CN106946267A - A kind of EU-1 molecular sieves and its synthetic method - Google Patents
A kind of EU-1 molecular sieves and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of EU-1 molecular sieves and its synthetic method, the crystal structure of the EU-1 molecular sieves is typical EUO structures.The EU-1 Zeolite synthesis method is to mix inorganic base, silicon source, silicon source, template and water, stirs into silica-alumina gel and crystallization certain time；It is subsequently added into water, the second template and aluminum oxide to stir, EU-1 molecular sieves is then obtained after hydrothermal crystallizing.The EU-1 composite molecular screens of the inventive method synthesis are low silica-alumina ratio zeolite, and crystallinity is high, not only effectively prevent the generation of stray crystal but also operation is simple.
Description
Technical field
The present invention relates to a kind of EU-1 molecular sieves and its synthetic method, specifically a kind of synthetic method of low silica-alumina ratio EU-1 molecular sieves belongs to molecular sieve catalytic material synthesis field.
Background technology
Zeolite molecular sieve is the important industrial catalyst of a class and catalyst carrier, is most crucial unit in catalytic reaction process.Zeolite molecular sieve is a kind of metastable crystal in crystallography, and its physicochemical properties such as silica alumina ratio, crystalline size and pattern can change because of the difference of synthetic method.And these physico-chemical properties influence and adjust the catalytic activity of zeolite.Therefore the demand of different catalytic reactions could can be met by synthesizing the zeolite of different physico-chemical properties.
A kind of synthetic method often defines raw material type, raw material proportioning scope, the synthesis condition such as crystallization temperature, time.So the excursion of the physico-chemical parameter such as the crystal morphology of zeolite product, size, silica alumina ratio is just limited by synthetic method, it is impossible to unrestricted arbitrarily change.Therefore, the zeolite product of the special natures such as low silica-alumina ratio, high silica alumina ratio, big crystal grain or little crystal grain that has that wanting to synthesize conventional method can not synthesize is accomplished by developing special synthesizing mean.
A kind of such as CN101096275A, synthetic method of rich aluminium Beta zeolites, discloses a kind of synthetic method of Beta zeolites.Its synthesis step is：1. impregnating silicon source with the aqueous solution containing silicon source or acid solution, stirring, with or without aging dehydration after AMMONIA TREATMENT, after grinding, is calcined at 600~1400 DEG C to solidifying, obtains silicon and aluminum source；2. again mixing tetraethylammonium cation compound and hydrofluoric acid, in normal pressure and under not higher than 130 DEG C or vacuum condition, part moisture is evaporated；3. in tetraethyl ammonium hydroxide and hydrofluoric acid mixed solution that silicon and aluminum source is added to concentration, then obtained reactant mixture is subjected to hydrothermal crystallizing and crystallization product is reclaimed.Although the patent can synthesize the Beta zeolites of low silica-alumina ratio, its building-up process is comparatively laborious, and additionally to use to the disagreeableness fluorine ion of environment, not only increases cost, and pollution environment.
A kind of CN101096274A, preparation method of rich aluminium Beta zeolites, discloses a kind of synthetic method of Beta zeolites.Its synthesis step is：1. silicon source and silicon source are prepared into silica-alumina cogels in the presence of hydrolytic reagent, crushed after aging and roasting as silicon and aluminum source；2. and then silicon and aluminum source is added in the solution being made up of tetraethylammonium cation, ammonium ion, fluorine ion and water, crystallization simultaneously reclaims crystallization product and obtains zeolite.Although the patent can synthesize the Beta zeolites of low silica-alumina ratio, additionally to use to the disagreeableness fluorine ion of environment, not only increase cost, and pollution environment.
CN1086791A, directing agent method synthesis Beta zeolites, discloses a kind of synthetic method of Beta zeolites, the Beta zeolites of synthesis fall within low silica-alumina ratio zeolite.Being mainly characterized by of the patent synthesizes Beta zeolites using directed agents.Its directed agents is to be dissolved in aluminium salt in tetraethyl ammonium hydroxide template and sodium hydrate aqueous solution, adds active silica to prepare directed agents, and its directed agents formula range is： SiO2/Al2O3=20~120, TEAOH/SiO2=0.2~0.5, Na2O/SiO2=0.40~0.10, H2O/SiO2=7.5~25, the preparation temperature of directed agents is 15~70 DEG C, and Aging Temperature is 50~150 DEG C, during synthetic zeolite, and added directed agents are 0.5%~10% with the volume ratio of synthesis material mixture.
