CN103693654A - Method for synthesis of IM-5 molecular sieve - Google Patents
Method for synthesis of IM-5 molecular sieve Download PDFInfo
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Abstract
A method for synthesis of an IM-5 molecular sieve comprises the following steps: (1) dissolving an inorganic alkali, an aluminum source and a template agent in deionized water, and evenly mixing to obtain a mixed solution; (2) adding solid silica gel into the mixed solution of the step (1), adding an additive or adding no additive, mixing evenly, and preparing a colloid or a solid-liquid mixture; and (3) transferring the colloid or the solid-liquid mixture of the step (2) to a crystallization kettle, carrying out hydrothermal crystallization for 1-10 days, after finishing crystallization, cooling to reduce the temperature, washing, filtering and drying the obtained mixed liquid, and thus obtaining an IM-5 molecular sieve raw powder. The molar ratio of the reactants is SiO2:Al2O3:M2O:SDA:H2O=60:(0.6-6):(6-30):(0.6-24):(300-3000), wherein M2O is an alkali metal oxide, and SDA is a template agent. The IM-5 molecular sieve synthesized by the method is of a stacking fault sheet-shaped structure, and has better catalytic performance.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular sieve, more particularly, is a kind of method of synthetic IM-5 molecular sieve.
Background technology
Molecular sieve plays a part more and more important in petrochemical industry.Along with the development of petrochemical complex and Fine Chemical Industry, in production process environmental requirement increasingly strict, new catalytic material demand is also constantly increased.Wherein ten-ring molecular sieve, due to its distinctive pore size and pore passage structure, makes it in shape selective catalysis field, have a wide range of applications.1997, Compaynie Francaise des Petroles (IFP) successfully synthesized IM-5 molecular sieve.This molecular sieve has two-dimentional ten-ring pore canal system, limited short duct in the third dimension, and its pore canal system and ZSM-5 molecular sieve are quite similar, in the reactions such as aromatic disproportion, isomerization, alkylation, have good shape selectivity.WO98/17581A1 discloses IM-5 molecular sieve and synthetic method thereof first, its synthetic method is for according to a certain ratio, water is joined in the blended solid sample that contains silicon source, template, be stirred to and obtain a kind of uniform mixture, then mixed solution sodium aluminate and caustic soda being dissolved into adds wherein, keep stirring, maintain 15 minutes, then being transferred to one is equipped with in teflon-lined autoclave, crystallization under certain condition, after filtration, washing, dry the synthetic crude product that obtains IM-5 molecular sieve.
IM-5 molecular sieve has good thermostability and hydrothermal stability, catalytic performance is good, has a wide range of applications, for example the disclosed a kind of catalyzer of US5989410 in catalyzed reaction, be that hydrogenation/dehydrogenation metallic element is loaded on IM-5 molecular sieve, this catalyzer can effectively improve paraffin pour point.The molecular sieve that the disclosed catalytic cracking catalyst of US6007698 comprises comprises IM-5 molecular sieve and USY molecular sieve, and this catalyzer, for heavy oil feedstock catalytic cracking process, can effectively improve reaction mass transformation efficiency, simultaneously high yield propylene, butylene.
Synthetic report about IM-5 molecular sieve is less, WO98/17581A1 discloses several synthetic 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-is as template, and under 160 ~ 170 ℃ of conditions, crystallization has synthesized pure phase IM-5 molecular sieve for 8 ~ 13 days.Synthesizing of IM-5 and NU-88 molecular sieve, characterize and catalysis characteristics (Synthesis, characterization, and catalytic properties of zeolites IM-5and NU-88.Journal of Catalysis 2003:215151 ~ 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) in, also reported respectively the synthetic method of IM-5 molecular sieve and comparatively at large set forth its synthesising law: in the synthetic method of having reported, only have employing white carbon black (Aerosil 130/200) can successfully synthesize the IM-5 molecular sieve of pure phase as silicon source, and synthesis cycle is longer, mostly need 10 to 14 days.Synthetic IM-5 molecular sieve is long rhabdolith, and length direction is of a size of 500-700nm.
