CN109694085A - The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet - Google Patents
The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet Download PDFInfo
- Publication number
- CN109694085A CN109694085A CN201710982567.7A CN201710982567A CN109694085A CN 109694085 A CN109694085 A CN 109694085A CN 201710982567 A CN201710982567 A CN 201710982567A CN 109694085 A CN109694085 A CN 109694085A
- Authority
- CN
- China
- Prior art keywords
- nanometer sheet
- zsm
- template
- ammonium type
- type zsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to the Template-free method synthetic methods of ammonium type ZSM-5 nanometer sheet, if mainly solving in previous nano-ZSM-5 molecular sieve synthesis process without using organic formwork agent or inorganic base, salt containing alkali or alkaline earth metal, it is difficult to obtain flake nano ZSM-5, post-processing needs to exchange by 2~3 nitroxylic acid ammoniums, material consumption the problems such as energy consumption is high.The present invention is with using a kind of new method of synthesis ammonium type ZSM-5 nanometer sheet molecular sieve, and without introducing alkali or alkaline earth metal ion during this, the small molecule alkali pollution used is few, small toxicity, not will cause serious environmental protection pressure.It can be used in the industrial production of ammonium type ZSM-5 nanometer sheet.
Description
Technical field
The present invention relates to a kind of Template-free method synthetic methods of ammonium type ZSM-5 nanometer sheet.
Background technique
The molecular sieve of industrial conventional method synthesis used, crystalline size are generally higher than 1 μm.This molecular sieve crystal
In, 400~1000 molecular sieve structure cells are contained in one-dimensional square.The molecular sieve prepared using improved method, general crystal can
Up to 0.1~1 μm of submicrometer scale, and the then more difficult synthesis of nano molecular sieve of the grain size less than 0.1 μm.The particle of molecular sieve
After granularity drops to nanoscale from micron order, certain physicochemical properties, such as catalytic performance, thermal stability and reactivity worth all can
It changes a lot, to have different properties.
In general, molecular sieve be by silica-alumina gel the regular hour and at a temperature of synthesized using hydro-thermal process.It is all
As mixing speed, crystal seed, crystallization temperature, gel composition, pH value, silica alumina ratio and template concentrations these parameters can control crystalline substance
The size of grain.
The dispersing agents such as electrolyte such as NaOH, NaCl are adsorbed in particle surface, on the one hand improve particle surface current potential significantly
Absolute value, to generate strong electric double layer electrostatic repulsion simultaneously, electrolyte can also enhance wetting of the particle surface to water
The granularity of nano zeolite can be effectively controlled to be effectively prevented the reunion of particle in water in degree.ZSM-5 nanometers of boilings of synthesis
Shi Shi, the content for increasing NaCl can make crystal grain be reduced to the left and right 70nm (XRD).When synthesizing ZSM-5 nano zeolite, in system
Appropriate NaCl, which is added, can make crystal grain drop to the left and right 60nm (TEM).Further result of study shows that the addition of common salt is to crystallization
Speed and grain form also have a significant effect, and suitable sodium chloride, which is added, can not only accelerate crystallization process, moreover it is possible to inhibit crystal grain long
Greatly.Expect that little crystal grain will control the ratio of sodium chloride and aluminium chloride between 30~60, cannot all be obtained higher or lower than 15
To the ultra micro crystal grain of ZSM-5 molecular sieve.
In nano-sized ZSM-5 zeolite synthesis, homogeneous and transparent colloidal sol in order to obtain, mostly using tetrapropylammonium hydroxide as alkali
Source, ethyl orthosilicate are silicon source, and the presence of alkali metal ion will make silicon-aluminum sol unstable and assemble in the system.Cause
This must be synthesized under the conditions of alkali free metal ion.In the case where supersaturated plastic matches hydrothermal condition (443K) synthesized 10~
The ZSM-5 zeolite of 100nm (TEM), and carried out system research to synthesis factor is influenced, discovery using aluminium isopropoxide as silicon source, compared with
Long ageing time, higher basicity and lower sodium content is conducive to the formation of little crystal grain zeolite；And the presence of sodium ion
It then reduces the crystallization velocity of ZSM-5 zeolite, crystal grain is caused to significantly increase.Low temperature (373K) system of alkali free metal ion is unfavorable
Enter zeolite skeleton in aluminium, it can only synthesizing high-silicon or pure silicon molecular sieve (silicalite-1) in organic formwork agent presence.
