CN1666956A - Method for synthesizing nanometer size mordenite - Google Patents
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Abstract
This invention discloses a synthetic method of nanometer level mordenite. The procedures are that silica resource and aluminum resource are added into water solution of tetraethyl or four-propyl organic amine-group compound, addictives are organic weak acid and NaCl. Ageing 1-10 hours in greenhouse, then crystallize at 140-2000C for 15-30 hours, the pH value of reaction system is 8-13, then the nanometer level mordenite can be collected from the reactive product. The feature of this invention is that few organic ammonium ion is used as template agent, the silica resource is inexpensive silica flour, the aluminum source is sold sodium aluminate. The synthetic nanometer level mordenite has high crystallinity and low cost, it is convenient for industrial generation.
Description
Technical field
The invention relates to the novel method of synthesis of nano size mordenite, the median size of this nano-sized molecular sieve is nano level.Technical field belongs to C01B 39/00 by International Classification of Patents.
Background technology
Nanotechnology is a kind of high-tech technology that is born the eighties in 20th century, and nanoparticle is meant the particle of particle diameter between 1～500nm.
Nano-sized molecular sieve is an important component part of nano material, claims the ultramicron molecular sieve again, is the former subgroup number seldom atom be made of of a class between solid and molecule.The physical properties of nano-sized molecular sieve, chemical property such as thermostability, chemically reactive etc. have a great difference with the regular particle size molecular sieve, and this special nature derives from surface effects and volume effect.Along with reducing of grain-size, the ratio of surface atom, the specific surface of crystal grain and surface energy increase sharply, and make it have the incomparable characteristics of traditional molecular sieve.The upper layer of nano-sized molecular sieve accounts for very big proportion, and specific surface is big, and the surface atom number is many, and promptly the surfactivity center is many, the catalytic efficiency height.The crystal grain of zeolite is little, and its inner duct volume is just little, and reactant residence time in the duct is just short, and the possibility of coking and deactivation has just descended.In high-temperature calcination process, the zeolite of little crystal grain is difficult for producing defective.Zeolite grain is excessive, then is easy to generate bigger intracrystalline pore, and the reaction preference of corresponding little crystal grain zeolite is higher.Aspect physical strength,, thereby have higher intensity and wear resistance because the particle of zeolite is little.Because little crystal grain zeolite has bigger external surface area and higher intracrystalline velocity of diffusion, strengthen conversion capability, improve catalyzer utilization ratio, reduce deep reaction, improve selectivity and reduce aspects such as catalyst deactivation all to show superior performance.Petroleum catalytic cracking, petrochemical complex and fine chemistry industry aspect have been widely used in as catalyst activity component nano-sized molecular sieve.Make cracking catalyst as the nano-scale NaY molecular sieve of high silica alumina ratio and can significantly improve the heavy oil cracking rate, improve gasoline octane rating, show higher cracking activity and cracking selectivity.Simultaneously, nano-sized molecular sieve also all has new application prospect in fields such as sorbing material, transmitter, photochromics and stupaliths.
Mordenite is one of human knowledge's zeolite the earliest.Usefulness yellow soda ash such as Barrer were mineralizer in 1948, made mixing silicic acid gel and sodium aluminate aqueous solution at 265 ℃～295 ℃ following hydrothermal crystallizings, synthesized mordenite first.Contain a large amount of five-rings in the structure of mordenite, these five-rings link together in couples by shared two silicon (aluminium) oxygen tetrahedron.Paired five-ring is connected to five-ring with another by oxo bridge again, has formed tetra-atomic ring in the place that connects thus, continues this structure and has just formed eight yuan and twelve-ring.Mordenite forms by multilayer planar structure is overlapping, therefore, has formed many ducts that are parallel to each other in the crystal of mordenite, wherein the duct of maximum diameter of hole is made up of twelve-ring, the octatomic ring arrangement of passages is irregular, aperture 2.8 , and general molecule is difficult for turnover.Mordenite structure has certain distortion, makes the twelve-ring ovalize, and major axis is 7.0 to diameter, and minor axis is 5.8 to diameter, and its mean diameter is 6.6 .But in practice, there is certain displacement each other in each of mordenite layer structure, causes duct existence distortion to a certain degree, and this has directly caused the minimizing of mordenite mean pore size---less than theoretic 6.6 , often reduce to about 4 .Mordenite has good heat-resisting, acidproof and anti-steam performance, industrial gas or the isolating sorbent material of liquid mixture and petrochemical complex and the fine chemistry industry catalyzer of being widely used as.It is synthetic that mordenite is used for methylamine catalysis, not only use temperature is lower than traditional catalyst, and it is active fairly good, selectivity to dimethylamine then is far superior to traditional catalyst, if as the low temperature modification catalyzer, both can delay the deactivation rate of catalyzer, reduce energy consumption again, and make the degree of freedom of selecting reactor material bigger.