In catalyzed reaction, the diffusional resistance of volume particle size molecular sieve is large, and active centre utilization ratio is low, easily inactivation.The molecular sieve of small grain size can effectively reduce diffusional resistance, improves active centre utilization ratio, and it is strong to hold charcoal ability.This patent has synthesized a kind of small grain size IM-5 molecular sieve, and the method effectively shortened the generated time of IM-5 molecular sieve, has widened the ratio range of raw material, has improved single still yield, can be applicable to pilot scale and industrial production.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and a kind of method of solid silicone as silicon source efficient synthesizing new IM-5 molecular sieve of take is provided.。
The method of a kind of synthetic IM-5 molecular sieve provided by the invention, comprises the following steps:
(1) mineral alkali, aluminium source, template are dissolved in deionized water, mix and make mixing solutions;
(2) in the mixing solutions of step (1), add solid silicone, add or do not add additive, mix, make colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in crystallizing kettle, hydrothermal crystallizing 1 ~ 10 day, after crystallization finishes, cools, and gained mixed solution obtains IM-5 molecular screen primary powder through washing, filtration, oven dry;
Mole consisting of of described reactant: SiO
2: Al
2o
3: M
2o:SDA:H
2o=60:(0.6 ~ 6): (6 ~ 30): (0.6 ~ 24): (300 ~ 3000), wherein, M
2o is alkalimetal oxide, and SDA is template.Preferably consist of: SiO
2: Al
2o
3: M
2o:SDA:H
2o=60:(0.75 ~ 3): (9 ~ 15): (3 ~ 12): (360 ~ 600), wherein, M
2o is alkalimetal oxide, and SDA is template.
Described solid silicone is one or more in silochrom, Kiselgel A or spherical silica gel, is preferably silochrom.Wherein, described solid silicone refers to Na
2o content ﹤ 1%, the impure less silica gel of a class of solid content >80wt%.Described silochrom is that mean pore size is 8-12nm, and specific surface area is 300-400m
2/ g, pore volume is at the solid silicone of 0.7-1.0ml/g.Described Kiselgel A is that mean pore size is 2-3nm, and specific surface area is 650-800m
2/ g, pore volume is at the solid silicone of 0.35-0.45ml/g.Described spherical silica gel be pore structure between silochrom, Kiselgel A, pore volume is 0.60-0.85ml/g, mean pore size is 4.5-7.0nm, the solid silicone that specific surface is 450-650m2/g.
Described aluminium source is selected from one or more in sodium metaaluminate, Tai-Ace S 150, aluminum chloride and aluminum nitrate.
Described mineral alkali is NaOH and/or KOH.
Described template is bi-quaternary ammonium salt, is preferably two (N-crassitude) the pentane bromine salt of 1,5-.
Described hydrothermal crystallizing refers at 120 ~ 200 ℃ hydrothermal crystallizing 1 ~ 10 day; Be preferably segmentation hydrothermal crystallizing, 80 ~ 140 ℃ of hydrothermal crystallizings are 0.5 ~ 2 day, 140 ~ 200 ℃ of hydrothermal crystallizings 2 ~ 6 days; More preferably 100 ~ 120 ℃ of hydrothermal crystallizings 1 ~ 2 day, 160 ~ 180 ℃ of hydrothermal crystallizings 2 ~ 4 days.
Described hydrothermal crystallizing can comprise the methods such as pre-depolymerization and ageing.Described pre-depolymerization method refers to that formerly not adding silicon source under template condition, aluminium source and mineral alkali first mixes pyroreaction for some time and make high poly-state silicon progressively be depolymerized to the silicon of oligomeric state; Described aging method refers in containing the solidliquid mixture of template first in low temperature crystallized for some time, and object is also to promote that depolymerization first occurs in silicon source.
The beneficial effect of method provided by the invention is:
Method provided by the invention adopts solid silicone as silicon source.Compare with the synthetic method of existing IM-5 molecular sieve, method provided by the invention has been synthesized the IM-5 molecular sieve with lamella Stacking Fault Structure.Meanwhile, the method has shortened the crystallization time of IM-5 molecular sieve effectively, and single still yield is high, can be applicable to pilot scale and industrial production.
