CN104229806A - Method for synthesizing magadiite by adopting catalytic nucleation method - Google Patents
Method for synthesizing magadiite by adopting catalytic nucleation method Download PDFInfo
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- CN104229806A CN104229806A CN201410458274.5A CN201410458274A CN104229806A CN 104229806 A CN104229806 A CN 104229806A CN 201410458274 A CN201410458274 A CN 201410458274A CN 104229806 A CN104229806 A CN 104229806A
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- catalysis
- magadiite
- nucleator
- mixture
- alkali source
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000010899 nucleation Methods 0.000 title claims abstract description 33
- 230000006911 nucleation Effects 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 catalyzer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The invention discloses a method for synthesizing magadiite by adopting a catalytic nucleation method. The method for synthesizing the magadiite by adopting the catalytic nucleation method comprises the following steps: mixing a silicon source, an alkali source, a catalysis nucleating agent and water to obtain a mixture, wherein components in the mixture meet the conditions that mole ratio of the silicon source to the alkali source is 3-7 and mole ratio of water to the alkali source is 20-100; putting the mixture into a closed container, and carrying out crystallization at the temperature of 110-170 DEG C for 6-72 hours at a self-generated pressure; and taking out a crystallization product, filtering, washing with water until pH value is 7-8, and drying at the temperature of 60-100 DEG C for 4-12 hours, so that a two-dimensional lamellar structural material magadiite is obtained. Compared with an existing synthesis method without adding a catalysis nucleating agent, the method for synthesizing the magadiite by adopting the catalytic nucleation method has the advantages that a synthesis period is shortened by 12-108 hours, a synthesis temperature is lowered by 30-40 DEG C, and the obtained magadiite can be used as a catalyst, an adsorbent, a pillar material, an ion exchanger, filler of a nano composite material and the like.
Description
Technical field
The present invention relates to the synthetic method of magadiite, be specifically related to the method for a kind of catalysis nucleation process synthesis magadiite.
Background technology
Magadiite is a kind of two-dimensional layered-structure material, and its laminate is by electronegative SiO
4tetrahedron forms, there are chemistry and thermostability preferably, interlayer has hydration sodium ion that can be exchanged, there is between laminate good swelling property, can hold the little proton that arrives and arrive greatly high-polymer molecular or group, these character facilitate the application of magadiite as aspects such as cationite, sorbent material, pillared composite, catalyzer, nano composite material fillers.
Document at present about magadiite synthesis focuses mostly in the difference in silicon source, the proportioning of silicon source, alkali source, water different and its with mordenite, β zeolite, ZSM-35 one or more be compounded to form coexisting material, the technique of synthesizing magadiite about catalysis nucleation process is not yet seen in word.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, the synthesis cycle of magadiite is longer, synthesis temperature is higher, a kind of catalysis nucleation process is provided to synthesize the method for magadiite, the method is characterized in that the chemical reaction rate also accelerating while improving nucleation rate and generate magadiite, this technique synthesis cycle compared with the existing synthetic method not adding catalysis nucleator shortens 6 ~ 72 hours, and synthesis temperature reduces 6 ~ 20 DEG C.
For solving the problem, the technical solution used in the present invention is as follows.
A method of catalysis nucleation process synthesis magadiite, comprises the following steps:
(1) by silicon source, alkali source, catalysis nucleator and water mixing, mixture is obtained; Silicon source is met: alkali source=3 ~ 7 with the component in molar ratio computing mixture; Water: alkali source=20 ~ 100; Catalysis nucleator volume is no more than 1/2nd of all volume of mixture, and more than 1/6th of all volume of mixture;
(2) mixture that step (1) obtains is put into encloses container at autogenous pressures, 110 ~ 170 DEG C of crystallization 6 ~ 144 hours;
(3) product good for crystallization is taken out, after filtration, be washed to 60 DEG C ~ 100 DEG C dryings 4 ~ 12 hours behind pH=7 ~ 8, obtained two-dimensional layered-structure material magadiite.
In aforesaid method, the silicon source described in step (1) is more than one in aerosil or precipitated silica.
In aforesaid method, the alkali source described in step (1) is the mixture of sodium hydroxide and sodium carbonate; With molar ratio computing, wherein Na
2cO
3: NaOH=2 ~ 5.
In aforesaid method, in step (1), described catalysis nucleator is the one in granulated glass sphere, ceramic bead or steel ball, and the diameter of described catalysis nucleator is 2mm ~ 7mm.
In aforesaid method, in step (1), described catalysis nucleator does not participate in chemosynthesis reaction, reuses.
In aforesaid method, described in step (1) by the concrete steps that silicon source, alkali source, catalysis nucleator and water mix be: first alkali source and water are mixed into solution, then mix with silicon source, finally mix with catalysis nucleator.