CN101723394A, a kind of nano-beta molecular sieve with low Si/Al ratio and preparation method thereof, disclose a kind of synthetic method of low silicon Beta zeolites.The patent is mainly characterized by using FAU molecular sieves as silicon source, and basicity and reduction Na ion concentration are adjusted with ammoniacal liquor.But the primary raw material silicon source used by the patent is FAU molecular sieves, FAU molecular sieves are also to need what hydrothermal crystallizing was synthesized, and compared to silicon sources such as conventional sodium aluminate, aluminum sulfate, cost is prohibitively expensive.
Also certain methods synthesize other type zeolites with low silicon features, and such as CN103601213A, low silicon-aluminum ratio nanosheet flower cluster-like mordenite molecular sieve preparation method discloses a kind of method of zeolite.Its preparation process includes：By silicon source, alkali source dissolving in deionized water, to obtaining adding Ludox in settled solution, obtained flat-white colloid, which is transferred in reactor, carries out hydro-thermal reaction, obtains low silica-alumina ratio mordenite molecular sieve.
CN102417190A, a kind of method that application activation silicon source prepares low silicon NaX zeolites, discloses a kind of method of low-silica X zeolite.The preparation that is mainly characterized by of the patent activates silicon source, the activation silicon source is that a certain amount of alkaline silicon source solution is added into common silicon source, it is oligomeric state silicate to make in common silicon source high poly- state silicate depolymerization, and is combined with aluminate and generate effective sial acid group presoma and faujasite microcrystals.
The content of the invention
There are existing low silicone zeolite molecular sieve some silica-rich zeolites not have the physico-chemical property of uniqueness, therefore have more preferable application effect in some specific areas.It is by thermodynamic (al) limitation in principle but because zeolite molecular sieve is a kind of metastable crystal, its physico-chemical property is restricted by synthetic method.When silica alumina ratio is too low, zeolite crystal processing energy level unstable state, therefore it is very difficult to synthesis.Low silicone zeolite is not also overripened relative to the synthetic technology of silica-rich zeolite, therefore the synthetic method of the new low silicone zeolite of exploitation just has important practical significance.
In view of the shortcomings of the prior art, the present invention provides a kind of EU-1 molecular sieves and its synthetic method, and the EU-1 molecular sieves of this method synthesis have the feature of low silica-alumina ratio, and whole preparation process is simple and easy to apply, is adapted to industrialized production.
The present invention provides a kind of EU-1 molecular sieves, and the crystal structure of the EU-1 molecular sieves is typical EUO structures, without other impurity crystal, the EU-1 molecular sieves alumina silicon al mole ratio is 11~20, it is preferred that 12~18, crystal size is less than 200nm, the m of specific surface area 300 ~ 7002/g。
The present invention also provides a kind of synthetic method of EU-1 molecular sieves recited above, comprises the following steps：
（1）Aluminum nitrate is calcined 1~5h at 450~700 DEG C, aluminum oxide is obtained；
（2）By inorganic base, silicon source, silicon source, water and template（M）According to 0.5~8Na of mol ratio2O：25~80SiO2:
A12O3：400~1800H2O：1~10（M）Ratio mixing, be fitted into after stirring in reactor in 2~20h of crystallization at 150~230 DEG C；
（3）By step（1）Obtained aluminum oxide and step（2）Obtained reactant mixing, then the second template and water are added, a certain amount of water is evaporated after being uniformly mixed at 80~150 DEG C, 30~180h of crystallization at 150~230 DEG C is reloaded into reactor, last separating, washing and EU-1 molecular sieves are dried to obtain.
In the synthetic method of EU-1 molecular sieves of the present invention, step（1）Described in sintering temperature be preferably 500~600 DEG C, roasting time is preferably 1.5~4h.
In the synthetic method of EU-1 molecular sieves of the present invention, step（2）Described in inorganic base can be one or more in NaOH, KOH, LiOH；Source of aluminium is the one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；The silicon source is the one or more in White Carbon black, silica gel, Ludox or waterglass；Template（M）For C6 [(HM) OBr2]。
In the synthetic method of EU-1 molecular sieves of the present invention, step（2）Described in inorganic base, silicon source, silicon source, the mol ratio of water and template be preferably 1~7Na2O：30~70SiO2:
A12O3：500~1300H2O：2~8（M）.
