CN106946271A - A kind of X-type molecular sieve and its synthetic method - Google Patents
A kind of X-type molecular sieve and its synthetic method Download PDFInfo
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- CN106946271A CN106946271A CN201610003079.2A CN201610003079A CN106946271A CN 106946271 A CN106946271 A CN 106946271A CN 201610003079 A CN201610003079 A CN 201610003079A CN 106946271 A CN106946271 A CN 106946271A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/22—Type X
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a kind of X-type molecular sieve and its synthetic method, the crystal structure of the X-type molecular sieve is FAU structures.The X-type molecular sieve synthetic method is first to prepare aluminum oxide, then mixes inorganic base, silicon source, silicon source and water, stirs into silica-alumina gel and crystallization certain time, is subsequently added into water and aluminum oxide stirs, then evaporate quantitative water；X-type molecular sieve is obtained after last hydrothermal crystallizing.The X-type molecular sieve of the inventive method synthesis is 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 X-type molecular sieve and its synthetic method, specifically a kind of low silica-alumina ratio X-type molecular sieve and its synthetic method belong 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.
Such as 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.
" base source step-feeding method synthesizing low silicon X-type zeolite molecular sieve "（Silicate journal, the second phases of volume 36 in 2008）Disclose a kind of synthetic method of low silicon X molecular sieve.This method is characterized in that alkali source is divided into many parts, and the control of alkali source feeds intake.By optimizing the basicity environment of core and nucleus growth process, the concentration of each stage polysilicon acid radical ion is adjusted, the stray crystal for reducing nucleation process carrys out synthesizing low silicon X molecular sieve.
Also certain methods synthesize other type zeolites with low silicon features, and 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.
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.
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.
A kind of CN104556102A, preparation method of low silica-alumina ratio molecular sieve, discloses a kind of method of zeolite.But the patent can not synthesize proper low silicon or rich aluminium zeolite.It is, as crystal seed, to add other raw materials, synthesize zeolite product by hydrothermal crystallizing with the zeolite of high silica alumina ratio.The silica alumina ratio of the zeolite is only to be less than original crystal seed silica alumina ratio, is not proper low silicon or rich aluminium zeolite.
Because there are low silicone zeolite molecular sieve some silica-rich zeolites not have the physico-chemical property of uniqueness, there is more preferably application effect in some fields.Although prior art discloses the synthetic method of several low silica-alumina ratio zeolites, it is due to that zeolite molecular sieve is a kind of metastable crystal, its physico-chemical property is restricted by synthetic method, is by thermodynamic (al) limitation in principle.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.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of X-type molecular sieve and its synthetic method.The synthesis material of the inventive method is general inorganic material, and without poisonous and harmful substance, whole preparation process environmental protection, operating procedure is simple and easy to apply.
The present invention provides a kind of X-type molecular sieve, and the crystal structure of affiliated molecular sieve is FAU structures, without other impurity crystal, and the silica alumina ratio of the molecular sieve is 2~2.5, preferably 2~2.4, and crystal size is 500~1500nm.
The present invention also provides a kind of synthetic method of X-type molecular sieve recited above, comprises the following steps：
（1）Aluminum nitrate is calcined 1~5h at 450~700 DEG C, aluminum oxide is obtained；
（2）According to 1~12Na2O：1~10SiO2：A12O3：80~700H2Inorganic base, silicon source, silicon source and water are stirred synthesizing Si-Al gel, are then charged into reactor in 2~7h of crystallization at 70~130 DEG C by O mol ratio；
（3）By step（1）Obtained aluminum oxide and step（2）Obtained reactant mixing, then add water it is well mixed after quantitative water is evaporated at 80~150 DEG C, be reloaded into reactor 10~40h of crystallization at 70~130 DEG C, last separating, washing and be dried to obtain X-type molecular sieve.
In the synthetic method of X-type molecular sieve 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 X-type molecular sieve of the present invention, step（2）Described in inorganic base be one or more in NaOH, KOH, LiOH；Silicon source is the one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is the one or more in White Carbon black, silica gel, Ludox or waterglass.
In the synthetic method of X-type molecular sieve of the present invention, step（2）Described in inorganic base, silicon source, silicon source, the mol ratio of water be preferably 2~11Na2O：1.5~9.5SiO2：A12O3：90~650H2O。
In the synthetic method of X-type molecular sieve of the present invention, step（2）Described in crystallization be preferably at 80~140 DEG C 3~6h of crystallization.