In previous report, NaOH, NaCl or KCl etc. are generallyd use as basicity and adjusts reagent or mineralizer, these
Method synthesis nano-ZSM-5 is relatively easy to, but the processing of filtering waste liquid and the exchange of molecular sieve can bring environmental issue, synthesize
Increased costs.
Nano pure silicone ZSM-5 (silicalite-1) synthesis is relatively simple, but generally under TEOS and TPA template environment
(102602959 B of CN) could be synthesized.In addition, using TPAOH or TPABr as template be also synthesis nano-ZSM-5
Main means.CN 105668586A uses TPAOH as point of template synthesis 50-200nm using segmentation crystallization method
Son sieve；Template is used in combination in 105712378 A of CN and surfactant achievees the purpose that reduce molecular sieve partial size.CN
103787367 A prepare nano molecular sieve formed body using template and crystal seed；102502696 A of CN uses acid, alkali, organic
Amine prepares nano molecular sieve；105565340 A of CN also uses TPAOH to synthesize nano molecular sieve as template；CN
102001680 B and 101643219 B of CN use NaOH to replace organic formwork agent as alkali source, but part in strong basicity environment
Molecular sieve dissolution, causes molecular sieve yield to decline, while needing to carry out ion exchange removing sodium processing.
Adding crystal seed is also one of the effective ways for synthesizing nano molecular sieve, but uses TPAOH or Na ionic complexes system (CN
102874843 B of 102666385 A, CN 101983921 A, CN), these can cause molecular sieve yield to decline.
104525246 A of CN 104085899 A and CN synthesizes nano-ZSM-5 using Template-free method, without crystal seed system,
But there must be NaOH component to promote crystallization, the sodium form molecular sieve of synthesis will divide during this by that could use except sodium processing
Son sieve has a certain amount of loss.
Summary of the invention
It is big the technical problem to be solved by the present invention is to not used in nano-ZSM-5 molecular sieve synthesis process in the prior art
The inorganic base of molecule organic formwork agent or alkali metal containing or alkaline-earth metal, salt, it is difficult to obtain flake nano ZSM-5, post-processing needs
It to be exchanged by 2~3 nitroxylic acid ammoniums, material consumption the problems such as energy consumption is high.Using a kind of side of new synthesis ammonium type ZSM-5 nanometer sheet
Method, without introducing alkali or alkaline earth metal ion during this, the small molecule alkali pollution used is few, small toxicity, not will cause
Serious environmental protection pressure.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet, comprising the following steps: a) silicon source, water are dissolved, added
Enter the small molecule alkali M1 that carbon atoms number is 0-3, forms solution A；B) after mixing by silicon source, water, add solution A, finish
ZSM-5 crystal seed is added afterwards；C) the small molecule alkali M2 that carbon atoms number is 0-3 is added again into above-mentioned alkaline Synthesis liquid, most
The mol ratio of whole Synthesis liquid are as follows: H2O/SiO2=3~150, SiO2/Al2O3=20~∞, (M1+M2)/SiO2=0.2~5；
D) by above-mentioned mixed solution crystallization；E) it is filtered, washed, dried after crystallization, obtain ammonium type ZSM-5 nanometer sheet.
In the above-mentioned technical solutions, it is preferable that the carbon atoms number of small molecule alkali M1, M2 are 0,1 or 2.
In the above-mentioned technical solutions, it is preferable that (M1+M2)/SiO2=0.2-1.
In the above-mentioned technical solutions, it is preferable that in step a), be added the small molecule alkali M1's that carbon atoms number is 0-3
Amount is M1/SiO2=0.05-1.
In the above-mentioned technical solutions, it is preferable that in step c), be added the small molecule alkali M2's that carbon atoms number is 0-3
Amount is M2/SiO2=0.15~4.
In the above-mentioned technical solutions, it is preferable that crystallization temperature is 100~200 DEG C, and crystallization time is 0.5~240 hour.
It is further preferable that 130-180 DEG C, 24-72h hours.
In the above-mentioned technical solutions, silicon source is in silica, silica solution, white carbon black, ethyl orthosilicate or atlapulgite
At least one.
