided by the invention.
With 4.80g NaOH and 0.89g AlCl
3Be dissolved in the 91.65g deionized water, add 27.47g1 then, two (N-crassitude) the pentane villaumite salt brine solutions of 5-mix, and in mixing solutions, add the 13.31g silica gel microball, process solidliquid mixture.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 18: 9: 1800, water silicon ratio is 30: 1.The solidliquid mixture that makes is transferred in the 50ml teflon-lined autoclave, under 180 ℃, rotates crystallization after 6 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 7
The compound method of embodiment 7 explanations IM-5 molecular sieve provided by the invention.
With 3.12g NaOH, 2.06g NaBr and 3.75g Al (NO
3)
39H
2O is dissolved in the 27.29g deionized water, adds 16.44g 1 then, and two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and in mixing solutions, adds 12.97g solids crude piece silica gel, processes solidliquid mixture.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 1.5: 11.7: 6: 5: 900, water silicon ratio was 15: 1.The solidliquid mixture that makes is transferred in the 50ml teflon-lined autoclave, under 180 ℃, rotates crystallization after 4 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 8
The compound method of embodiment 8 explanations IM-5 molecular sieve provided by the invention.
2.05g NaOH is dissolved in the 14.39g deionized water, adds the NaAlO of preparation in 12.04g embodiment 1 step (1) then
2The aqueous solution and 36.54g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under stirring condition, slowly drip the 40g alkaline silica sol, add SiO again
2Synthetic precursor after the 10wt% roasting of weight is processed colloid, continues to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 3: 15: 12: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in the 50ml teflon-lined autoclave, under 160 ℃, rotates crystallization after 3 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 9
The compound method of embodiment 8 explanations IM-5 molecular sieve provided by the invention.
With 3.36g NaOH, 2.06g NaBr and 3.75gAl (NO
3)
39H
2O is dissolved in the 31.10g deionized water, adds 20.61g 1 then, and two (N-crassitude) the pentane villaumite salt brine solutions of 5-mix, and under stirring condition, slowly drip the 40g alkaline silica sol, add SiO again
2IM-5 molecular sieve after the 5wt% roasting of weight is processed colloid as crystal seed, continues to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 1.5: 12.6: 6: 9: 1200.The colloid that makes is transferred in the 50ml teflon-lined autoclave, under 180 ℃, rotates crystallization after 3 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
The effect of the synthetic IM-5 molecular sieve of embodiment 2 liters of crystallization devices of 10 explanation employings provided by the invention.
49.76g NaOH is dissolved in the 643.70g deionized water, adds the NaAlO of preparation in 100.35g embodiment 1 step (1) then
2The aqueous solution and 319.71g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and in mixing solutions, add 324.32g solids crude piece silica gel, process solidliquid mixture.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 9.9: 4: 600, water silicon ratio is 10: 1.The solidliquid mixture that makes is transferred in the 2L stainless steel crystallizing kettle, under 160 ℃, rotates crystallization after 4 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
Embodiment 11
The effect of the synthetic IM-5 molecular sieve of embodiment 2 liters of crystallization devices of 11 explanation employings provided by the invention.
36.88g NaOH is dissolved in the 319.65g deionized water, adds the NaAlO of preparation in 50.18g embodiment 1 step (1) then
2The aqueous solution and 342.54g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under stirring condition, slowly Dropwise 5 00g alkaline silica sol adds SiO again
2IM-5 molecular sieve after the 5wt% roasting of weight is processed colloid as crystal seed, continues to stir 2 hours.The mole of reaction mixture consists of: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 13.5: 9: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred to 2L stainless steel crystallizing kettle, under 160 ℃, rotates crystallization after 3 days, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and promptly obtained the IM-5 molecular sieve.
The synthetic molecular sieve is carried out X diffraction analysis (XRD) and ESEM is taken pictures, and the result sees Fig. 2-4.The used instrument of X diffraction analysis is a Japan reason D/MAX-III A type diffractometer, and test condition is the Cu target, K α radiation, and tube voltage is 35KV, tube current is 35mA.
ESEM is taken pictures (SEM), and used instrument is the Quanta 200F of a FEI Co. type ESEM, acceleration voltage 20.0KV.
The used instrument of transmission electron microscope photo is the TECNAIG of FEI Co.
2F20, acceleration voltage 200KV.
Visible by accompanying drawing 2, method provided by the invention can in the bigger crystallization device, be utilized the synthetic IM-5 molecular screen primary powder of short crystallization time at low water silicon ratio.Visible with accompanying drawing 4 by accompanying drawing 3, synthetic IM-5 molecular sieve crystal pattern is bar-shaped for length, uniform crystal particles, and better crystallinity degree, no amorphous substance exists.
Claims (10)
1. the method for a synthetic IM-5 molecular sieve may further comprise the steps:
(1) mineral alkali, aluminium source, template are dissolved in the deionized water, mix;
(2) in the mixing solutions of step (1), add the silicon source, add or do not add additive, mix, process colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in the crystallizing kettle, the hydro-thermal dynamic crystallization is 1～10 day under 120～200 ℃ temperature, and crystallization cools after finishing, and the gained mixed solution promptly obtains the IM-5 molecular screen primary powder through washing, filtration, oven dry;
The mole of said reactant consists of SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.3～6): (6～20): (0.6～18): (300～1800), M
2O is an alkalimetal oxide, and R is a template.
2. according to the method for claim 1, it is characterized in that the mole of said reactant consists of: SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.5～4): (6～19.5): (3～12): (600～1200), M
2O is an alkalimetal oxide, and R is a template
3. according to the method for claim 1 or 2, it is characterized in that, in the step (1) mineral alkali, aluminium source, template are dissolved in the deionized water, mix, leave standstill more than 30 minutes.
4. according to the method for claim 1 or 2, it is characterized in that said silicon source is water glass, silicon sol or solid silicone.
5. according to the method for claim 1 or 2, it is characterized in that said aluminium source is sodium metaaluminate, Tai-Ace S 150, aluminum chloride or aluminum nitrate.
6. according to the method for claim 1 or 2, it is characterized in that said mineral alkali is NaOH and/or KOH.
7. according to the method for claim 1 or 2, it is characterized in that said template is a bi-quaternary ammonium salt.
8. according to the method for claim 7, it is characterized in that described template is 1, the salt of two (N-crassitude) pentanes of 5-.
9. according to the method for claim 1 or 2, it is characterized in that described additive is the synthetic precursor of IM-5 crystal seed, IM-5, NaBr, NaNO
3And NaClO
4In one or more.
10. according to the method for claim 1, it is characterized in that, described hydrothermal crystallizing condition be 140～180 ℃ with autogenous pressure under hydrothermal crystallizing 3～5 days.
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