The liquid phase synthesizing method that US 4081514,1978 provides has prepared the mordenite of 20～150um 180 ℃ of following crystallization, and crystallization time 24 hours need to use a large amount of template and crystal seed, and product granularity is bigger;
People such as Zhang Yanfeng (Zhang Yanfeng, Xu Zhongqiang, Chen Qingling.The preparation of microcrystal mordenites film and sign [J].Catalysis journal 2002,23 (2): 145～149) adopt under the tetraethyl ammonium ionization, it is 20～30 microns mordenite membrane that grain-size has been synthesized in utilization under silicon sol, sodium aluminate and the sodium hydroxide effect, needed before the crystallization to stir aging 3 days, finished in 3～4 days at 170 ℃ of following crystallization times, but the minimum (H of crystallization mother liquor concentration in this method
2O/SiO
2=62.5), raw material is very expensive, is unfavorable for the needs of a large amount of synthetic zeolites of industry.
In the microcrystal mordenites field, the progress of study on the synthesis is comparatively slow, and still nobody delivers patented technology now.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of method for synthesizing nanometer size mordenite, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
Silicon source and aluminium source are joined in the aqueous solution that contains the tetraethyl ammonium compounds, with organic monoacid and NaCl is additive, aged at room temperature 1～10 hour, then at 140～200 ℃, crystallization, crystallization time is 15～30 hours, and the pH value of reaction system is 8～13, collects the nanometer size mordenite product then from reaction product.
Said organic ammonium compounds is selected from a kind of in tetraethylammonium bromide, tetraethyl-oxyammonia, the tetrapropyl amine bromide;
Said silicon source is a kind of or its mixture that is selected from pulverous water glass, potassium silicate, barium silicate or the zinc silicate, is commonly called as silica gel;
Used aluminium source is selected from one or more in sodium aluminate, aluminium hydroxide, Tai-Ace S 150, aluminum nitrate or the aluminum chloride;
Organic monoacid is used for the pH value of conditioned reaction system, and used organic monoacid is selected from formic acid, acetate or propionic acid etc.;
The degree of crystallinity that can regulate synthesizing flokite by the content of regulating NaCl.
According to method provided by the invention, can pass through the particle diameter of modulation digestion time, crystallization temperature, crystallization time adjusting nanometer size mordenite;
Utilize its phase structure of X-ray diffraction technical Analysis and degree of crystallinity, analyze its composition with elemental analyser or chemical analysis.
Characteristics of the present invention be adopt NaCl, organic monoacid make synthetic additive, to the suitable aged method of crystallization mother liquor synthesis of nano size mordenite, crystallization time weak point, product degree of crystallinity height, average grain size are little.
The used material molar ratio of the inventive method synthesis of nano size mordenite scope:
SiO
2/Al
2O
3 15～20
Na
2O/SiO
2 0.1～0.3
H
2O/SiO
2 5.0～12.0
Organic ammonium compounds/SiO
20.05～0.3
NaCl/SiO
2 0～0.2
Organic monoacid/SiO
20～0.2.
With the nanometer size mordenite that the method for the invention provides makes, can adopt conventional method, as " natural zeolite ion-exchange performance and application thereof " document disclosed method, after exchanging, ammonium chloride solution changes into Hydrogen through the roasting removed template method.Can be by ion-exchange, dipping or other method with various metals or its compound, introduce the zeolite that wherein makes it to become the different metal modification as element such as basic metal, alkaline-earth metal, rare earth metal, Pt, Pd, Re, Sn, Ni, W, Co or its compound; The compound that also can introduce elements such as different compounds such as P, Ga, Ti, B makes it to become the zeolite with special purpose; Can also be by method dealuminzations such as pickling, chemical extractings to improve the nano mordenite silica alumina ratio and to increase secondary pore.Can be used as multiple catalyzer, catalyst adjuvant and sorbent material with present method synthetic nanometer size mordenite and modified version thereof.