In the synthetic method of EU-1 molecular sieves of the present invention, step（2）Described in crystallization be at 150~230 DEG C 5~12h of crystallization.
In the synthetic method of EU-1 molecular sieves of the present invention, step（3）Described in aluminum oxide and step（2）Described in silicon source mol ratio be 15~1SiO2:A12O3, preferably 10~2SiO2:A12O3。
In the synthetic method of EU-1 molecular sieves of the present invention, step（3）Described in the second template be tetraethylammonium bromide, the second template and step（2）The mol ratio of middle template is 0.5~2, preferably 0.8~1.5.
In the synthetic method of EU-1 molecular sieves of the present invention, step（3）Described in addition water volume and step（2）Described in water volume ratio be 0.5~1.5, preferably 0.8~1.2.
In the synthetic method of EU-1 molecular sieves of the present invention, step（3）Described in need to evaporate a certain amount of water, evaporate after a certain amount of water, inorganic base, silicon source, silicon source, the mol ratio of water and template should be maintained at 0.5~8Na2O：25~80SiO2: A12O3：40~200H2O：1~10 [(HM) OBr2], preferably 1~7Na2O：30~70SiO2:
A12O3：60~150H2O：2~8 [(HM) OBr2]。
In the synthetic method of EU-1 molecular sieves of the present invention, step（3）Described in evaporating temperature be 80~140 DEG C.
In the synthetic method of EU-1 molecular sieves of the present invention, step（3）Described in crystallization be preferably at 180~220 DEG C 48~144h of crystallization.
In the synthetic method of EU-1 molecular sieves of the present invention, described separation and washing is routine operation well known to those skilled in the art, and as separated the method that can take filtering, washing generally refers to be washed with deionized.Generally include separating for several times and washing operation, generally 1~6 time.Drying condition is usually that 5~15h is dried under the conditions of 100~140 DEG C.
The EU-1 molecular sieves that the present invention is provided may be used as gas, liquid mixture separation adsorbent, can also as catalyst carrier or acidic catalyst component, can be widely applied to petrochemical industry.
Compared with prior art, the EU-1 molecular sieves and synthetic method that the present invention is provided have advantages below：
（1）The characteristics of EU-1 molecular sieves that the present invention is synthesized have high-crystallinity and low silica-alumina ratio, and low silica-alumina ratio EU-1 molecular sieves can be synthesized in the range of ultralow silica alumina ratio.The molecular sieve has higher sour density, has higher catalytic reaction efficiency in some catalytic reactions.
（2）The general sial element required in synthetic system of the synthesis of EU-1 molecular sieves is in high silica alumina ratio state, otherwise can not synthesize EU-1 molecular sieves.In the synthetic method of EU-1 molecular sieves of the present invention, aluminum nitrate roasting is allowed to be decomposed into a kind of inert aluminum oxide, this special inert alumina can show strong inertia in EU-1 Crystallization of Zeolite courses of reaction, i.e., relative to step（2）Described in common silicon source can delay participation crystallization, crystallization is divided into two stages, first stage：Step（2）Described in common silicon source first reacted with other raw materials, generate EU-1 molecular sieve nucleus；Second stage：Treat step（2）And step（3）Described in common silicon source run out of it is complete after, special aluminum oxide can just participate in reaction, and be slowly to discharge aluminium species, can so ensure that the sial element that can be utilized during whole crystallization maintains a high silica alumina ratio level all the time.So be conducive to the growth of EU-1 molecular sieves, and the generation of impurity crystal can be suppressed, it is possible to synthesize the low silica-alumina ratio EU-1 molecular sieves of high-purity in the case of low silica-alumina ratio raw material proportioning.
（3）The step of the inventive method（3）It is middle that appropriate water is added into reaction system, step can be substantially reduced（2）The viscosity of half obtained crystallization product, plays diluting effect, greatly improves decentralization of the inert alumina in half crystallization product, prevents due to the stock dispersion uneven caused reduction of product crystallinity and the generation of stray crystal.