Accompanying drawing explanation
Fig. 1 is the IM-5 molecular sieve X-ray diffractogram (XRD) of reporting in document;
Fig. 2 is the X-ray diffractogram (XRD) of the IM-5 molecular sieve of embodiment 1 preparation;
Fig. 3 is the transmission electron microscope shape appearance figure (TEM) of the IM-5 molecular sieve of comparative example 1 preparation;
Fig. 4 is the transmission electron microscope shape appearance figure (TEM) of the IM-5 molecular sieve of comparative example 2 preparations;
Fig. 5 is the scanning electron microscope shape appearance figure (SEM) of the IM-5 molecular sieve of comparative example 2 preparations;
Fig. 6 is the scanning electron microscope shape appearance figure (SEM) of the IM-5 molecular sieve of embodiment 1 preparation;
Fig. 7 is the scanning electron microscope shape appearance figure (SEM) of the IM-5 molecular sieve of embodiment 2 preparations.
Embodiment
The method concrete steps of synthesizing IM-5 molecular sieve by using composite template provided by the invention are as follows:
The method of a kind of synthetic IM-5 molecular sieve provided by the invention, comprises the following steps:
(1) mineral alkali, aluminium source, template are dissolved in deionized water, mix and make mixing solutions;
(2) in the mixing solutions of step (1), add solid silicone, add or do not add additive, mix, make colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in crystallizing kettle, hydrothermal crystallizing 1 ~ 10 day, after crystallization finishes, cools, and gained mixed solution obtains IM-5 molecular screen primary powder through washing, filtration, oven dry;
Wherein, mole consisting of of described reactant: SiO
2: Al
2o
3: M
2o:SDA:H
2o=60:(0.6 ~ 6): (6 ~ 60): (0.6 ~ 24): (300 ~ 3000), wherein, M
2o is alkalimetal oxide, and SDA is template.Preferably consist of: SiO
2: Al
2o
3: M
2o:SDA:H
2o=60:(0.75 ~ 3): (9 ~ 15): (3 ~ 12): (360 ~ 600), wherein, M
2o is alkalimetal oxide, and SDA is template.
In method provided by the invention, step (1) can at room temperature be dissolved in deionized water by the mineral alkali of certain proportioning, aluminium source, two kinds of template together, by the method stirring, mix, also can the mineral alkali of certain proportioning, aluminium source, template be dissolved in respectively in deionized water, be prepared into respectively solution, then the solution preparing is mixed, the present invention is not limited in this respect.After solution prepares, standing for some time, preferably standing more than 30 minutes.
Described in step (1), solid silicone is one or more in silochrom, Kiselgel A or spherical silica gel, is preferably silochrom.Wherein, described solid silicone is Na
2o content ﹤ 1wt%, the impure less silica gel of a class of solid content >80wt%.Described gross porosity class silica gel is mean pore size 8.0-13.0nm, specific surface area 300-400m
2/ g, pore volume is at the solid silicone of 0.7-1.0ml/g.Described Kiselgel A is that mean pore size is 2.0-10.0nm, and specific surface area is 400-800m
2/ g, pore volume is at the solid silicone of 0.35-0.70ml/g.Described spherical silica gel be pore structure between silochrom, Kiselgel A, pore volume is 0.60-0.85ml/g, mean pore size is 4.5-15.0nm, the solid silicone that specific surface area is 350-650m2/g.
In prior art, the silicon source of using in sieve synthesis procedure can be selected from one or more in soft silica, water glass, silicon sol, solid oxidation silicon, solid silicone, diatomite, white carbon black and tetraethoxy.Wherein the key distinction in solid silicone and other silicon sources is that solid silicone solid content is higher, has larger specific surface and pore volume.
Described aluminium source is selected from one or more in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum phosphate, aluminum chloride, aluminum nitrate, aluminium hydroxide, aluminum oxide and pseudo-boehmite, is preferably sodium metaaluminate and/or aluminum nitrate.
