CN109748289A - A kind of method and products thereof preparing multi-stage porous silica zeolite - Google Patents
A kind of method and products thereof preparing multi-stage porous silica zeolite Download PDFInfo
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- CN109748289A CN109748289A CN201711067698.9A CN201711067698A CN109748289A CN 109748289 A CN109748289 A CN 109748289A CN 201711067698 A CN201711067698 A CN 201711067698A CN 109748289 A CN109748289 A CN 109748289A
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Abstract
The present invention provides a kind of methods for preparing multi-stage porous silica zeolite, the present invention is by being added silicon source in the aqueous solution to structure directing agent, so that silicon source is carried out a period of time hydrolysis and be placed on progress hydrothermal crystallizing reaction in reaction kettle, obtains multi-stage porous silica zeolite after post treatment later.The present invention does not use mesoporous template, the molecular sieve of synthesis external surface area with higher and mesopore volume, and a large amount of faintly acid position, can be used in all kinds of catalysis reactions for preparing alkene.
Description
Technical field
The invention belongs to technical field of molecular sieve preparation, and in particular to prepare the method for multi-stage porous silica zeolite and by this
Multi-stage porous silica zeolite made from method.
Background technique
Geometry duct and higher specific surface area of the molecular sieve due to rule itself, are widely used in the absorption of gas, divide
It is used as in all kinds of catalysis reactions from and as catalyst or catalytic carrier.However, the catalytic activity of micro porous molecular sieve is deposited
In the diffusion restricted problem of reactant and reaction product in micropore canals.Therefore, in conjunction with micro porous molecular sieve, mesoporous material advantage
Multi-stage pore canal molecular sieve come into being.Currently, the synthetic method of multi-stage pore canal molecular sieve is roughly divided into two classes: one kind be to point
Son sieve is post-processed, and mainly includes desiliconization method and dealuminzation method;Another kind of is direct synthesis multi-stage pore canal molecular sieve, mainly includes
The method that hard template method, soft template method and small molecule template assemble in situ prepare nanometer particle congery.But use bimodulus
Maximum problem, which is between template, when plate synthesizes is the mutually separation of competition and non-synergistic effect generation, and uses double template
It not only increases cost and preparation process is complicated, therefore, be not suitable for large-scale application.Have in the prior art and uses difunctionalization
Template prepares multi-stage pore canal molecular sieve, although difunctionalization template can avoid mutually separating, difunctionalization template
Expensive and complex synthetic route is time-consuming and limits its industrial applications.
The method for how seeking simply to prepare multistage porous molecular sieve is the content that people study extensively at this stage.
Hayasaka et al. discovery ZSM-22 bar-like grains can be merged by intercrystalline arrangement forms aggregation.In addition, ZSM-12,
The nanometer particle congery of the molecular sieves such as ZSM-5, Beta is successfully synthesized under conditions of not adding secondary template agent.Fang etc.
Polyanion nucleation accelerating agent (H is added in synthetic system2PO4 -) primary particle for being nucleated obtained 20-30nm is promoted to pass through certainly
Assembling forms ZSM-12 nanoparticle aggregate, and size is l microns, possesses and the comparable macro of tradition ZSM-12
While property, the excellent 0.12cm out of mesopore volume3/ g, and this ZSM-12 nanometer particle congery has good hydrothermally stable
Property.
In molecular sieve, silica zeolite is acid very weak due to there is only micro Al, during this is inhibited to a certain extent
Between the isomerization of product and the generation of secondary hydrogenation reaction, be conducive to improve product selectivity.Wherein, with MFI structure
Silica zeolite Silicalite-1 is due to a large amount of faintly acid position, high-specific surface area, at the same with active component have compared with
Weak interaction will be undoubtedly many heavy effective catalytic carrier to be reacted.However, the cellular structure of micro porous molecular sieve is to urging
Changing reaction has biggish resistance to reduce catalytic activity, therefore it provides a kind of simple preparation has the total silicon of multi-stage porous
Molecular sieve is this field urgent problem.