By above-mentioned disclosed technical scheme as seen, the characteristics of method of the present invention are to use a small amount of tetraethyl ammonium ionic compound to make template, do the silicon source with the silica-gel powder of cheapness, commercially available sodium aluminate is done the aluminium source, institute's synthetic nanometer size mordenite, degree of crystallinity height, low cost is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray powder diffraction collection of illustrative plates of standard specimen mordenite.
Fig. 2 is the electromicroscopic photograph of the product of embodiment 1.
Fig. 3 is the state after the product crystal further growth shown in Figure 2 of embodiment.
Embodiment
The following examples will the present invention will be further described, but not thereby limiting the invention.
The mordenite standard substance:
The mordenite that provides with Shanghai Petroleum Chemical Engineering Institute is a standard specimen, adopts Rigaku D/Max2550 VB/PC type x-ray powder diffraction instrument to carry out the analysis of crystal phase structure, uses CuK
αRay, Ni filtering, it is 5 °～30 ° that crystalline phase is measured 2 θ, 2 °/min of sweep velocity, power 40KV*100mA.Its XRD measures (as Fig. 1) degree of crystallinity as 100%, and the degree of crystallinity of the embodiment of the invention and comparative example all contrasts with its characteristic diffraction peak and benchmark sample, represents with relative crystallinity.
According to 2 θ angle values on the X ray diffracting spectrum is that 9.77,13.51,19.68,22.42,23.30,25.75,26.42,27.67 places, 8 characteristic diffraction peak peak heights sum compares, and is calculated as follows the relative crystallinity of sample:
P
i＝(∑I
i/ΣI
m)P
m
(Σ I in the formula
m, Σ I
iThe individual features peak-to-peak height that is standard specimen and sample respectively adds and is worth, P
m, P
iBe respectively the degree of crystallinity of standard specimen and sample).
Embodiment 1
According to method synthesis of nano size mordenite provided by the invention
Raw material is
(A) silica-gel powder: contain SiO
292.44wt%.
(B) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(C) tetraethylammonium bromide: content 61.61wt%, industrial goods.
(D) sodium-chlor: content 99.5wt%, chemical pure.
(E) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(F) propionic acid: content 99.0wt%, chemical pure.
Get 17.02 gram sodium aluminates, 12.03 gram sodium hydroxide, 5.27 gram sodium-chlor, 91.09 gram tetraethylammonium bromide solution, under condition of stirring, be dissolved in the 96.49 gram deionized waters, under constantly stirring, 100 gram silica-gel powders are added in the above-mentioned solution, with third acid for adjusting pH value to 12.85, after stirring, change in the stainless steel pressure still, aging 30 minutes of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 145 ℃, and crystallization time is 20 hours, 400 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt its degree of crystallinity of XRD analysis and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 81.90% as a result, grain-size is 50.9nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: tetraethylammonium bromide: NaCl=1: 2.8: 17: 120: 3: 1.0
The electromicroscopic photograph of mordenite such as Fig. 1 and Fig. 2.By Fig. 1 and Fig. 2 as seen, because little crystal grain zeolite has great surface-area, under the effect of surface free energy, tend to flock together, promptly SEM institute energy is observed all is the state of aggregation of a plurality of crystal grain.From figure a part as can be seen, prepared mordenite is 0.3 * 1.0 μ m rhabdolith.Fig. 3 is the state after the crystal further growth, under the condition that stirs crystallization, and the passivation of crystalline sharp corners, crystal growth to 4～6 μ m sizes.
Embodiment 2
Raw material is:
(G) silica-gel powder: contain SiO
292.44wt%.
(H) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(I) 4-propyl bromide: content 61.61wt%, industrial goods.
(J) sodium-chlor: content 99.5wt%, chemical pure.
(K) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(L) acetate: content 99.0wt%, chemical pure.
12.82 gram sodium aluminate, 9.06 gram sodium hydroxide, 5.96 gram sodium-chlor, 116.1 gram 4-propyl bromide solution, under condition of stirring, be dissolved in the 216.01 gram deionized waters, under constantly stirring, 75 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 12 with formic acid, after stirring, change in the stainless steel pressure still, aging 9 hours of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 195 ℃, and crystallization time is 18 hours, 200 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt its degree of crystallinity of XRD analysis and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 80.90% as a result, grain-size is 45.6nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: 4-propyl bromide: NaCl=1: 2.9: 17: 210: 5: 1.5
Embodiment 3
Raw material is
(M) silica-gel powder: contain SiO
292.44wt%.