Described mineral alkali is NaOH and/or KOH.Be preferably NaOH, the M in the general formula of proportioning raw materials
2o is alkalimetal oxide.
Described template is bi-quaternary ammonium salt, is preferably two (N-crassitude) the pentane bromine salt of 1,5-.
In method provided by the invention, in step (2), in the solution making in step (1), add solid silicone, the process adding is preferably slowly added solid silicone, can react plastic after making silica gel add solution with very slow speed.In method provided by the invention, can add or not add additive, more preferably add additive, additive can with other materials common dissolve or plastic after add solid state additive, with SiO
2weight be benchmark, the add-on of additive is SiO
2the 1-20wt% of weight.
Described additive is selected from IM-5 molecular sieve crystal seed, NaBr, NaNO
3and NaClO
4in one or more, IM-5 molecular sieve crystal seed more preferably.Described crystal seed refers to the IM-5 molecular sieve after roasting.
In method provided by the invention, in step (3), the colloid of step (2) gained or solidliquid mixture are moved to and in crystallizing kettle, carry out hydrothermal crystallizing, described hydrothermal crystallizing is the usual manner of hydrothermal crystallizing in prior art, comprises static hydrothermal crystallization or Dynamic Hydrothermal crystallization.Hydrothermal crystallizing in method provided by the invention refer at the temperature of 120 ~ 200 ℃ and autogenous pressure under hydrothermal crystallizing 1 ~ 10 day, be preferably segmentation hydrothermal crystallizing, 80 ~ 140 ℃ of hydrothermal crystallizings are 0.5 ~ 2 day, 140 ~ 200 ℃ of hydrothermal crystallizings 2 ~ 6 days; More preferably 100 ~ 120 ℃ of hydrothermal crystallizings 1 ~ 2 day, 160 ~ 180 ℃ of hydrothermal crystallizings 2 ~ 4 days.After crystallization finishes, cool, gained mixed solution is obtained to IM-5 molecular screen primary powder through washing, filtration, oven dry.Wherein, the mode that washing, filtration, oven dry are various routines in this area, the present invention is not limited in this respect.Preferably at 80 ℃, dry and spend the night, obtain IM-5 molecular screen primary powder.
Described hydrothermal crystallizing also comprises the methods such as pre-depolymerization and ageing.Described pre-depolymerization method refers to that formerly not adding silicon source under template condition, aluminium source and mineral alkali first mixes pyroreaction for some time and make high poly-state silicon progressively be depolymerized to the silicon of oligomeric state; Described aging method refers in containing the solidliquid mixture of template first in low temperature crystallized for some time, and object is also to promote that depolymerization first occurs in silicon source.
The advantage of method provided by the invention is:
Method provided by the invention adopts solid silicone as silicon source, has synthesized the IM-5 molecular sieve with lamella Stacking Fault Structure.Meanwhile, method provided by the invention can shorten the IM-5 Crystallization of Zeolite time effectively, promotes molecular sieve nucleation in building-up process, is suppressed to the generation of the stray crystal phase in nuclear process, has solved and has amplified difficult problem.Method provided by the invention is widened the ratio range of raw material, improves single still yield, is easy to amplify produce.
Below by example in detail the present invention, but therefore the present invention is not restricted.
In embodiment and comparative example, the specification of all ingredients used and source are as follows:
NaOH, AlCl
3, Al (NO
3)
39H
2o is chemical pure, by Beijing Chemical Plant, is produced;
Two (N-crassitude) the pentane bromine salt brine solutions of 1,5-, solid content is 43.79wt%, by Guangzhou, has greatly Fine Chemical Works to produce;
Alkaline silica sol, SiO
2solid content 30wt%, by Beijing, flying dragon horse scientific & trading Co., Ltd. produces;
Solid silochrom, SiO
2solid content 92.5wt%, is produced by Qingdao Marine Chemical Co., Ltd.;
Solid Kiselgel A, SiO
2solid content 95.13wt%, is produced by Qingdao Marine Chemical Co., Ltd.;
Solid spherical silica gel, SiO
2solid content 90.13wt%, is produced by Qingdao Marine Chemical Co., Ltd.;
Pseudo-boehmite, solid content is 66.3wt%, by Chang Ling catalyzer branch office of limited-liability company of China Petrochemical Industry, is produced.