Summary of the invention
In order to solve problems in the prior art, the present invention provides a kind of methods for preparing multi-stage porous silica zeolite, originally
Invention utilizes hydrothermal crystallisation methods, does not use mesoporous template, only with single structure directing agent, one-step synthesis method goes out multi-stage porous
Silica zeolite.
One aspect of the present invention provides a kind of preparation method of multi-stage porous silica zeolite, comprising:
Silicon source is added into the aqueous solution of structure directing agent, make silicon source carry out a period of time hydrolysis be placed in reaction kettle into
The reaction of row hydrothermal crystallizing, obtains multi-stage porous silica zeolite for obtained product is post-treated.
According to the present invention, the structure directing agent is 4-propyl bromide and/or tetrapropylammonium hydroxide.Of the invention
In one specific embodiment, structure directing agent is tetrapropylammonium hydroxide.
According to the present invention, the silicon source in silester, silica solution, Silica hydrogel, methyl silicate and white carbon black extremely
Few one kind, preferably silester and/or methyl silicate, the silicon source be more preferably silester -28, silester -32 and
At least one of silester -40.
According to the present invention, the mass ratio of the silicon source and structure directing agent is 1:(0.1-5), preferably 1:(0.5-2), more
Preferably 1:(1-2).The present invention when preparing porous grade silica zeolite, the selection of silicon source and structure directing agent and the two
Dosage has an important influence to preparing multi-stage porous silica zeolite, and the mass ratio of silicon source and structure directing agent is bigger than normal or less than normal,
It is unfavorable for forming the silica zeolite with hierarchical porous structure, or the mesoporous form of the silica zeolite formed is undesirable,
Mesoporous effect cannot be effectively played in actual production process.
According to the present invention, the mass concentration of the aqueous solution of the structure directing agent is 10%-25%.
According to the preferred embodiment of the present invention, the process that the silicon source is added to structure directing agent needs slowly to carry out.
Preferably, silicon source is added in the aqueous solution of structure directing agent with 0.02-1mL/s speed, preferably in a manner of dropwise addition.At this
In one specific embodiment of invention, silicon source is added in the aqueous solution of structure directing agent with 0.2mL/s speed.
According to the present invention, it after in the aqueous solution that silicon source is added to structure directing agent, stirs so that silicon source hydrolysis, hydrolysis
It carries out at room temperature, hydrolysis time 2-5h, preferably 2-3h.Inventor is the study found that hydrolytic process is formed conducive to molecular sieve
It is mesoporous.
According to the preferred embodiment of the present invention, the reaction kettle is water heating kettle, hydrothermal crystallizing reaction condition in reaction kettle
It is 160-180 DEG C of temperature, time 12-60h, preferably 48h.
According to the present invention, the post-processing includes washing product, dried and being roasted, it is preferable that the roasting item
Part are as follows: in air atmosphere, with the heating rate of 0.5-2 DEG C/min, be warming up to 550-600 DEG C, time 4-10h.
According to another aspect of the present invention, a kind of multi-stage porous silica zeolite is provided, foregoing preparation is used
Method is made, and the molecular sieve includes the micropore that diameter is 2-15 angstroms, preferably 5 angstroms of micropore, Jie that diameter is 3-12 nanometers
Hole and 50-100 nanometers of macropore, the partial size of the molecular sieve are 50-300nm, and the external surface area of molecular sieve is 400-
500cm2/ g, mesopore volume and macropore volume summation are 0.4-0.7cm3/ g, micro pore volume 0.1-0.2cm3/ g, and molecular sieve
With Lewis acid position.
The sour position of molecular sieve is in NH in the present invention3In adsorption desorption curve, desorption temperature is at 200 DEG C hereinafter, in pyridine
It adsorbs in infrared test curve, in 1450cm-1Occur absorption peak at left and right, is adsorbed in Lewis acidic site corresponding to Pyridine Molecules
The absorption peak of suction-operated occurs.
The present invention only uses single structure directed agents, the nanoscale multi-stage porous total silicon point of synthesis without mesoporous template
Son sieve silicalite-1, due to external surface area with higher and mesopore volume, and a large amount of position Lewis, it can be used for
In all kinds of catalysis reactions for preparing alkene.The preparation method of multi-stage porous silica zeolite provided by the invention is simple, after being not necessarily to
Reason, is directly prepared using one-step method.It is at low cost due to not using mesoporous template, it is suitable for large-scale industrial production.