In the above-mentioned technical solutions, silicon source is selected from aluminium isopropoxide, aluminium oxide, aluminium hydroxide, metallic aluminium, Aluminum sol, sulfuric acid
At least one of aluminium, aluminum nitrate or aluminium chloride.It is more in previous literature in order to synthesize the preferable ammonium type nano-ZSM-5 of pattern
Using aluminium isopropoxide (AIP), although Product size is smaller, yield is not high, is generally not more than 50% and cost of material is high, uses
A large amount of organic formwork agents, pressure is higher in synthesis process, and there are certain risks.
In the above-mentioned technical solutions, molecular sieve alkali M1, M2 that carbon atoms number is 0-3 are selected from ethamine, diethylamine, second
At least one of diamines, triethylamine, ammonium hydroxide, urea, n-propylamine.
In the above-mentioned technical solutions, the additional amount of ZSM-5 crystal seed is the 0.5%~5% of Synthesis liquid weight；More preferably
Ground, the additional amount of ZSM-5 crystal seed are the 1%~2% of Synthesis liquid weight.
Alkali or alkaline earth metal ion is not contained in molecular sieve product；Amount of solid after roasting is that amount of solid is added
90% or more.
The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet of the present invention in synthesis process, first will using small molecule alkali
Part small molecule alkali is mixed with silicon source, adds crystal seed, adds part small molecule alkali after crystal seed is added, nano-sheet can be obtained
ZSM-5 molecular sieve.The technical program uses common inorganic raw material, does not use alkali or alkaline earth metal, does not need subsequent friendship
Processing is changed, replaces organic formwork agent using small molecule alkali, small molecule alkali small toxicity is readily volatilized, and processing is simple, can save a large amount of
Production cost reaches high income, at low cost, environmentally friendly purpose.
Detailed description of the invention
Fig. 1 is the XRD spectra of product in embodiment 5；
Fig. 2 is the SEM spectrogram of product in embodiment 5.
The present invention will be further described below by way of examples, but the present invention is not limited thereto.
Specific embodiment
In embodiment, raw materials used in synthesis is chemical pure level reagent.
[embodiment 1]
At solution A after 2 grams of aluminum nitrates, 5 grams of ethamine (M1) and 30 grams of water stirring and dissolvings, 40 grams of tetraethyl orthosilicates and 50 grams
5 hours are stirred at room temperature after deionized water mixing into solution B, solution B is slowly added to solution A, strong stirring 2 hours, is added
It is stirred 1 hour after 1wt%ZSM-5 crystal seed, 15 grams of ammonium hydroxide (M2) are added, and this mixed system moves into stainless steel crystallizing kettle afterwards, and 150
DEG C crystallization 72 hours.The XRD spectrum of gained sample has the characteristic diffraction peak of ZSM-5 zeolite molecular sieve, sheet in SEM figure
Molecular sieve thickness is about 80nm.Product SiO2/Al2O3Molar ratio is 63, Na+Content is 0.02%, and molecular sieve yield is 96%.
[embodiment 2]
At solution A, 50 grams of silica solution (40%) after 1.5 grams of aluminum sulfate, 2 grams of diethylamine (M1) and 30 grams of water stirring and dissolvings
It is stirred at room temperature 0.5 hour after being mixed with 10 grams of deionized waters and is slowly added in solution A at solution B, by solution B, strong stirring 2 is small
When, it is stirred 1 hour after 2wt%ZSM-5 crystal seed is added, this mixed system moves into stainless steel crystalline substance after 5 grams of ethamine (M2) solution are added
Change kettle in, 170 DEG C crystallization 24 hours.The XRD spectrum of gained sample has the characteristic diffraction peak of ZSM-5 zeolite molecular sieve,
Sheet molecular sieve thickness is about 50nm in SEM figure.Product SiO2/Al2O3Molar ratio is 147, Na+Content is 0.01%, molecular sieve
Yield is 98%
[embodiment 3]
At solution A after 5 grams of aluminum nitrates, 2 grams of ethylenediamines (M1) and 30 grams of deionized water stirring and dissolvings, 40 grams of white carbon blacks are added
50 grams of water continue to be uniformly mixing to obtain solution B, and solution B is slowly added in solution A, and strong stirring 2 hours, 0.5wt% is added
It is stirred 1 hour after ZSM-5 crystal seed, is eventually adding 8 grams of ammonium hydroxide (M2) and is uniformly mixed, move into stainless steel crystallizing kettle, 130 DEG C of crystalline substances
Change 72 hours.The XRD spectrum of gained sample has the characteristic diffraction peak of ZSM-5 zeolite molecular sieve, sheet molecule in SEM figure
Sieving thickness is about 30nm.Product SiO2/Al2O3Molar ratio is 98, Na+Content is 0.01%, and molecular sieve yield is 97%
[embodiment 4]
0.31 gram of aluminium hydroxide, 20 grams of ammonium hydroxide (M1) and the formation of 50 grams of deionized waters sealing stirring and dissolving 1 hour A, 104
Gram silica solution (40%) and 32 grams of deionized waters mixing, solution B are slowly added in solution A, strong stirring 2 hours, are added
It stirring 1 hour after 1wt%ZSM-5 crystal seed, this mixed system moves into stainless steel crystallizing kettle after 16 grams of ammonium hydroxide (M2) solution are added,
170 DEG C crystallization 12 hours.The XRD map of gained sample has the characteristic diffraction peak of ZSM-5 zeolite molecular sieve, in SEM figure
Sheet molecular sieve thickness is about 100nm.Product SiO2/Al2O3Molar ratio is 350, Na+Content is 0.02%, molecular sieve yield
It is 99%.