Comparative example 1
By two (N-crassitude) the pentane bromine salt (MPPBr) of 1,5-and NaOH, Al (NO)
39H
2(98%, Junsei), colloid is made in the combination of white carbon black (Aerosil200, Degussa) and deionized water to O, mole the consisting of of reaction mixture: SiO
2: Al
2o
3: Na
2o:R:H
2o=60:1:21.9:9:2400.After gained reactant room temperature is stirred to 24h, be transferred in 45ml teflon-lined autoclave, rotate crystallization (100r/min) after 14 days at 160 ℃, stop crystallization, product, after washing, filtering, is dried and is obtained IM-5 molecular sieve.
Synthetic, the sign of comparative example 1 explanation documents 1(IM-5 and NU-88 molecular sieve and catalysis characteristics; Synthesis, characterization, and catalytic properties of zeolites IM-5andNU-88.Journal of Catalysis 2003:215151 ~ 170) in the effect of the synthetic IM-5 molecular sieve of disclosed method.
By salt and the NaOH(50% aqueous solution of two (N-crassitude) pentanes of 1,5-, Aldrich), Al (NO
3)
39H
2(98%, Junsei), (Aerosil 200, Degussa) are mixed and made into colloid with deionized water, mole the consisting of of reaction mixture: 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 making in 45ml teflon-lined crystallizing kettle, rotates crystallization after 14 days at 160 ℃, and rotating speed is 100rpm.Stop crystallization, product obtains IM-5 molecular sieve after washing, filtration, oven dry.IM-5 sieve sample is strip, and length direction is 500-700nm, as shown in Figure 3.
Comparative example 2
(1) prepare sodium metaaluminate (NaAlO
2) solution
Take 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, cooling standby.Sodium metaaluminate (NaAlO
2) Al in solution
2o
3quality percentage composition is 8.5%, Na
2o quality percentage composition is 6.3%.
(2) 2.95g NaOH is dissolved in 25.57g deionized water, then adds the NaAlO of preparation in 4.01g step 1
2solution and 27.40g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under the condition stirring, slowly drip 40g alkaline silica sol (SiO
2quality percentage composition is 30%), make oyster white colloid, continue to stir 2h.Mole consisting of of reaction mixture: SiO
2: Al
2o
3: Na
2o:SDA:H
2o=60:1:13.5:9:1200.The colloid making is transferred in 50ml teflon-lined autoclave, rotates crystallization after 6 days at 160 ℃, stop crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and obtained IM-5 molecular sieve.Its pattern is consistent with bibliographical information, as shown in Figure 4 and Figure 5.
Embodiment 1
The effect of embodiment 1 explanation IM-5 Zeolite synthesis method provided by the invention.
By 2.6g NaAlO
2, 1.30g NaOH, 12.18g SDA be dissolved in 14.50g deionized water, mixes, and under the condition stirring, adds solid gross porosity silica gel particle 8.65g(specific surface area 358m
2/ g, pore volume 0.87ml/g, pore distribution 10.0-13.0nm), stir.Reaction mixture mole consist of SiO
2: Al
2o
3: Na
2o:SDA:H
2o=60:1:9.9:6:600.The colloid making is transferred in 50ml teflon-lined autoclave, and crystallization is 1 day at 120 ℃, and crystallization is 5 days at 160 ℃, stops crystallization, and product is after washing, filtering, and 80 ℃ of oven dry are spent the night and obtained IM-5 molecular sieve.The X-ray diffractogram (XRD) of synthetic IM-5 sample as described in Figure 2; As shown in Figure 6, IM-5 molecular sieve is lamella Stacking Fault Structure to the scanning electron microscope (SEM) photograph of synthetic IM-5 sample, lamella diameter 200-600nm.