(N) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(O) tetraethyl ammonium hydroxide: content 61.61wt%, industrial goods.
(P) sodium-chlor: content 99.5wt%, chemical pure.
(Q) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(R) acetate: content 99.0wt%, chemical pure.
Get 8.55 gram sodium aluminates, 6.04 gram sodium hydroxide, 7.94 gram sodium-chlor, 46.03 gram tetraethyl ammonium hydroxide solution, under condition of stirring, be dissolved in the 92.86 gram deionized waters, under constantly stirring, 50 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 8.15 with acetate, after stirring, change in the stainless steel pressure still, aging 13 hours of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 180 ℃, and crystallization time is 28 hours, 200 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt XRD analysis to play degree of crystallinity and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 87.5% as a result, grain-size is 50.7nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: tetraethylammonium bromide: NaCl=1: 2.9: 17: 150: 3.0: 3.0.
Embodiment 4
Raw material is:
(S) silica-gel powder: contain SiO
292.44wt%.
(T) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(U) tetraethyl ammonium hydroxide: content 61.61wt%, industrial goods.
(V) sodium-chlor: content 99.5wt%, chemical pure.
(W) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(X) formic acid: content 99.0wt%, chemical pure.
Get 10.35 gram sodium aluminates, 2.01 gram sodium hydroxide, 6.11 gram sodium-chlor, 46.03 gram TPAOH solution, under condition of stirring, be dissolved in the 123.43 gram deionized waters, under constantly stirring, 50 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 11 with acetate, after stirring, change in the stainless steel pressure still, aging 1 hour of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 170 ℃, and crystallization time is 16 hours, 300 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt XRD analysis to play degree of crystallinity and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 61.7% as a result, grain-size is 40.0nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: template: NaCl=1: 1.0: 15: 180: 3: 2.5
Embodiment 5
Raw material is
(Y) silica-gel powder: contain SiO
292.44wt%.
(Z) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(AA) tetraethylammonium bromide: content 61.61wt%, industrial goods.
(BB) sodium-chlor: content 99.5wt%, chemical pure.
(CC) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(DD) propionic acid: content 99.0wt%, chemical pure.
Get 10.92 gram sodium aluminates, 9.06 gram sodium hydroxide, 69.50 gram tetraethylammonium bromide solution, under condition of stirring, be dissolved in the 102.3 gram deionized waters, under constantly stirring, 75 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 10 with propionic acid, after stirring, change in the stainless steel pressure still, aging 13 hours of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 160 ℃, and crystallization time is 22 hours, 300 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt XRD analysis to play degree of crystallinity and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 72.0% as a result, grain-size is 92.9nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: tetraethylammonium bromide: NaCl=1: 2.9: 20: 100: 0: 1.5
Embodiment 6
Raw material is:
(EE) silica-gel powder: contain SiO
292.44wt%.
(FF) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(GG) TPAOH: content 61.61wt%, industrial goods.
(HH) sodium-chlor: content 99.5wt%, chemical pure.
(II) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(JJ) formic acid: content 99.0wt%, chemical pure.
Get 8.63 gram sodium aluminates, 6.04 gram sodium hydroxide, 3.97 gram sodium-chlor, 30.69 gram TPAOH solution, under condition of stirring, be dissolved in the 148.15 gram deionized waters, under constantly stirring, 50 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 9 with acetate, after stirring, change in the stainless steel pressure still, aging 1 hour of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 190 ℃, and crystallization time is 2 hours, 400 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt XRD analysis to play degree of crystallinity and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 88.4% as a result, grain-size is 48.0nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: tetraethylammonium bromide: NaCl: HAc=1: 2.9: 18: 196: 3: 1.0: 1
Embodiment 7
Raw material is
(KK) silica-gel powder: contain SiO
292.44wt%.
(LL) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(MM) TPAOH: content 61.61wt%, industrial goods.
(NN) sodium-chlor: content 99.5wt%, chemical pure.
(OO) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(PP) formic acid: content 99.0wt%, chemical pure.
Get 9.65 gram sodium aluminates, 3.31 gram sodium hydroxide, 4.87 gram sodium-chlor, 46.03 gram tetrapropyl hydrogen-oxygen solution, under condition of stirring, be dissolved in the 61.72 gram deionized waters, under constantly stirring, 50 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 13 with formic acid, after stirring, change in the stainless steel pressure still, aging 5 hours of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 150 ℃, and crystallization time is 22 hours, 500 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt XRD analysis to play degree of crystallinity and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 67.1% as a result, grain-size is 39.7nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: TPAOH: NaCl=1: 1.6: 16: 90: 3: 2.0
Embodiment 8
Raw material is
(QQ) silica-gel powder: contain SiO
292.44wt%, self-control.