In the present invention, synthesis temperature reduces 6 ~ 20 DEG C degrees Celsius, its principle can be interpreted as: its katalysis adds that some group making reactant is first fixing with nucleating agent contact reacts forms intermediate product due to catalysis nucleator, carry out into nuclear reaction more afterwards, intermediate product is reduced to nucleation catalytic machine and generates target product, the generation of such intermediate product changes response path, reduce the activation energy of reaction, and then reduce temperature of reaction, improve speed of reaction; Nucleogenesis can be regarded as when not having catalysis nucleator, is homogeneous nucleation, and nucleation rate is:
N in formula---the atomicity in unit volume liquid phase;
κ---Boltzmann constant;
Δ G
a---atom crosses the intensity of activation through liquid-solid interface:
α---nucleus shape-dependent constant, to spherical nucleus, π/3, α=16;
Δ G
v---volume free energy is poor.
The free Δ G of forming core of heterogeneous nucleation
sand the nucleation rate μ in the unit surface of heterogeneous nucleus
scalculating formula be respectively:
Δ G
s=Δ G
allf (θ)
In formula
The contact angle of θ---nascent crystals and heterogeneous nucleus
N
s---the atomicity in unit surface
All the other symbols are identical with not having the homogeneous nucleation formula of nucleator.
From three formula above, unless θ=180 °, otherwise f (θ) is always less than 1, so volume forming core free energy is always less than the free energy of average forming core needed for Heterogeneous Nucleation, and nucleation rate height overall is in the nucleation rate of homogeneous nucleation, and θ angle is less, and difference is larger, that is when reactant solution and nucleator show that wetting property is better, nucleation rate is higher.[Xing Jiandong, epitaxis [M], press of Xi'an Communications University, 2008.5,5-7].There is the effect of catalysis and nucleation so simultaneously, tentatively be referred to as " catalyses nucleation ".
Compared with prior art, tool of the present invention has the following advantages and technique effect:
The present invention is under limited processing condition, add catalysis nucleator, synthesized the magadiite of simple phase, the method synthesis cycle compared with the existing synthetic method not adding catalysis nucleator shortens 6 ~ 96 hours, and synthesis temperature reduces 6 ~ 20 DEG C degrees Celsius.Obtained material has two-dimensional layered structure and interlayer has tradable positively charged ion, is widely used in ion-exchange, catalysis, absorption etc.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of gained magadiite in embodiment 1.
Fig. 2 is the X-ray diffracting spectrum of gained magadiite in embodiment 2.
Fig. 3 is the X-ray diffracting spectrum of gained magadiite in embodiment 3.
Fig. 4 is the X-ray diffracting spectrum of gained magadiite in embodiment 4.
Fig. 5 a and Fig. 5 b is the scanning electron microscope collection of illustrative plates of gained magadiite in embodiment 4.
Embodiment
Below by embodiment in detail the present invention is described in detail, but protection scope of the present invention is not limited to these embodiments.
Thermal silica (the SiO used in following examples
2content wt.%>=99.8), buy in Jiangxi Jia Jie novel material company limited; Precipitated silica (93%SiO
2, 7%H
2o), buy in Shanghai Zhen Jiang Chemical Co., Ltd..
Embodiment 1
Get 0.40 gram of sodium hydroxide and 2.12 grams of sodium carbonate to be successively dissolved in 53.05 grams of water and to make mixing solutions, add 50 ceramic beads (diameter 5mm) after fully being mixed with 13.55 grams of precipitated silicas (moisture 7wt%) by mixing solutions and stir 15 minutes, adding after stirring in autoclave and at 110 DEG C, carry out hydrothermal crystallizing 36 hours.Product after filtration, to be washed to behind pH=7 ~ 8 at 80 DEG C dry 6 hours, obtain magadiite.Qualitative analysis (its X-ray diffraction spectrogram is shown in accompanying drawing 1) is carried out by X-ray diffraction method, this magadiite known is simple phase, and from do not add catalysis nucleator and the different product of method the same terms is the same, crystallization degree is suitable, and the catalyses nucleation of known ceramic bead at 110 DEG C makes reaction approximate shortening generated time 108h.
Embodiment 2
Get 0.40 gram of sodium hydroxide and 2.12 grams of sodium carbonate to be successively dissolved in 42.39 grams of water and to make mixing solutions, add 50 ceramic beads (diameter 5mm) after fully being mixed with 11.61 grams of precipitated silicas (moisture 7wt%) by mixing solutions and stir 15 minutes, adding after stirring in autoclave and at 110 DEG C, carry out hydrothermal crystallizing 36 hours.Product after filtration, to be washed to behind pH=7 ~ 8 at 80 DEG C dry 6 hours, obtain magadiite, (the electron-microscope scanning figure of the present embodiment products obtained therefrom can refer to Fig. 5 b).Qualitative analysis (its X-ray diffraction spectrogram is shown in accompanying drawing 2) is carried out by X-ray diffraction method, this magadiite known is simple phase, crystallization degree is suitable, known 150 DEG C, under the product that synthesizes under the 36h condition catalysis nucleation at ceramic bead 110 DEG C, 36h just can be synthesized, and approximately reduces synthesis temperature 40 DEG C.
