CN107512728A - The preparation method of card plugging structure multi-stage porous FAU type zeolite molecular sieves - Google Patents
The preparation method of card plugging structure multi-stage porous FAU type zeolite molecular sieves Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of " plug-in card " structure multi-stage porous FAU type zeolite molecular sieves, belong to technical field of inorganic.Inorganic alkali source, silicon source are dissolved in deionized water first, are then slowly added to silicon source, is stirred, obtains homogeneous colloidal sol, colloidal sol is then subjected to hydrothermal crystallizing processing, obtains " plug-in card " structure multi-stage porous FAU type zeolite molecular sieves.Present invention synthesis under the conditions of organic-free template and inorganic additives has " plug-in card " structure multi-stage porous FAU type zeolite molecular sieves, significantly reduces synthesis cost, and preparation method is simple and environmentally friendly.In addition, " plug-in card " structure FAU type zeolite molecular sieves have obvious micropore, mesoporous and macroporous structure characteristic, and external surface area is big, acid strong, and stability is good, had a wide range of applications in washing assisant, water softening, catalyst, adsorbent and catalyst carrier etc..
Description
Technical field
The invention belongs to the synthesis technical field of inorganic porous material, and in particular to a kind of inexpensive, green, quick
The preparation method of " plug-in card " structure multi-stage porous FAU type zeolite molecular sieves.
Background technology
Faujasite-type (FAU) molecular sieve has a three-dimensional twelve-ring pore passage structure, and micropore size is about 0.74 nm, bone
Frame silica alumina ratio is relatively low, including X-type molecular sieve and Y type molecular sieve, wherein, SiO2/Al2O3Than being X-type molecular sieve less than 3,
SiO2/Al2O3Than being Y type molecular sieve between 3~6.The X-type molecular sieve knot of low silicon type has good ion exchange and suction
Attached ability, it is industry important detergent builders and water softening agent.The Y type molecular sieve of high-silicon type is in PETROLEUM PROCESSING field
The most widely used fluid catalytic cracking (fluidized catalytic cracking, FCC) catalyst.It is vertical well known,
The performance of molecular sieve and application have close relationship with its pattern and physical dimension.For example, the nanometer chip architecture (letter of self-supporting
Referred to as " plug-in card " structure) zeolite molecular sieve generally there is higher external surface area, bulky molecular catalysis reaction in show it is excellent
Different reactivity.Preparation on self-supporting nanometer chip architecture zeolite molecular sieve at present, more using soft template method.For example,
A.Inayat et al. use organosilan [3- (trimethoxy silicon substrate) propyl group] hexadecyldimethyl benzyl ammonium ammonium chloride (TPHAC) for
Template, is prepared for the X-type zeolite molecular sieve of " plug-in card " (house-of-cards-like) pattern, this " plug-in card " zeolite be by
The X zeolite sheets composition of rounded projections arranged.But organosilan surfactant is expensive, and sintering removal process can cause
Environmental pollution, its large-scale industrial application is set to be obstructed.In order to reduce the industrially prepared cost of " plug-in card " structure molecular screen, middle promulgated by the State Council
Bright patent discloses one kind with organic molecule 1-METHYLPYRROLIDONE (C5H9NO, NMP) it is that structure directing agent prepares multi-stage porous
The method of " plug-in card " structure ZSM-5 zeolite molecular sieve.The preparation method is avoided using expensive long-chain organic amine template,
Synthesis cost is reduced, but still has unavoidably used organic compound.In the recent period, A.Inayat et al. is with zinc nitrate or lithium carbonate
For inorganic additives, X-type molecular sieve pattern is modified, is prepared for laminated structure X-type molecular sieve, but largely use lithium
The inorganic salts such as salt, zinc salt, its synthesis cost is not also low, is unfavorable for industrialized production.
For the problems of above-mentioned prior art and defect, the present invention provides a kind of economical, environmentally friendly, quick " slotting
The preparation method of card " structure multi-stage porous FAU type molecular sieves, it is intended to further reduce synthesis cost and energy consumption, promote " plug-in card " knot
Structure multi-stage porous FAU type zeolite molecular sieve large-scale productions.