In the synthetic method of X-type molecular sieve of the present invention, step（3）Described in aluminum oxide and step（2）Described in silicon source mol ratio be 3~0.5SiO2:A12O3, preferably 2.5~1SiO2:A12O3。
In the synthetic method of X-type molecular sieve 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 X-type molecular sieve of the present invention, step（3）Described in need to evaporate quantitative water, the volume and step of the water evaporated（3）The volume of the water of middle addition is identical.
In the synthetic method of X-type molecular sieve of the present invention, step（3）Described in crystallization be at 80~140 DEG C 12~35h of crystallization.
In the synthetic method of X-type molecular sieve of the present invention, step（3）Described in separation and washing be routine operation well known to those skilled in the art, as separate can take filtering method, washing generally refer 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 low-silicon X-shaped molecular screen ion-exchange capacity and absorption property that the present invention is provided are high, can apply in multiple fields such as washing assisant, environmental improvement, chemical separating, petrochemical industries, especially apply in terms of PSA making oxygen by air separation gas separation.
Compared with prior art, the X-type molecular sieve and synthetic method that the present invention is provided have advantages below：
（1）The characteristics of X-type molecular sieve that the present invention is synthesized has high-crystallinity and low silica-alumina ratio；And low silica-alumina ratio X-type molecular sieve zeolite can be synthesized in the range of ultralow silica alumina ratio.The zeolite has higher sour density, has broader purposes with adsorbing domain in some catalytic reactions.
（2）Because the silica alumina ratio of low-silicon X-shaped molecular screen is low, interior energy is higher, thus crystal stability is poor, and synthesis can be caused difficult, impurity crystal easily occur.In the synthetic method of X-type molecular sieve 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 during X-type molecular sieve crystallization, i.e., relative to step（3）Described in common silicon source can delay participate in zeolite crystallization, X-type molecular sieve crystallization is divided into two stages, first stage：Step（3）Described in common silicon source first reacted with other raw materials, generate X-type molecular sieve nucleus；Second stage：Treat step（3）Described in common silicon source completely consumption after, step（1）Special aluminum oxide then participates in reaction, aluminium species can slowly be discharged, it can so ensure that the silica alumina ratio of whole reaction system maintains a higher level all the time, be conducive to the growth of X-type molecular sieve, and the generation of impurity crystal can be suppressed, and then the low silica-alumina ratio X-type molecular sieve of high-purity can be synthesized.
Brief description of the drawings
Fig. 1 is the XRD spectra for the X-type molecular sieve that embodiment 1 is obtained.
Embodiment
The synthetic method of X-type molecular sieve of the present invention is described in detail below by specific embodiment, but is not limited to embodiment.
Embodiment 1
30g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 500 DEG C, obtains aluminum oxide.Then 4g NaOH, 3.7 g sodium aluminates is taken to be placed in 50 mL distilled water, stirring is until all dissolvings.3.5 g white carbons, stirring 30 are slowly added again
min.It is fitted into 90 DEG C of crystallization 3h in reactor.50mL distilled water and aluminum oxide are added, 30min is stirred；Then 50mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 90 DEG C of crystallization 15h 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 X-type molecular sieve, without other impurity.
Embodiment 2
32g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 550 DEG C, obtains aluminum oxide.Then 4.5g NaOH, 3 g sodium aluminates is taken to be placed in 50 mL distilled water, stirring is until all dissolvings.3.5 g white carbons, stirring 30 are slowly added again
min.It is fitted into 95 DEG C of crystallization 3h in reactor.60mL distilled water and aluminum oxide are added, 30min is stirred；Then 60mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 90 DEG C of crystallization 15h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample is X-type molecular sieve, and numbering is CL2.
Embodiment 3
25g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 450 DEG C, obtains aluminum oxide.Then 4.7g NaOH, 3 g sodium aluminates is taken to be placed in 50 mL distilled water, stirring is until all dissolvings.4 g silica gel are slowly added again black, stirring 30
min.It is fitted into 100 DEG C of crystallization 3h in reactor.50mL distilled water and aluminum oxide are added, 30min is stirred；Then 50mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 100 DEG C of crystallization 20h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample is X-type molecular sieve, and numbering is CL3
Embodiment 4
38g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 550 DEG C, obtains aluminum oxide.Then 5g NaOH, 3 g sodium aluminates is taken to be placed in 40 mL distilled water, stirring is until all dissolvings.4.7 g white carbons, stirring 30 are slowly added again
min.It is fitted into 9 DEG C of crystallization 3.5h in reactor.55mL distilled water and aluminum oxide are added, 30min is stirred；Then 55mL distilled water is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 90 DEG C of crystallization 13h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h then is dried at 120 DEG C, gained sample is X-type molecular sieve, and numbering is CL4
Comparative example 1
4g NaOH, 3.7 g sodium aluminates, 30g aluminum nitrates is taken to be placed in 50 mL distilled water, stirring is until all dissolvings.3.5 g white carbons, stirring 30 are slowly added again
min.It is fitted into 90 DEG C of crystallization 18h in reactor.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL5 then are dried at 120 DEG C, gained sample is P type zeolite, it is impossible to synthesize X-type molecular sieve.