The effect of embodiment 2 explanation IM-5 Zeolite synthesis method provided by the invention.
By 0.30AlCl
3, 2.13g NaOH, 18.26g SDA be dissolved in 13.31g deionized water, mixes, and under the condition stirring, adds Kiselgel A particle 8.41g(specific surface area 458m2/g, pore volume 0.67ml/g, pore distribution 4.5-10.0nm), stir.Reaction mixture mole consist of SiO
2: Al
2o
3: Na
2o:SDA:H
2o=60:1:12:9:600.The solidliquid mixture making is transferred in 50ml teflon-lined autoclave, and crystallization is 1 day at 120 ℃, and crystallization is 5 days at 160 ℃, stops crystallization, and product is after washing, filtering, and 80 ℃ of oven dry are spent the night and obtained IM-5 molecular sieve.Sample is lamella Stacking Fault Structure, lamella diameter 200-600nm, as shown in Figure 7.
Embodiment 3
The effect of embodiment 3 explanation IM-5 Zeolite synthesis method provided by the invention.
By 2.6g NaAlO
2, 1.70g NaOH, 24.35g SDA be dissolved in 5.03g deionized water, mix, under the condition stirring, add spherical silica gel 8.88g(spherical, specific surface area 357m2/g, pore volume 0.78ml/g, pore distribution 4.5-10.4nm) and 0.4g crystal seed as additive (the IM-5 molecular sieve of roasting).Mole consisting of of reaction mixture: SiO
2: Al
2o
3: Na
2o:SDA:Seed:H
2o=60:1:12:12:3:360.The colloid making is transferred in 50ml teflon-lined autoclave, ageing 20h, crystallization, after 4 days, stops crystallization at 160 ℃, and product is after washing, filtering, and 80 ℃ of oven dry are spent the night and are obtained IM-5 molecular sieve.Sample is lamella Stacking Fault Structure.
Embodiment 4
The effect of embodiment 4 explanation IM-5 Zeolite synthesis method provided by the invention.
By 2.00g NaAlO
2, 2.34g NaOH, be dissolved in 5.00g deionized water and mix, under the condition stirring, add spherical silica gel 8.88g.The colloid making is transferred to 120 ℃ of pre-depolymerization 20h in 50ml teflon-lined autoclave, then adds 18.26g SDA, 160 ℃ of crystallization 4 days.Mole consisting of of reaction mixture: SiO
2: Al
2o
3: Na
2o:SDA:H
2o=60:1:15:9:420.After crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and obtained IM-5 molecular sieve.Stereoscan photograph shows that the IM-5 molecular sieve making is lamella Stacking Fault Structure.
The effect of embodiment 5 explanation IM-5 Zeolite synthesis method provided by the invention.
By 8.01g NaAlO
2, 0.30g NaOH, 6.09g SDA be dissolved in 14.54g deionized water, mixes, and under the condition stirring, adds solid gross porosity silica gel particle 8.65g(specific surface area 358m
2/ g, pore volume 0.87ml/g, pore distribution 10.0-13.0nm) and 0.4g crystal seed as additive (the IM-5 molecular sieve of roasting).Mole consisting of of reaction mixture: SiO
2: Al
2o
3: Na
2o:SDA:Seed:H
2o=60:3:9:3:3:600.The colloid making is transferred to 120 ℃ of ageing 20h in 50ml teflon-lined autoclave, and crystallization, after 4 days, stops crystallization at 180 ℃, and product is after washing, filtering, and 80 ℃ of oven dry are spent the night and obtained IM-5 molecular sieve.Sample is lamella Stacking Fault Structure.
Embodiment 6
The effect of embodiment 6 explanation IM-5 Zeolite synthesis method provided by the invention.
By 52.0g NaAlO
2, 24.54g NaOH, 228.36g SDA be dissolved in 270.31g deionized water, mixes, and under the condition stirring, adds solid gross porosity silica gel particle 162.2g, stir.Reaction mixture mole consist of SiO
2: Al
2o
3: Na
2o:SDA:H
2o=60:1:9.9:6:600.The colloid making is transferred in the autoclave that 1L band stirs, and crystallization is 1 day at 120 ℃, and crystallization is 5 days at 160 ℃, stops crystallization, and product is after washing, filtering, and 80 ℃ of oven dry are spent the night and obtained IM-5 molecular sieve.Sample is lamella Stacking Fault Structure.