The content of the invention
The present invention is added without any organic formwork agent and inorganic additives, has " plug-in card " by one step hydro thermal method synthesis
Structure multi-stage porous FAU types zeolite molecular sieve (house-of-cards-likeFAU, abbreviation HCL-FAU).HCL-FAU is by FAU
The globoid particle (referred to as " plug-in card " structure) that type zeolite nanometer sheet is formed through triangle intersection stacking, about 0.5-5 μm of aggregate particle size.
HCL-FAU has micropore (about 0. 74nm), mesoporous (2~50nm) and macropore duct characteristic, and external surface area is big, and stability is good, and
It is acid strong, there is potential application prospect in catalysis, absorption, separation and ion exchange etc..
To reach above-mentioned purpose, the present invention provides a kind of preparation side of multi-stage porous " plug-in card " structure FAU type zeolite molecular sieves
Method, specific synthetic method are as follows：
(1) inorganic alkali source, silicon source are dissolved in deionized water, are stirred processing；
(2) to adding silicon source under step (1) stirring condition, and stir and form starting sol；
(3) product that step (2) obtains is fitted into reactor, it is closed, carry out hydrothermal crystallizing；, will after treating crystallization
Solid product carries out calcination processing in separation of solid and liquid, washing, drying, air, obtains " plug-in card " structure multi-stage porous FAU types zeolite point
Son sieve.
Preferably, in step (1), inorganic alkali source be sodium oxide molybdena, sodium hydroxide, sodium carbonate, one kind in sodium acid carbonate or
It is a variety of, preferably sodium hydroxide.Silicon source is sodium aluminate (sodium metaaluminate), aluminum sulfate, aluminum nitrate, boehmite, aluminum oxide, hydrogen
One or more in aluminum oxide, aluminium carbonate, aluminium isopropoxide, aluminium acetate, preferably sodium aluminate (sodium metaaluminate).
Preferably, in step (2), silicon source is waterglass, white carbon, sodium metasilicate, Ludox, tetraethyl orthosilicate, silica gel, silicon
One or more in diatomaceous earth, preferably waterglass.
Preferably, in step (2), the inorganic alkali source generates M according to theory2O gauge, silicon source generate Al according to theory2O3
Gauge, the silica source generate SiO according to theory2Gauge, the addition of each reactant is controlled, make starting sol i.e. sial
Possess following molar ratio relations in precursor liquid：1.0~15Na2O： 1.0Al2O3：1.8~15SiO2：40~450H2O。
Preferably, in step (2), silicon source is added at a slow speed under step (1) stirring condition, wherein, silicon source is added at a slow speed
Speed be 0.001mol/min~5mol/min.
Preferably, in step (3), the crystallization temperature be 50~90 DEG C, preferably 55~75 DEG C, crystallization time be 5~
240h, preferably 6~72h.
Preferably, in step (3), the calcining heat is 400~700 DEG C, and preferably 450~550 DEG C, calcination time is
0.5~24h, preferably 3~9h, heating rate are 0.2~5 DEG C of min-1, preferably 1~2 DEG C of min-1。
The present invention compared with prior art, has advantages below and gain effect：
(1) " plug-in card " structure multi-stage porous FAU types molecular sieve (HCL-FAU) prepared by the present invention, its primary structure is FAU
Type zeolite nanometer sheet, adjacent nano piece are accumulated to form globoid through triangle intersection, and particle diameter distribution is homogeneous, more traditional FAU types molecule
Sifter device has abundant micropore, mesoporous and macropore multi-stage artery structure, and external surface area is big, and heat endurance is good, and acid strong, is urging
The fields such as change, absorption, separation and ion exchange have a wide range of applications.