Detailed description of the invention
Fig. 1 is the SEM figure of multistage grade silica zeolite silicalite-1 prepared by embodiment 1.
Fig. 2 is the SEM figure of multistage grade silica zeolite silicalite-1 prepared by embodiment 2.
Fig. 3 is the N of multistage grade silica zeolite silicalite-1 prepared by embodiment 12Adsorption desorption curve.
Fig. 4 is the NH of molecular sieve prepared by embodiment 1 and comparative example 13Adsorption desorption curve.
Fig. 5 is molecular sieve pyridine adsorption FT-IR curve prepared by embodiment 1 and comparative example 1.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
Embodiment 1
Using silester -40 (mass content of silica for 40%) TEOS is silicon source, tetrapropylammonium hydroxide
TPAOH is template, and TEOS is slowly added into the aqueous solution (tetrapropylammonium hydroxide of TPAOH by the ratio with mass ratio for 1:1
Mass concentration be 25%) in, in conical flask, magnetic agitation 2h at room temperature.It is then transferred in stainless steel water heating kettle,
Isothermal reaction 48h under the conditions of 180 DEG C.Deionized water washing, filtering, 120 DEG C drying 12 hours.Further, products therefrom is put
It is placed in tube furnace, in air atmosphere, is warming up to 550 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 6h, it is complete to obtain porous grade
Si molecular sieves silicalite-1, SEM figure is as shown in Figure 1.The average grain diameter of molecular sieve obtained is 200nm, molecular sieve it is outer
Specific surface area is 450cm2/ g, mesoporous and macropore total volume are 0.34cm3/ g, micro pore volume 0.13cm3/g.Molecular sieve has
The macropore that the mesoporous and average pore size that micropore that average pore size is 5 angstroms, average pore size are 6nm is 50nm.
The specific surface map of molecular sieve made from Fig. 3, as the figure can be seen that made from molecular sieve have meso-hole structure.
Fig. 4 is the molecular sieve NH prepared3There is the biggish peak of intensity within 200 DEG C in adsorption desorption curve, is NH3It is
The chemisorption at weaker acid position, this illustrates molecular sieve manufactured in the present embodiment, and there are faintly acid centers, are being higher than 200 DEG C not
Appearance illustrates molecular sieve strong and strong acid center without in.And SBA-15 molecular sieve is compared, the desorption peaks of NH3 are remarkably reinforced, explanation
Porous grade silica zeolite silicalite-1 manufactured in the present embodiment has more faintly acid positions.
The infrared curve of pyridine adsorption is located at 1450cm as shown in figure 5, in the infrared adsorption curve of pyridine-1Peak at left and right
It is adsorbed in the absorption peak that suction-operated occurs for Lewis acidic site corresponding to Pyridine Molecules, and in 1540cm-1Bronsted it is acid
There is not absorption peak in position, illustrates that the molecular sieve of the present embodiment only has L sour, does not have stronger B acid.But it can see
The peak of silicalite-1 is deviated compared to SBA-15 to lower wave number, may also indicate that it is acid slightly weak.
Embodiment 2
Use silester -40TEOS for silicon source, it is 1.5:1 with mass ratio that tetrapropylammonium hydroxide TPAOH, which is template,
Ratio TEOS is slowly added into the aqueous solution (mass concentration of tetrapropylammonium hydroxide be 25%) of TPAOH, in beaker
In, magnetic agitation 2h at room temperature.It is then transferred in stainless steel water heating kettle, isothermal reaction 48h under the conditions of 180 DEG C.Deionization
Water washing, filtering, 120 DEG C dry 12 hours.Further, by products therefrom place tube furnace in, in air atmosphere, with 2 DEG C/
The heating rate of min is warming up to 550 DEG C, keeps the temperature 6h.The SEM of molecular sieve obtained is as shown in Figure 2.Molecular sieve obtained is averaged
Partial size is 150nm, and the external surface area of molecular sieve is 500cm2/ g, mesoporous and macropore total volume are 0.36cm3/ g, micro pore volume
For 0.12cm3/g.It is 75nm that molecular sieve, which has the mesoporous and average pore size that the micropore that average pore size is 5 angstroms, average pore size are 4nm,
Macropore.