Comparative example 3
The performance of the catalysis alkylation of toluene methanol reaction of the IM-5 molecular sieve of comparative example 3 explanation comparative example 2 preparations.
(1) prepare H-IM-5 molecular sieve.
The ammonium nitrate solution that is 0.5mol/L by concentration respectively by the NaIM-5 molecular sieve of preparation in comparative example 2 carries out ion-exchange 3 times, each 2 hours in 80 ℃.By the molecular sieve deionized water wash of gained after exchange, then in 90 ℃ of dry 2 hours, 550 ℃ roastings 5 hours, make H-IM-5 molecular sieve.
(2) catalytic performance of H-IM-5 molecular sieve in alkylation of toluene methanol reaction.
On fixed-bed reactor, in filling 4.08g step (1), obtain) H-IM-5 molecular sieve, use N
2for carrier gas, the amount that is 2 ︰ 1 by Jia Ben ︰ methyl alcohol mol ratio passes into toluene and methyl alcohol, at 440 ℃, 0.5MPa, and charging mass space velocity 2.0h
-1, carrier gas N
2under the condition that is 10 with mixing raw material mol ratio, react, react 5 hours, 15 hours, 30 hours the results are shown in Table 1.In table 1:
Toluene conversion=[toluene quality in (in reactant in toluene Zhi Liang – resultant toluene quality)/reactant] * 100%;
Selectivity for paraxylene=(in resultant in p-Xylol quality/resultant xylol quality) * 100%;
Dimethylbenzene selective=(xylol quality in resultant/(in resultant in mass mixing dimethylbenzene quality+resultant in benzene quality+resultant the quality of ethylbenzene quality+resultant Zhong≤C9) * 100%.
Embodiment 7
The performance of embodiment 7 explanation IM-5 molecular sieve catalytic alkylation of toluene methanol reaction provided by the invention.
Adopt the method for comparative example 3, the NaIM-5 molecular sieve hydrogenation by preparation in embodiment 1, makes H-IM-5 molecular sieve.And evaluate the catalytic performance of H-IM-5 molecular sieve in alkylation of toluene methanol reaction.React 5 hours, 15 hours, 30 hours the results are shown in Table 1.
As shown in Table 1, in embodiment 1, the IM-5 molecular sieve of preparation is compared with the IM-5 molecular sieve of preparation in comparative example 2, has higher toluene conversion, and toluene conversion approximately exceeds 8 percentage points.
From accompanying drawing 1,2, method provided by the invention adopts solid silicone as silicon source, can, at low water silicon ratio, in larger crystallization device, utilize shorter crystallization time to synthesize IM-5 molecular screen primary powder.From accompanying drawing 6,7 and accompanying drawing 3,4,5 contrasts, synthetic IM-5 molecular sieve crystal pattern is lamella Stacking Fault Structure.From table 1, the catalytic performance of the IM-5 molecular sieve of lamella Stacking Fault Structure provided by the invention is better.
Table 1
Claims (11)
1. a method for synthetic IM-5 molecular sieve, is characterized in that, comprises the following steps:
(1) mineral alkali, aluminium source, template are dissolved in deionized water, mix and make mixing solutions;
(2) in the mixing solutions of step (1), add solid silicone, add or do not add additive, mix, make colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in crystallizing kettle, hydrothermal crystallizing 1 ~ 10 day, after crystallization finishes, cools, and gained mixed solution obtains IM-5 molecular screen primary powder through washing, filtration, oven dry;
Wherein, mole consisting of of described reactant: SiO
2: Al
2o
3: M
2o:SDA:H
2o=60:(0.6 ~ 6): (6 ~ 30): (0.6 ~ 24): (300 ~ 3000), wherein, M
2o is alkalimetal oxide, and SDA is template.