(2) present invention is a kind of economic, efficient, environmentally friendly " plug-in card " structure multi-stage porous FAU type zeolite molecular sieves synthesis side
Method, the preparation process can avoid, using expensive organic formwork agent and/or inorganic additives, greatly reducing the manufacture of material
Process costs, it is expected to realize large-scale commercial production.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous FAU type molecular sieves
(XRD)；
Fig. 2 is (A) stereoscan photograph that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous FAU type molecular sieves
(SEM), (B) transmission electron microscope photo (TEM)；
Fig. 3 is the N that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous FAU type molecular sieves2Absorption/desorption isothermal
Line；
Fig. 4 is the BJH graph of pore diameter distribution that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous FAU type molecular sieves.
Embodiment
The present invention is made with reference to following instance and being further described, but the scope of protection of present invention is not limited to reality
Apply the scope of example statement.
Embodiment 1
(1) 0.5g sodium hydroxides, 1.2g sodium aluminates are added in 6.7g deionized waters, stir to clarify solution；
(2) 3.88g waterglass is slowly added dropwise to the settled solution of step (1) (wherein the content of effective ingredient is SiO2
27.13wt%, Na2O 8.74wt%), stir, ultrasound, obtain uniform dilute colloid；
(3) dilute colloid that step (2) obtains is fitted into hydrothermal reaction kettle, 75 DEG C of thermostatic crystallization 48h, wherein reaction mixing
Thing mol ratio is Na2O:Al2O3:SiO2:H2O=1.43:1.0:2.4:70.2；
(4) after crystallization terminates, solid product is through filtering, carrying out washing treatment, and 24h is dried in 70 DEG C of convection ovens, then in sky
(heating rate is 1 DEG C of min to 450 DEG C of constant temperature calcination 5h in gas-1), obtain " plug-in card " structure multi-stage porous FAU type zeolite molecular sieves.
Phenetic analysis is carried out to " plug-in card " type multi-stage porous FAU types molecular sieve (HCL-FAU) that embodiment 1 synthesizes.
Thing is carried out using X-ray diffractometer to HCL-FAU samples mutually to characterize.As a result as shown in figure 1, HCL-FAU samples
The characteristic peak of XRD spectra and standard FAU type molecular sieves is completely the same, shows that synthesized HCL-FAU samples are FAU type molecules
Sieve.
Using the SiO of X-ray fluorescence spectra analysis HCL-FAU samples2/Al2O3Than being FAU type X zeolite molecules for 2.44
Sieve.
Morphology characterization is carried out to HCL-FAU samples using SEM.As shown in Fig. 2A, 2B, HCL-FAU samples
The pattern of product is that thickness about 100nm FAU zeolites nanometer sheet is arranged by triangle intersections mode, i.e. adjacent nano piece intersects
" plug-in card " type globoid particle is piled into, aggregate particle size is about 1~2 μm, and distribution is homogeneous.Synthesized by transmission electron microscope further confirms
HCL-FAU samples are " plug-in card " structure, and HCL-FAU has substantial amounts of mesoporous and macropore hole, and this is beneficial to macromolecular
Quick transmission.
Using N2Sorption Analyzer carries out microstructure analysis to HCL-FAU samples.As shown in figure 3, N2Adsorption/desorption isothermal is bent
Line shows as typical IV- types adsorption isotherm, shows that HCL-FAU has hierarchical porous structure characteristic, this and tem analysis result phase
Unanimously.It is about 541m by the way that its BET specific surface area is calculated2 g-1, external surface area 100m2g-1.HCL-FAU BJH apertures
Distribution map is as shown in figure 4, mesoporous pore size between 3.3~16nm, is concentrated near 7.8nm.