（4）Step in the inventive method（2）Described in template be relatively expensive template, with higher structure-directing effect, in step（2）Described in crystallization process in easily formed molecular sieve nucleus.Step（3）Described in the second template be relatively inexpensive template, it may have structure-directing effect, in step（3）Described in crystallization process in can promote the synthesis of molecular sieve, substitute expensive template, reduction synthesis cost.
Brief description of the drawings
Fig. 1 is the XRD spectra for the EU-1 molecular sieves that embodiment 1 is obtained.
Embodiment
The synthetic method of EU-1 molecular sieves of the present invention is described in detail below by specific embodiment, but is not limited to embodiment.
Embodiment 1
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 500 DEG C, obtains aluminum oxide.Then 1.11g NaOH, 0.82g sodium aluminates, 6g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 8.3g white carbons, are fitted into 190 DEG C of crystallization 7h in reactor.50mL distilled water, 4g tetraethylammonium bromides and aluminum oxide are added, 30min is stirred；Then 90mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 190 DEG C of crystallization 72h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample number into spectrum CL1, gained sample are as shown in figure 1, be pure EU-1 molecular sieves, without other impurity.
Embodiment 2
10g aluminum nitrates are placed in high temperature furnace first, 2h is calcined at 550 DEG C, obtains aluminum oxide.Then 1.11g NaOH, 0.5g sodium aluminates, 5g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 8.3g silica gel, are fitted into 190 DEG C of crystallization 6h in reactor.50mL distilled water, 3g tetraethylammonium bromides and aluminum oxide are added, 30min is stirred；Then 85mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 190 DEG C of crystallization 65h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL2 then are dried at 120 DEG C, is EU-1 molecular sieves.
Embodiment 3
12g aluminum nitrates are placed in high temperature furnace first, 2.5h is calcined at 700 DEG C, obtains aluminum oxide.Then 0.8g NaOH, 0.25g aluminum nitrates, 6g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 8.3g white carbons, are fitted into 200 DEG C of crystallization 7h in reactor.60mL distilled water, 4g tetraethylammonium bromides and aluminum oxide are added, 30min is stirred；Then 80mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 200 DEG C of crystallization 80h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample number into spectrum is CL3, is EU-1 molecular sieves.
Embodiment 4
17g aluminum nitrates are placed in high temperature furnace first, 2h is calcined at 580 DEG C, obtains aluminum oxide.Then 0.3g NaOH, 0.3 aluminum sulfate, 5.5g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 7.5g white carbons, are fitted into 210 DEG C of crystallization 5h in reactor.35mL distilled water, 3g tetraethylammonium bromides and aluminum oxide are added, 30min is stirred；Then 75mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 210 DEG C of crystallization 50h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample number into spectrum is CL4, is EU-1 molecular sieves.
Comparative example 1
1.11g NaOH, 0.82g sodium aluminates, 16g aluminum nitrates, 6g C6s and 4g tetraethylammonium bromides is taken to be placed in 50mL distilled water, stirring is until all dissolvings, 8.3g white carbons are added again, are fitted into after stirring in closed reactor, 190 DEG C of crystallization 79h in baking oven.By resulting product with water washing is distilled 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum CL5, gained sample is P type zeolite, it is impossible to synthesize EU-1 molecular sieves.
Comparative example 2
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 500 DEG C, obtains aluminum oxide；Then 1.11g NaOH, 0.82g sodium aluminates, 6g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 8.3g white carbons, are fitted into 190 DEG C of crystallization 7h in reactor.4g tetraethylammonium bromides and aluminum oxide are added, 30min is stirred；It is then charged into closed reactor, 190 DEG C of crystallization 72h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample number into spectrum CL6, is EU-I molecular sieves, but crystallinity is relatively low.
Comparative example 3
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 900 DEG C, obtains aluminum oxide；Then 1.11g NaOH, 0.82g sodium aluminates, 6g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 8.3g white carbons, are fitted into 190 DEG C of crystallization 7h in reactor.50mL distilled water, 4g tetraethylammonium bromides and aluminum oxide are added, 30min is stirred；Then 90mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 190 DEG C of crystallization 72h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample number into spectrum is CL7, and gained sample is crystalline alumina, it is impossible to synthesize EU-I molecular sieves.