Comparative example 2
16g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 500 DEG C, obtains aluminum oxide；Then 4g NaOH, 3.7 g sodium aluminates are taken, are placed in 50mL distilled water, stirring is until all dissolvings, then add 3.5 g white carbons, are fitted into 90 DEG C of crystallization 3h in reactor.Aluminum oxide is added, 30min is stirred；It is then charged into closed reactor, 90 DEG C of crystallization 15h 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 X-type molecular sieve, but crystallinity is relatively low.
Comparative example 3
30g aluminum nitrates are placed in high temperature furnace first, 3h is calcined at 900 DEG C, obtains aluminum oxide；Then 4g NaOH, 3.7 g sodium aluminates is taken to be placed in 50 mL distilled water, stirring is mixed with aluminum oxide after stirring, is fitted into after stirring in closed reactor up to all dissolvings, then add 3.5g white carbons, 90 DEG C of crystallization 18h in baking oven.By resulting product with distillation water washing 4 times to neutral, 12h, gained sample number into spectrum CL6 then are dried at 120 DEG C, gained sample is crystalline alumina, it is impossible to synthesize X-type molecular sieve.
Table 1 is embodiment and the crystalline phase property of comparative example products therefrom
Note：The relative crystallinity that table 1 is given is using CL1 crystallinity as reference.
Claims (11)
1. a kind of X-type molecular sieve, the crystal structure of affiliated molecular sieve is FAU structures, without other impurity crystal, and the silica alumina ratio of the molecular sieve is 2~2.5, preferably 2~2.4, and crystal size is 500~1500nm.
2. the synthetic method of X-type molecular sieve 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）According to 1~12Na2O：1~10SiO2：A12O3：80~700H2Inorganic base, silicon source, silicon source and water are stirred synthesizing Si-Al gel, are then charged into reactor in 2~7h of crystallization at 70~130 DEG C by O mol ratio；
（3）By step（1）Obtained aluminum oxide and step（2）Obtained reactant mixing, then add water it is well mixed after quantitative water is evaporated at 80~150 DEG C, be reloaded into reactor 10~40h of crystallization at 70~130 DEG C, last separating, washing and be dried to obtain X-type molecular sieve.
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；Silicon source is the one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is the one or more in White Carbon black, silica gel, Ludox or waterglass.
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 be 2~11Na2O：1.5~9.5SiO2：A12O3：90~650H2O。
6. in accordance with the method for claim 2, it is characterised in that：Step（2）Described in crystallization 3~6h of crystallization at 80~140 DEG C.
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 3~0.5SiO2:A12O3, preferably 2.5~1SiO2:A12O3。
8. 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.
9. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in need to evaporate quantitative water, the volume and step of the water evaporated（3）The volume of the water of middle addition is identical.
10. in accordance with the method for claim 2, it is characterised in that：, step（3）Described in crystallization be at 80~140 DEG C 12~35h of crystallization.
11. in accordance with the method for claim 2, it is characterised in that：Step（3）Described in drying be under the conditions of 100~140 DEG C dry 5~15h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177280A (en) * | 2007-11-06 | 2008-05-14 | 广东工业大学 | Method for quickly synthesizing nano X-type molecular sieve by low-temperature ultrasonic crystallization process |
| CN104174356A (en) * | 2014-08-20 | 2014-12-03 | 洛阳市建龙化工有限公司 | Preparation method of potassium-free low-aluminum-silicon-ratio X-type molecular sieve adsorbent |
| CN104477937A (en) * | 2014-12-05 | 2015-04-01 | 上海绿强新材料有限公司 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177280A (en) * | 2007-11-06 | 2008-05-14 | 广东工业大学 | Method for quickly synthesizing nano X-type molecular sieve by low-temperature ultrasonic crystallization process |
| CN104174356A (en) * | 2014-08-20 | 2014-12-03 | 洛阳市建龙化工有限公司 | Preparation method of potassium-free low-aluminum-silicon-ratio X-type molecular sieve adsorbent |
| CN104477937A (en) * | 2014-12-05 | 2015-04-01 | 上海绿强新材料有限公司 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
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