2. according to the method for claim 1, it is characterized in that mole the consisting of of described reactant: SiO
2: Al
2o
3: M
2o:SDA:H
2o=60:(0.75 ~ 3): (9 ~ 15): (3 ~ 12): (360 ~ 600), wherein, M
2o is alkalimetal oxide, and SDA is template.
3. according to the method for claim 1 or 2, it is characterized in that, in step (1), mineral alkali, aluminium source, template are dissolved in deionized water, mix and make mixing solutions, standing more than 30 minutes.
4. according to the method for claim 1 or 2, it is characterized in that, described solid silicone is one or more in silochrom, Kiselgel A or spherical silica gel.
5. according to the method for claim 4, it is characterized in that, described solid silicone is silochrom.
6. according to the method for claim 1 or 2, it is characterized in that, described aluminium source is one or more in sodium metaaluminate, Tai-Ace S 150, aluminum chloride and aluminum nitrate.
7. according to the method for claim 1 or 2, described mineral alkali is NaOH and/or KOH.
8. according to the method for claim 1 or 2, it is characterized in that, described template is bi-quaternary ammonium salt.
9. according to the method for claim 1 or 2, it is characterized in that described additive is selected from crystal seed, NaBr, the NaNO of IM-5 molecular sieve
3and NaClO
4in one or more.
10. according to the method for claim 9, it is characterized in that described additive is the crystal seed of IM-5 molecular sieve.
11. according to the method for claim 1, it is characterized in that, described hydrothermal crystallizing condition is hydrothermal crystallizing 0.5 ~ 2 day at 80 ~ 140 ℃, and at 140 ~ 200 ℃, hydrothermal crystallizing is 2 ~ 6 days.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574032A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The synthetic method of IM-5 molecular sieve |
| CN109593020A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | A kind of method of alkylated reaction |
| CN109592697A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | IM-5 molecular sieve and its synthetic method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234012A (en) * | 1996-10-21 | 1999-11-03 | 法国石油公司 | IM-5 zeolite, method of prpen. and catalytic application thereof |
| CN101573182A (en) * | 2006-12-27 | 2009-11-04 | 雪佛龙美国公司 | Preparation of small pore molecular sieves |
| CN102040230A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of europium oxide (EUO) type molecular sieve |
| CN102452666A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for synthesizing IM-5 molecular sieve |
| CN102464326A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon mordenite |
-
2012
- 2012-09-28 CN CN201210367111.7A patent/CN103693654B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234012A (en) * | 1996-10-21 | 1999-11-03 | 法国石油公司 | IM-5 zeolite, method of prpen. and catalytic application thereof |
| CN101573182A (en) * | 2006-12-27 | 2009-11-04 | 雪佛龙美国公司 | Preparation of small pore molecular sieves |
| CN102040230A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of europium oxide (EUO) type molecular sieve |
| CN102452666A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for synthesizing IM-5 molecular sieve |
| CN102464326A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon mordenite |
Non-Patent Citations (4)
| Title |
|---|
| MINWEI SUN ET AL.: ""A Dynamic Organic Structuring-Directing Agent for Pure-Silica-Zeolite AST and LTA Syntheses"", 《催化学报》 * |
| 冯会 等: ""硅胶原位合成ZSM-5分子筛及其催化性能的研究"", 《燃料化学学报》 * |
| 李天文 等: ""模板剂在分子筛合成中的作用"", 《化工中间体》 * |
| 王殿中 等: ""硅源对合成高硅ZSM-5分子筛的影响"", 《石油炼制与化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574032A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The synthetic method of IM-5 molecular sieve |
| CN109593020A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | A kind of method of alkylated reaction |
| CN109592697A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | IM-5 molecular sieve and its synthetic method |
| CN109593020B (en) * | 2017-09-30 | 2022-04-08 | 中国石油化工股份有限公司 | Alkylation reaction method |
| CN109592697B (en) * | 2017-09-30 | 2022-07-12 | 中国石油化工股份有限公司 | IM-5 molecular sieve and synthetic method thereof |
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