(RR) sodium aluminate: content Al
2O
3: 5.301*10
-3Mol/g; Na
2O:6.541*10
-3Mol/g, chemical pure.
(SS) tetraethylammonium bromide: content 61.61wt%, industrial goods.
(TT) sodium-chlor: content 99.5wt%, chemical pure.
(UU) sodium hydroxide: content Na
2O:0.0125mol/g, chemical pure.
(VV) acetate: content 99.0wt%, chemical pure.
Get 8.16 gram sodium aluminates, 6.07 gram sodium hydroxide, 3.99 gram sodium-chlor, 23.93 gram 4-propyl bromide solution, under condition of stirring, be dissolved in the 123.15 gram deionized waters, under constantly stirring, 50 gram silica-gel powders are added in the above-mentioned solution, regulate pH value to 8 with acetate, after stirring, change in the stainless steel pressure still, aging 9 hours of stirring at room is carried out crystallization by certain heating schedule.Crystallization temperature is 170 ℃, and crystallization time is 22 hours, 350 rev/mins of stirring velocitys.Crystallization finishes and carries out suction filtration, washing, drying, obtain the nano mordenite product, adopt XRD analysis to play degree of crystallinity and phase structure, chemical analysis is analyzed its chemical constitution, the XRD figure spectrum is gone up each characteristic peak data (deduction instrument body broadening) utilization Scherrer formula ask the average grain size of calculating zeolite, SEM observes its brilliant looks.Its degree of crystallinity is 92.61% as a result, grain-size is 45.6nm.The original constitutive molar ratio that feeds intake is:
Al
2O
3: Na
2O: SiO
2: H
2O: 4-propyl bromide: NaCl=1: 2.9: 19: 180: 1.5: 1.5
Mordenite has best degree of crystallinity and grain-size under this condition.
Claims (8)
1. method for synthesizing nanometer size mordenite, it is characterized in that, comprise the steps: silicon source and aluminium source are joined in the aqueous solution that contains the organic ammonium compounds, with organic monoacid and NaCl is additive, aged at room temperature 1～10 hour, then at 140～200 ℃, crystallization, the pH value of reaction system is 8～13, collects the nanometer size mordenite product then from reaction product.
2. method according to claim 1 is characterized in that, crystallization time is 15～30 hours.
3. method according to claim 1 is characterized in that, said tetraethyl ammonium compounds is selected from a kind of in tetraethylammonium bromide, tetraethyl-oxyammonia, tetrapropyl amine bromide, the tetrapropyl oxyammonia.
4. method according to claim 1 is characterized in that, said silicon source is a kind of or its mixture that is selected from pulverous water glass, potassium silicate, barium silicate or the zinc silicate.
5. method according to claim 1 is characterized in that, used aluminium source is selected from one or more in sodium aluminate, aluminium hydroxide, Tai-Ace S 150, aluminum nitrate or the aluminum chloride.
6. method according to claim 1 is characterized in that used organic monoacid is selected from formic acid or acetate.
7. according to each described method of claim 1～6, it is characterized in that used material molar ratio scope:
SiO
2/Al
2O
3 15～20
Na
2O/SiO
2 0.1～0.3
H
2O/SiO
2 5.0～12.0
Organic ammonium compounds/SiO
20.05～0.3
NaCl/SiO
2 0～0.2
Organic monoacid/SiO
20～0.2.
8. according to the nanometer size mordenite of each described method preparation of claim 1～7.
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| CN100436320C (en) * | 2006-05-08 | 2008-11-26 | 浙江大学 | Method for synthesizing high-silicon mordenite in the absence of amine |
| CN100453461C (en) * | 2006-04-24 | 2009-01-21 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN101519217B (en) * | 2008-02-28 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Preparation method of microcrystal mordenites |
| CN102188993A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Preparation method for MFI/MOR composite zeolite molecular sieve catalyst without binder |
| CN102602958A (en) * | 2012-04-13 | 2012-07-25 | 华东师范大学 | Preparation method of mesoporous mordenite |
| CN102060308B (en) * | 2009-11-18 | 2012-08-22 | 中国科学院大连化学物理研究所 | Synthesis method of nano fibrous mordenite |
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