Embodiment 2
(1) 0.5g sodium hydroxides, 1.2g sodium aluminates are added in 6.7g deionized waters, stir to clarify solution；
(2) 3.88g waterglass is slowly added dropwise to the settled solution of step (1) (wherein the content of effective ingredient is SiO2
27.13wt%, Na2O 8.74wt%), stir, ultrasound, obtain uniform dilute colloid；
(3) dilute colloid that step (2) obtains is fitted into hydrothermal reaction kettle, 60 DEG C of thermostatic crystallization 72h, wherein reaction mixing
Thing mol ratio is Na2O:Al2O3:SiO2:H2O=1.43:1.0:2.4:70.2；
(4) after crystallization terminates, solid product is through filtering, washing, in 70 DEG C of convection oven constant pressure and dry 24h, then in sky
(heating rate is 1 DEG C of min to 500 DEG C of constant temperature calcination 4h in gas-1), obtain " plug-in card " type multi-stage porous FAU type molecular sieve 2.2g, yield
For 18% (product accounts for the mass ratio always to feed intake).
The X-ray powder diffraction figure of the sample and Fig. 1 are essentially identical, and scanned photograph is substantially similar to Fig. 2, XRF
The SiO of spectrum analysis sample2/Al2O3Than being FAU type X zeolite molecular sieves for 2.44.Nitrogen adsorption-desorption isothermal curve and Jie
Hole pore-size distribution and Fig. 3, Fig. 4 are substantially similar, and it is 385m to measure BET specific surface area2g-1, mesoporous pore size between 2.9~5.7nm it
Between, concentrate near 4.4nm.
Embodiment 3
(1) 0.5g sodium hydroxides, 1.2g sodium aluminates are added in 4.7g deionized waters, stir to clarify solution；
(2) 3.88g waterglass is slowly added dropwise to the settled solution of step (1) (wherein the content of effective ingredient is SiO2
27.13wt%, Na2O 8.74wt%), stir, ultrasound, obtain uniform dilute colloid；
(3) dilute colloid that step (2) obtains is fitted into hydrothermal reaction kettle, 75 DEG C of thermostatic crystallization 48h, wherein reaction mixing
Thing mol ratio is Na2O:Al2O3:SiO2:H2O=1.43:1.0:2.4:54.8；
(4) after crystallization terminates, solid product is through filtering, washing, in 70 DEG C of convection oven constant pressure and dry 24h, then in sky
(heating rate is 1 DEG C of min to 450 DEG C of constant temperature calcination 4h in gas-1), obtain " plug-in card " type multi-stage porous FAU type molecular sieve 2.1g, yield
For 20.4% (product accounts for the mass ratio always to feed intake).
The X-ray powder diffraction figure of the sample and Fig. 1 are essentially identical, and scanned photograph is substantially similar to Fig. 2, XRF
The SiO of spectrum analysis sample2/Al2O3Than being FAU type X zeolite molecular sieves for 2.44.
Embodiment 4
(1) 0.6g sodium hydroxides, 1.2g sodium aluminates are added in 6.7g deionized waters, stir to clarify solution；
(2) 3.88g waterglass is slowly added dropwise to the settled solution of step (1) (wherein the content of effective ingredient is SiO2
27.13wt%, Na2O 8.74wt%), stir, ultrasound, obtain uniform dilute colloid；
(3) dilute colloid that step (2) obtains is fitted into hydrothermal reaction kettle, 70 DEG C of thermostatic crystallization 6h, wherein reaction mixing
Thing mol ratio is Na2O:Al2O3:SiO2:H2O=1.6:1.0:2.4:70.2；
(4) after crystallization terminates, solid product is through filtering, washing, in 70 DEG C of convection oven constant pressure and dry 24h, then in sky
(heating rate is 1 DEG C of min to 450 DEG C of constant temperature calcination 4h in gas-1), obtain " plug-in card " type multi-stage porous FAU type molecular sieve 2.1g, yield
For 17% (product accounts for the mass ratio always to feed intake).
The X-ray powder diffraction figure of the sample and Fig. 1 are essentially identical, and scanned photograph is substantially similar to Fig. 2, XRF
The SiO of spectrum analysis sample2/Al2O3Than being FAU type X zeolite molecular sieves for 2.44.