[embodiment 5]
1.5 grams of Aluminum sols (30%), 3 grams of n-propylamines (M1) and 32 grams of deionized water stirring and dissolvings formation solution As, 25 grams
Tetraethyl orthosilicate and 20 grams of deionized water mixing, are stirred at room temperature 5 hours formation solution Bs, solution B are slowly added in solution A,
It strong stirring 2 hours, is stirred 1 hour after 5wt%ZSM-5 crystal seed is added, is eventually adding 20 grams of diethylamine (M2) and is uniformly mixed,
Move into stainless steel crystallizing kettle in, 180 DEG C crystallization 36 hours.The XRD spectrum of gained sample has ZSM-5 zeolite molecular sieve
Characteristic diffraction peak, sheet molecular sieve thickness is about 120nm in SEM figure.Product SiO2/Al2O3Molar ratio is 24, Na+Content
It is 0.01%, molecular sieve yield is 93%.
[comparative example 1]
It is formulated according to document [Chem.Mater.2005,17,2494-2513],
9TPAOH:0.16Na2O:1Al2O3:50Si:300-495H2O:0/100EtOH (S), at 165 DEG C crystallization for 24 hours,
The product obtained after being filtered, washed is spherical shape ZSM-5, and particle size 50nm, molecular sieve yield is only 60%, to obtain Hydrogen
Molecular sieve is also needed through multiple steps such as peracid friendship, ammonium friendships, and ultimate yield is 45% or so, a large amount of loss of material.
[comparative example 2]
Using the method for 104525246 A of patent CN, 1g aluminum nitrate and 25ml 1mol/L sodium hydroxide solution are mixed
Stirring.Add 20g silica solution, moved into stainless steel crystallizing kettle after stirring 10h, 170 DEG C crystallization 48 hours, crystallization product is
3~5 μm of partial size of cylindric ZSM-5, rather than nano molecular sieve.
[comparative example 3]
Using the method for 104085899 A of patent CN, 4KgNaOH, 1.64KgNaAlO2 are dissolved in 1.46L deionization
In water, 83.8L silica solution is added, stir crystallization after aging 12h, 130 DEG C of first crystallization 0.5h, 170 DEG C of crystallization 9h again, filtering,
The ball particle that the small-grain ZSM-5 wash, being dried to obtain is 0.5 μm, molecular sieve yield are 75%；It is handed over by ammonium nitrate solution
The ammonium type ZSM-5 molecular sieve yield obtained after changing drops to 60%.
[comparative example 4]
Experimentation is only added without 1wt%ZSM-5 crystal seed, after crystallization, washing, drying with embodiment 1 during plastic
The XRD spectra of product be it is amorphous, SEM spectrogram be irregular particle.
[comparative example 5]
Experimentation only forms solution A and is added without ethamine in the process, before moving into stainless steel crystallizing kettle with embodiment 1
Be added 20 grams of ammonium hydroxide, crystallization, washing, dried product exhibited XRD spectra be ZSM-5, product SiO2/Al2O3Molar ratio is also 63,
But nanometer sheet and nanometer spherical particle coexist in SEM spectrogram.