Embodiment 3
Using silester -28 (mass content of silica for 28%) TEOS is silicon source, tetrapropylammonium hydroxide
TPAOH is template, and TEOS is slowly added into aqueous solution (the tetrapropyl hydroxide of TPAOH by the ratio with mass ratio for 1:1.5
The mass concentration of ammonium be 25%) in, in beaker, magnetic agitation 2h at room temperature.Solution is transferred in stainless steel water heating kettle,
160 DEG C of isothermal reaction 48h.It is washed with deionized, filters later, dried 12 hours using 120 DEG C of vacuum oven.Into one
Step in air atmosphere, is warming up in gained sample putting tube formula furnace 550 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 6h,
Obtain porous grade silica zeolite silicalite-1.The average grain diameter of molecular sieve obtained is 250nm, and the outer of molecular sieve compares table
Area is 440cm2/ g, mesoporous and macropore total volume are 0.3cm3/ g, micro pore volume 0.15cm3/g.Molecular sieve has average hole
The macropore that the mesoporous and average pore size that micropore that diameter is 5 angstroms, average pore size are 3.5nm is 60nm.
Embodiment 4
Use silester -28TEOS for silicon source, (quality of tetrapropylammonium hydroxide is dense by tetrapropylammonium hydroxide TPAOH
TEOS is slowly added into the aqueous solution of TPAOH with mass ratio for the ratio of 1.5:1,25%) to be template in beaker by degree
In, magnetic agitation 2h at room temperature.It is then transferred in stainless steel water heating kettle, in 160 DEG C of isothermal reaction 48h.Deionization is used later
Water washing, filtering, uses the drying 12 hours of 120 DEG C of vacuum oven.Further, by gained sample putting tube formula furnace, in sky
In gas atmosphere, 550 DEG C are warming up to the heating rate of 2 DEG C/min, 6h is kept the temperature, obtains porous grade silica zeolite
silicalite-1.The average grain diameter of molecular sieve obtained is 250nm, and the external surface area of molecular sieve is 400cm2/ g, it is mesoporous
It is 0.32cm with macropore total volume3/ g, micro pore volume 0.12cm3/g.Molecular sieve has the micropore that average pore size is 5 angstroms, is averaged
The macropore that the mesoporous and average pore size that aperture is 3nm is 70nm.
Embodiment 5
Use silester -40TEOS for silicon source, (quality of tetrapropylammonium hydroxide is dense by tetrapropylammonium hydroxide TPAOH
TEOS is slowly added into the aqueous solution of TPAOH with mass ratio for the ratio of 1:2,25%) to be template in beaker by degree
In, magnetic agitation 2h at room temperature.It is then transferred in stainless steel water heating kettle, isothermal reaction 48h under the conditions of 180 DEG C.Deionization
Water washing, filtering, 120 DEG C dry 12 hours.Further, by products therefrom place tube furnace in, in air atmosphere, with 2 DEG C/
The heating rate of min is warming up to 550 DEG C, keeps the temperature 6h.The average grain diameter of molecular sieve obtained is 300nm, and the outer of molecular sieve compares table
Area is 400cm2/ g, mesoporous and macropore total volume are 0.5cm3/ g, micro pore volume 0.14cm3/g.Molecular sieve has average hole
The macropore that the mesoporous and average pore size that micropore that diameter is 5 angstroms, average pore size are 3nm is 60nm.
Embodiment 6
Identical as the preparation method of embodiment 5, difference is, the mass ratio of silicon source and structure directing agent is 1:0.1, system
The average grain diameter of the molecular sieve obtained is 150nm, and the external surface area of molecular sieve is 300cm2/ g, mesoporous and macropore total volume are
0.3cm3/ g, micro pore volume 0.05cm3/g.It is the mesoporous of 4nm that molecular sieve, which has the micropore that average pore size is 5 angstroms, average pore size,
The macropore for being 80nm with average pore size.
Embodiment 7
Identical as the preparation method of embodiment 5, difference is, the mass ratio of silicon source and structure directing agent is 1:5, is made
The average grain diameter of molecular sieve be 350nm, the external surface area of molecular sieve is 480cm2/ g, mesoporous and macropore total volume are
0.3cm3/ g, micro pore volume 0.2cm3/g.It is the mesoporous of 2nm that molecular sieve, which has the micropore that average pore size is 5 angstroms, average pore size,
The macropore for being 60nm with average pore size.
Comparative example 1
16.4gP123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) is dissolved in 120mL
In ionized water, then stirring is added the HCl that 320ml concentration is 2mol/L, stirs 1h, and 40.6g tetraethyl orthosilicate, heating is added dropwise
To 40 DEG C, stirring for 24 hours, temperature maintains 42 DEG C, after material is transferred in the rustless steel container with tetrafluoro liner with 2 DEG C/min
120 DEG C are risen to, crystallization for 24 hours, is filtered, washed, is dried, roasted and to obtain white powder SBA-15.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of multi-stage porous silica zeolite, comprising:
Silicon source is added into the aqueous solution of structure directing agent, silicon source is made to carry out hydrolyzing to be placed in reaction kettle for a period of time carrying out water
Thermal crystallisation reaction, obtains multi-stage porous silica zeolite for obtained product is post-treated.
2. preparation method according to claim 1, which is characterized in that the structure directing agent is tetrapropylammonium hydroxide
And/or 4-propyl bromide.
3. preparation method according to claim 1 or 2, which is characterized in that the silicon source be selected from silester, silica solution,
At least one of Silica hydrogel, methyl silicate and white carbon black, preferably silester -28, silester -32 and silester -40
At least one of.
4. preparation method according to any one of claim 1-3, which is characterized in that the silicon source and structure directing agent
Mass ratio is 1:(0.1-5).
5. preparation method described in any one of -4 according to claim 1, which is characterized in that the silicon source and structure directing agent
Mass ratio is 1:(0.5-2).
6. preparation method according to any one of claims 1-5, which is characterized in that the aqueous solution of the structure directing agent
Mass concentration be 10%-25%.
7. preparation method according to claim 1 to 6, which is characterized in that the hydrolysis carries out at room temperature,
The time of hydrolysis is 2-12h, preferably 2-3h.
8. preparation method described in any one of -7 according to claim 1, which is characterized in that hydrothermal crystallizing reacts item in reaction kettle
Part is 160-180 DEG C of temperature, time 12-60h.
9. a kind of multi-stage porous silica zeolite uses preparation method of any of claims 1-8 to be made, and described point
Son sieve include aperture be 2-15 angstroms micropore, aperture be 3-12 nanometers mesoporous and aperture be 50-100 nanometers macropore.
10. silica zeolite according to claim 9, which is characterized in that the partial size of the molecular sieve is 50-300nm, point
The external surface area of son sieve is 400-500cm2/ g, mesoporous and macropore total pore volume are 0.4-0.7cm3/ g, micro pore volume 0.1-
0.2cm3/ g has Lewis acidic site in the molecular sieve.
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Cited By (1)
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CN112007690A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102515193A (en) * | 2011-12-31 | 2012-06-27 | 中国天辰工程有限公司 | Synthetic method of siliceous molecular sieve |
CN106032278A (en) * | 2015-03-18 | 2016-10-19 | 中国石油大学(华东) | Preparation method of total-silicon molecular sieve Silicalite-1 having high hydrogen bond silicon hydroxyl content |
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- 2017-11-03 CN CN201711067698.9A patent/CN109748289A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102515193A (en) * | 2011-12-31 | 2012-06-27 | 中国天辰工程有限公司 | Synthetic method of siliceous molecular sieve |
CN106032278A (en) * | 2015-03-18 | 2016-10-19 | 中国石油大学(华东) | Preparation method of total-silicon molecular sieve Silicalite-1 having high hydrogen bond silicon hydroxyl content |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112007690A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction |
CN112007690B (en) * | 2019-05-31 | 2022-12-09 | 中国石油化工股份有限公司 | Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction |
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