Comparative example 4
1.11g NaOH, 0.82g sodium aluminates, 6g C6s is taken to be placed in 50mL distilled water, stirring is until all dissolvings, then add 8.3g white carbons, are fitted into 190 DEG C of crystallization 7h in reactor.50mL distilled water, 4g tetraethylammonium bromides and 16g aluminum nitrates are added, 30min is stirred；Then 90mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 190 DEG C of crystallization 72h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL8 then are dried at 120 DEG C, gained sample is P type zeolite, it is impossible to synthesize EU-1 molecular sieves.
Table 1 is embodiment and the property of comparative example products therefrom
Note：The relative crystallinity that table 1 is given is using CL1 crystallinity as reference.
Claims (13)
1. a kind of EU-1 molecular sieves, the crystal structure of the EU-1 molecular sieves is typical EUO structures, without other impurity crystal, and the EU-1 molecular sieves alumina silicon al mole ratio is 11~20, preferably 12~18, and crystal size is less than 200nm, the m of specific surface area 300 ~ 7002/g。
2. the synthetic method of EU-1 molecular sieves as claimed in claim 1, comprises the following steps：
（1）Aluminum nitrate is calcined 1~5h at 450~700 DEG C, aluminum oxide is obtained；
（2）By inorganic base, silicon source, silicon source, water and template（M）According to 0.5~8Na of mol ratio2O：25~80SiO2: A12O3：400~1800H2O：1~10（M）Ratio mixing, be fitted into after stirring in reactor in 2~20h of crystallization at 150~230 DEG C；
（3）By step（1）Obtained aluminum oxide and step（2）Obtained reactant mixing, then the second template and water are added, a certain amount of water is evaporated after being uniformly mixed at 80~150 DEG C, 30~180h of crystallization at 150~230 DEG C is reloaded into reactor, last separating, washing and EU-1 molecular sieves are dried to obtain.
3. in accordance with the method for claim 2, it is characterised in that：Step（1）Described in sintering temperature be 500~600 DEG C, roasting time be 1.5~4h.
4. in accordance with the method for claim 2, it is characterised in that：Step（2）Described in inorganic base be one or more in NaOH, KOH, LiOH；Source of aluminium is the one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；The silicon source is the one or more in White Carbon black, silica gel, Ludox or waterglass；Template（M）For C6 [(HM) OBr2]。
5. in accordance with the method for claim 2, it is characterised in that：Step（2）Described in inorganic base, silicon source, silicon source, the mol ratio of water and template be 1~7Na2O：30~70SiO2: A12O3：500~1300H2O：2~8（M）.
6. in accordance with the method for claim 2, it is characterised in that：Step（2）Described in crystallization be at 150~230 DEG C 5~12h of crystallization.
7. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in aluminum oxide and step（2）Described in silicon source mol ratio be 15~1SiO2:A12O3, preferably 10~2SiO2:A12O3。
8. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in the second template be tetraethylammonium bromide.
9. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in the second template and step（2）The mol ratio of middle template is 0.5~2, preferably 0.8~1.5.
10. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in addition water volume and step（2）Described in water volume ratio be 0.5~1.5, preferably 0.8~1.2.
11. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in need to evaporate a certain amount of water, evaporate after a certain amount of water, inorganic base, silicon source, silicon source, the mol ratio of water and template are 0.5~8Na2O：25~80SiO2:
A12O3：40~200H2O：1~10 [(HM) OBr2], preferably 1~7Na2O：30~70SiO2:
A12O3：60~150H2O：2~8 [(HM) OBr2]。
12. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in evaporating temperature be 80~140 DEG C.
13. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in crystallization be at 180~220 DEG C 48~144h of crystallization
。
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Cited By (3)
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| CN109516471A (en) * | 2018-12-24 | 2019-03-26 | 大连理工大学 | A kind of synthetic method of surface richness aluminium profiles ZSM-23 molecular screen |
| CN109704356A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The synthetic method of EU-1 zeolite molecular sieve |
| CN111170333A (en) * | 2018-11-13 | 2020-05-19 | 中国科学院大连化学物理研究所 | Synthesis method of large-grain EU-1 molecular sieve |
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| CN109516471B (en) * | 2018-12-24 | 2021-11-05 | 大连理工大学 | Synthesis method of ZSM-23 molecular sieve with aluminum-rich surface |
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| CN106946267B (en) | 2019-03-19 |
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