Embodiment 5
(1) 0.5g sodium hydroxides, 1.2g sodium aluminates are added in 6.7g deionized waters, stir to clarify solution；
(2) 4.9g waterglass is slowly added dropwise to the settled solution of step (1) (wherein the content of effective ingredient is SiO2
27.13wt%, Na2O 8.74wt%), stir, ultrasound, obtain uniform dilute colloid；
(3) dilute colloid that step (2) obtains is fitted into hydrothermal reaction kettle, 70 DEG C of thermostatic crystallization 48h, wherein reaction mixing
Thing mol ratio is Na2O:Al2O3:SiO2:H2O=1.6:1.0:3.0:75；
(4) after crystallization terminates, solid product, in 70 DEG C of convection oven constant pressure and dry 24h, obtains through filtering, washing
" plug-in card " type multi-stage porous FAU type molecular sieve 2.2g, yield are 17% (product accounts for the mass ratio always to feed intake).
The X-ray powder diffraction figure of the sample and Fig. 1 are essentially identical, and scanned photograph is substantially similar to Fig. 2, XRF
The SiO of spectrum analysis sample2/Al2O3Than being FAU type Y zeolite molecular sieves for 3.02.
It is described above, only it is several case study on implementation of the present invention, any formal limitation not is done to the present invention,
Protection scope of the present invention not limited to this.
Claims (7)
- The preparation method of " 1. plug-in card " structure multi-stage porous FAU type zeolite molecular sieves, is comprised the following steps that：(1) inorganic base Yuan ﹑ silicon sources are added in deionized water and are stirred processing；(2) silicon source is added under step (1) stirring condition, and stirs and forms starting sol；(3) product that step (2) obtains is fitted into reactor, it is closed, carry out hydrothermal crystallizing；After treating crystallization, by solid Product carries out calcination processing in separation of solid and liquid, washing, drying, air, obtains " plug-in card " structure multi-stage porous FAU type zeolite molecules Sieve.
- 2. preparation method as claimed in claim 1, it is characterised in that：The inorganic alkali source generates M according to theory2O gauge, aluminium Source generates Al according to theory2O3Gauge, the silica source generate SiO according to theory2Gauge, each group in the starting sol The molar ratio divided is 1.0~15Na2O：1.0Al2O3：1.8~15SiO2：40~450H2O。
- 3. the preparation method as described in claim 1-2 is any, it is characterised in that：The inorganic alkali source is sodium oxide molybdena, hydroxide One or more in sodium, sodium carbonate, sodium acid carbonate.
- 4. the preparation method as described in claim 1-2 is any, it is characterised in that source of aluminium is sodium aluminate, aluminum sulfate, nitric acid One kind in aluminium, aluminium chloride, boehmite, aluminum oxide, aluminium hydroxide, aluminium carbonate, pure aluminum, aluminium isopropoxide, aluminium acetate or It is a variety of.
- 5. the preparation method as described in claim 1-2 is any, it is characterised in that the silicon source is waterglass, white carbon, silicic acid One or more in sodium, Ludox, tetraethyl orthosilicate, silica gel, diatomite.
- 6. the method as described in claim 1, it is characterised in that the crystallization temperature be 50~90 DEG C, crystallization time be 5~ 240h。
- 7. the method as described in claim 1, it is characterised in that the calcining heat is 400~700 DEG C, calcination time 0.5 ~24h, heating rate are 0.2~5 DEG C of min-1。
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| CN110357123A (en) * | 2019-07-31 | 2019-10-22 | 深圳大学 | A kind of high crystalline multi-stage porous nano X-type molecular sieve and preparation method thereof |
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| CN111960430A (en) * | 2020-09-01 | 2020-11-20 | 常州工学院 | Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve |
| CN112138724A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Hydroalkylation catalyst and process therefor |
| CN114105165A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Method for recycling synthetic mother liquor of low-silica-alumina-ratio X-type molecular sieve |
| CN115672265A (en) * | 2022-04-28 | 2023-02-03 | 中国科学院过程工程研究所 | Copper-loaded FAU type molecular sieve and preparation method and application thereof |
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