[comparative example 6]
0.2wt%ZSM-5 crystal seed, crystallization, washing, drying is only added with embodiment 1 in experimentation during plastic
The XRD spectra of product is ZSM-5 afterwards, but diffraction peak intensity is not high；Nanometer sheet and irregular spherical particle coexist in SEM spectrogram,
Illustrate with the presence of amorphous substance；Roasting weighing results show that molecular sieve yield is 67%.
Claims (10)
1. a kind of Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet, comprising the following steps:
A) silicon source, water are dissolved, the small molecule alkali M1 that carbon atoms number is 0-3 is added, forms solution A；
B) after mixing by silicon source, water, add solution A, after be added ZSM-5 crystal seed；
C) the small molecule alkali M2 that carbon atoms number is 0-3 is added again into above-mentioned alkaline Synthesis liquid, final Synthesis liquid is rubbed
You match are as follows: H2O/SiO2=3~150, SiO2/Al2O3=20~∞, (M1+M2)/SiO2=0.2~5；
D) by above-mentioned mixed solution crystallization；
E) it is filtered, washed, dried after crystallization, obtain ammonium type ZSM-5 nanometer sheet.
2. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, it is characterised in that silicon source is selected from
Aluminium isopropoxide, at least one of aluminium oxide, aluminium hydroxide, metallic aluminium, Aluminum sol, aluminum sulfate, aluminum nitrate or aluminium chloride.
3. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, it is characterised in that silicon source is selected from
At least one of silica, silica solution, white carbon black, ethyl orthosilicate or atlapulgite.
4. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, it is characterised in that ZSM-5 is brilliant
The additional amount of kind is the 0.5%~5% of Synthesis liquid weight.
5. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, it is characterised in that carbon atoms
Number be 0-3 molecular sieve alkali include in ethamine, diethylamine, ethylenediamine, triethylamine, ammonium hydroxide, urea, n-propylamine extremely
Few one kind.
6. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, it is characterised in that step e) is produced
Alkali or alkaline earth metal ion is not contained in object.
7. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, it is characterised in that step e) is produced
Amount of solid after object roasting is 90% or more that amount of solid is added.
8. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, which is characterized in that step d)
In, crystallization temperature is 100~200 DEG C, and crystallization time is 0.5~240 hour.
9. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, which is characterized in that step a)
In, the amount that the small molecule alkali M1 that carbon atoms number is 0-3 is added is M1/SiO2=0.05-1.
10. the Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet according to claim 1, which is characterized in that step c)
In, the amount that the small molecule alkali M2 that carbon atoms number is 0-3 is added is M2/SiO2=0.15~4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710982567.7A CN109694085B (en) | 2017-10-20 | 2017-10-20 | Template-free synthesis method of ammonium type ZSM-5 nanosheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710982567.7A CN109694085B (en) | 2017-10-20 | 2017-10-20 | Template-free synthesis method of ammonium type ZSM-5 nanosheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109694085A true CN109694085A (en) | 2019-04-30 |
| CN109694085B CN109694085B (en) | 2021-05-11 |
Family
ID=66226382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710982567.7A Active CN109694085B (en) | 2017-10-20 | 2017-10-20 | Template-free synthesis method of ammonium type ZSM-5 nanosheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109694085B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028175A (en) * | 2022-06-10 | 2022-09-09 | 太原理工大学 | Preparation method of lamellar ZSM-5 molecular sieve |
| CN115340104A (en) * | 2022-08-22 | 2022-11-15 | 淮安六元环新材料有限公司 | Method for synthesizing all-silicon ZSM-5 zeolite molecular sieve by using crystal seed-oriented sodium-free method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175114A (en) * | 1973-12-13 | 1979-11-20 | Mobil Oil Corporation | Method for producing zeolites |
| US20020037805A1 (en) * | 2000-03-24 | 2002-03-28 | Timken Hye Kyung C. | Production of alkylated aromatic compounds using dealuminated catalysts |
| CN102897790A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Synthesis method for ZSM-5 molecular sieve |