Embodiment 3
Get 0.40 gram of sodium hydroxide and 2.12 grams of sodium carbonate to be successively dissolved in 26.32 grams of water and to make mixing solutions, add 50 granulated glass spherees (diameter 5mm) after fully being mixed with 9.68 grams of precipitated silicas (moisture 7wt%) by mixing solutions and stir 15 minutes, adding after stirring in autoclave and at 130 DEG C, carry out hydrothermal crystallizing 24 hours.Product after filtration, to be washed to behind pH=7 ~ 8 at 80 DEG C dry 6 hours, obtain magadiite, (the electron-microscope scanning figure of the present embodiment products obtained therefrom can refer to Fig. 5 b).Qualitative analysis (its X-ray diffraction spectrogram is shown in accompanying drawing 3) is carried out by X-ray diffraction method, this magadiite known is simple phase, and from do not add catalysis nucleator and the different product of method the same terms is the same, and from do not add catalysis nucleator and the different product of method the same terms is the same, known 160 DEG C, under the product that synthesizes under the 24h condition catalysis nucleation at ceramic bead 130 DEG C, 24h just can be synthesized, and approximately reduces synthesis temperature 30 DEG C.
Embodiment 4
Get 0.40 gram of sodium hydroxide and 2.12 grams of sodium carbonate to be successively dissolved in 10.26 grams of water and to make mixing solutions, add 50 steel balls (diameter 5mm) after fully being mixed with 7.74 grams of precipitated silicas (moisture 7wt%) by mixing solutions and stir 15 minutes, adding after stirring in autoclave and at 170 DEG C, carry out hydrothermal crystallizing 6 hours.Product after filtration, to be washed to behind pH=7 ~ 8 at 80 DEG C dry 6 hours, obtain magadiite, (the electron-microscope scanning figure of the present embodiment products obtained therefrom can refer to Fig. 5 b).As found out that it has the Rose valvular structure of stratiform in the magadiite electron-microscope scanning soil in Fig. 5 a and Fig. 5 b (wherein Fig. 5 a does not add catalysis nucleator 170 DEG C of hydrothermal crystallizing 18h), namely there is two-dimensional layered structure, can be found out by contrast, the product adding nucleating agent has more perfect crystallization structure and more orderly laminate structure, qualitative analysis (its X-ray diffraction spectrogram is shown in accompanying drawing 4) is carried out by X-ray diffraction method, this magadiite known is simple phase, and from do not add catalysis nucleator and the different product of method the same terms is the same, the catalyses nucleation of known steel ball at 170 DEG C makes reaction approximate shortening generated time 12h.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (6)
1. a method of catalysis nucleation process synthesis magadiite, is characterized in that, comprise the following steps:
(1) by silicon source, alkali source, catalysis nucleator and water mixing, mixture is obtained; Silicon source is met: alkali source=3 ~ 7 with the component in molar ratio computing mixture; Water: alkali source=20 ~ 100; Catalysis nucleator volume is no more than 1/2nd of all volume of mixture, and more than 1/6th of all volume of mixture;
(2) mixture that step (1) obtains is put into encloses container at autogenous pressures, 110 ~ 170 DEG C of crystallization 6 ~ 144 hours;
(3) product good for crystallization is taken out, after filtration, be washed to 60 DEG C ~ 100 DEG C dryings 4 ~ 12 hours behind pH=7 ~ 8, obtained two-dimensional layered-structure material magadiite.
2. the method for catalysis nucleation process synthesis magadiite according to claim 1, is characterized in that, the silicon source described in step (1) is more than one in aerosil or precipitated silica.
3. catalysis nucleation process synthesizes the method for magadiite according to claim 1, and it is characterized in that, the alkali source described in step (1) is the mixture of sodium hydroxide and sodium carbonate; With molar ratio computing, wherein Na
2cO
3: NaOH=2 ~ 5.
4. catalysis nucleation process synthesizes the method for magadiite according to claim 1, and it is characterized in that, in step (1), described catalysis nucleator is the one in granulated glass sphere, ceramic bead or steel ball, and the diameter of described catalysis nucleator is 2mm ~ 7mm.
5. catalysis nucleation process synthesizes the method for magadiite according to claim 1, and it is characterized in that, in step (1), described catalysis nucleator does not participate in chemosynthesis reaction, reuses.
6. catalysis nucleation process synthesizes the method for magadiite according to claim 1, it is characterized in that, described in step (1) by the concrete steps that silicon source, alkali source, catalysis nucleator and water mix be: first alkali source and water are mixed into solution, then mix with silicon source, finally mix with catalysis nucleator.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174209A (en) * | 2011-01-25 | 2011-09-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing controlled degradable polypropylene foamed particles |
| CN103073004A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Preparation method of two-dimensional layered-structure material magadiite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102174209A (en) * | 2011-01-25 | 2011-09-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing controlled degradable polypropylene foamed particles |
| CN103073004A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Preparation method of two-dimensional layered-structure material magadiite |
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