| CN103086399A (en) * | 2011-10-31 | 2013-05-08 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
| CN104261427A (en) * | 2014-09-29 | 2015-01-07 | 吉林大学 | Preparation method of house-of-cards-like hierarchical porous ZSM-5 molecular sieve |
| CN104843740A (en) * | 2014-02-13 | 2015-08-19 | 中国科学院过程工程研究所 | ZSM-5 molecular sieve and preparation method thereof |
| CN105600804A (en) * | 2015-12-25 | 2016-05-25 | 宁夏大学 | Method for directly preparing HZSM-5 molecular sieve and molding HZSM-5 molecular sieve |
-
2017
- 2017-10-20 CN CN201710982567.7A patent/CN109694085B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175114A (en) * | 1973-12-13 | 1979-11-20 | Mobil Oil Corporation | Method for producing zeolites |
| US20020037805A1 (en) * | 2000-03-24 | 2002-03-28 | Timken Hye Kyung C. | Production of alkylated aromatic compounds using dealuminated catalysts |
| CN102897790A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Synthesis method for ZSM-5 molecular sieve |
| CN103086399A (en) * | 2011-10-31 | 2013-05-08 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
| CN104843740A (en) * | 2014-02-13 | 2015-08-19 | 中国科学院过程工程研究所 | ZSM-5 molecular sieve and preparation method thereof |
| CN104261427A (en) * | 2014-09-29 | 2015-01-07 | 吉林大学 | Preparation method of house-of-cards-like hierarchical porous ZSM-5 molecular sieve |
| CN105600804A (en) * | 2015-12-25 | 2016-05-25 | 宁夏大学 | Method for directly preparing HZSM-5 molecular sieve and molding HZSM-5 molecular sieve |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028175A (en) * | 2022-06-10 | 2022-09-09 | 太原理工大学 | Preparation method of lamellar ZSM-5 molecular sieve |
| CN115028175B (en) * | 2022-06-10 | 2023-08-08 | 太原理工大学 | Preparation method of lamellar ZSM-5 molecular sieve |
| CN115340104A (en) * | 2022-08-22 | 2022-11-15 | 淮安六元环新材料有限公司 | Method for synthesizing all-silicon ZSM-5 zeolite molecular sieve by using crystal seed-oriented sodium-free method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109694085B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tabatabaei et al. | Experimental study of the synthesis and characterisation of silica nanoparticles via the sol-gel method | |
| CN110975795A (en) | Synthesis method of lithium extraction adsorbent | |
| CN102408120B (en) | Method for preparing high-purity ultrafine lithium-carbonate micro powder | |
| CN104556176B (en) | A kind of preparation method of aluminum oxide nanoparticle | |
| Zhang et al. | Hydrothermal synthesis, influencing factors and excellent photocatalytic performance of novel nanoparticle-assembled Bi 25 FeO 40 tetrahedrons | |
| CN105148950A (en) | Preparing method for flower-shaped BiOI microspheres | |
| CN112357955B (en) | Method for preparing titanium dioxide powder with different morphologies by solid phase method | |
| CN109694085A (en) | The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet | |
| CN107162047A (en) | A kind of preparation method of titanium dioxide hollow ball | |
| CN108928834A (en) | MCM-41 mesopore molecular sieve and its preparation method and application | |
| CN109485062A (en) | A kind of low temperature preparation method of lithium slag base NaA molecular sieve | |
| CN102795664A (en) | Preparation method of mesoporous titanium dioxide microballoons with controllable particle size | |
| CN105776253B (en) | A kind of method that utilization kaliophilite powder prepares potassium nitrate and nano-kaolinite | |
| CN105621449A (en) | NaY type molecular sieve and preparation method thereof | |
| CN101774533A (en) | Preparation method for gamma-alumina nanotube with prior exposure of (111) face | |
| CN107344721A (en) | A kind of Modified Zeolite Y and its preparation method and application | |
| CN102181929A (en) | Process for synthesizing TiO2 mesoporous single crystals | |
| Chen et al. | Morphology control of rutile TiO2 with tunable bandgap by preformed β-FeOOH nanoparticles | |
| CN100534904C (en) | Method for preparing nano Al2O3 adopting salt-melting calcination process | |
| CN1948167A (en) | Synthesis method of cobaltosic oxide nano-tube | |
| CN107840349A (en) | The preparation method of the nanometer multi-stage porous aggregations of ZSM 5 | |
| CN105271287A (en) | Method for preparation of Beta molecular sieve from modified diatomite without organic template | |
| CN109692704A (en) | Aromatic hydrocarbons methylation catalyst and preparation method thereof | |
| CN100512960C (en) | Method for preparing modified MCM-41/aluminium oxide composite carrier | |
| CN104310424B (en) | A kind of preparation method of Al-MCM-41 mesopore molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |