CN114988430B - Synthesis method of nanorod ZSM-23 molecular sieve - Google Patents
Synthesis method of nanorod ZSM-23 molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 57
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002073 nanorod Substances 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000012452 mother liquor Substances 0.000 claims abstract description 8
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical group CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7046—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a synthesis method of a nanorod ZSM-23 molecular sieve, which comprises the following steps: sequentially placing sodium hydroxide, deionized water, an aluminum source, seed crystal mother liquor, a template agent and a silicon source into a hydrothermal reaction kettle, uniformly stirring, aging for 0.5-2 hours at room temperature, sealing the hydrothermal reaction kettle, placing into a reactor, stirring for 3-5 hours at 25 ℃, and crystallizing at a high speed at two sections of temperatures; washing, drying and roasting the hydrothermal crystallization product to obtain the nano rod-shaped ZSM-23 molecular sieve with high crystallinity. The average grain diameter of the synthesized nano rod-shaped ZSM-23 molecular sieve is not more than 300nm, and the specific surface area is larger; the operation is simple in the synthesis process, and the crystallization time is short; low cost, high yield and wide prospect of industrial production and application.
Description
Technical Field
The invention relates to preparation of a molecular sieve material, and in particular belongs to a synthesis method of a nanorod ZSM-23 molecular sieve.
Background
ZSM-23 molecular sieve having MTT topology is a typical high silica molecular sieve. The skeleton structure of the molecular sieve is composed of five-membered ring, six-membered ring and ten-membered ring, and a typical one-dimensional non-intersecting pore canal is formed, wherein the pore canal size is 0.56nm multiplied by 0.45nm and is slightly smaller than a ZSM-5 molecular sieve. Because of its special pore structure (size, dimensions, etc.) and acidity, it is widely used in industrial fields such as: plays a very critical role in the reactions such as catalysis, alkane isomerization and the like.
Templates used in the conventional synthesis method of ZSM-23 molecular sieve are N, N-dimethylformamide, pyrrolidine, diquat-7, diquat-12 and the like. The ZSM-23 molecular sieves of the patents CN 101613114B, US 4076482, US 4490342, US 5405596 and the like are synthesized by adopting different templates. The use of single or mixed templates in these patents has the disadvantages of high synthesis cost, long crystallization period, etc.; the problem of low crystallinity and serious wall sticking phenomenon often exists in the amplifying process; and no investigation of the grain size of the ZSM-23 molecular sieve has been made in these patents.
Compared to microscale molecular sieves, nanoscale molecular sieves have more surface active centers and short mass transfer pathways, such that they exhibit higher catalytic efficiency. Therefore, the research and application of the nano-scale molecular sieve become an important sign of technical progress in the catalysis field, and interest of scientific researchers is brought about.
In order to solve a plurality of problems in the synthesis process of the ZSM-23 molecular sieve and to explore the size of synthesized crystal grains, the isopropyl amine with relatively low price is used as a template agent to synthesize the ZSM-23 molecular sieve, and aims to synthesize the nanorod-shaped ZSM-23 molecular sieve with pure phase and high crystallinity, and further perform pilot scale-up research, thereby providing a suitable reference for industrial production.
Disclosure of Invention
The invention aims to provide a synthesis method of a nanorod ZSM-23 molecular sieve, which aims to solve the problems of low crystallinity and serious wall sticking phenomenon in the amplification process of the ZSM-23 molecular sieve.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for synthesizing a nanorod ZSM-23 molecular sieve comprises the following steps: sequentially placing sodium hydroxide, deionized water, an aluminum source, seed crystal mother liquor, a template agent and a silicon source into a hydrothermal reaction kettle, uniformly stirring, aging for 0.5-2 h at room temperature, sealing the hydrothermal reaction kettle, placing into a reactor, stirring for 3-5 h at 25 ℃, and crystallizing at high-speed stirring at two stages of temperature; washing, drying and roasting the hydrothermal crystallization product to obtain the nano rod-shaped ZSM-23 molecular sieve with high crystallinity;
the molar ratio of the silicon source to the aluminum source to the sodium hydroxide to the template agent to the water is 55-59:1:2-2.6:35-60:750-1100; wherein the silicon source, the aluminum source and the sodium hydroxide are oxidizedSiO (SiO) substance 2 、Al 2 O 3 、Na 2 An O meter;
the seed crystal mother liquor is micron-sized ZSM-23 molecular sieve mother liquor, and the addition amount is 0.4% -2% of the mass of silicon dioxide in the raw material silicon source. The preparation method of the seed crystal mother solution comprises the steps of carrying out hydrothermal crystallization for 12-64 h at the temperature of 80-110 ℃ and the rotating speed of 20-30 rpm under the conditions that the mol ratio of silica sol to aluminum sulfate to sodium hydroxide to N, N-dimethylformamide to water is 95-105:1:35-36:67-68:4300-4321, and washing and drying a hydrothermal crystallization product.
As preferable:
the silicon source is silica sol.
The aluminum source is at least one of sodium aluminate, pseudo-boehmite and aluminum sulfate octadeca-hydrate.
The template agent is isopropylamine.
The crystallization at two sections is carried out at a low temperature of 90-120 ℃ for 3-24 hours; the crystallization temperature is 170-200 ℃ and the crystallization time is 36-84 h at high temperature.
The rotating speed of the high-speed stirring is 200-300 rpm.
The roasting temperature is 400-550 ℃ and the roasting time is 6-12 h.
The washing is carried out by adopting deionized water.
The sodium hydroxide may be replaced with potassium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
1. the average grain diameter of the synthesized nano rod-shaped ZSM-23 molecular sieve is not more than 300nm, and the nano rod-shaped ZSM-23 molecular sieve has larger specific surface area. Compared with a micron-sized ZSM-23 molecular sieve, the catalyst has higher catalytic activity and selectivity.
2. The invention obtains the nano rod-shaped ZSM-23 molecular sieve with 100 percent of purity and more than 98 percent of crystallinity, and effectively solves the problems of low crystallinity and serious wall sticking phenomenon existing in the prior industrial production of the ZSM-23 molecular sieve.
3. The synthesis method of the nanorod ZSM-23 molecular sieve is simple to operate and short in crystallization time.
4. The synthesis method of the nanorod ZSM-23 molecular sieve under the dynamic condition has the advantages of low cost and high yield, and has wide prospect of industrial production and application.
Drawings
FIG. 1 is an XRD spectrum of ZSM-23 molecular sieve prepared in example 1.
FIG. 2 is an SEM spectrum of a ZSM-23 molecular sieve prepared according to example 1.
FIG. 3 is a diagram showing the non-sticking state of the ZSM-23 molecular sieve prepared in example 1 to the pot.
FIG. 4 is an XRD spectrum of the ZSM-23 molecular sieve prepared in comparative example 1.
FIG. 5 is an SEM spectrum of the ZSM-23 molecular sieve prepared according to comparative example 1.
FIG. 6 is a graph showing the state of sticking to the walls of a sieve of ZSM-23 prepared in comparative example 1.
FIG. 7 is an XRD spectrum of ZSM-23 molecular sieve prepared in comparative example 2.
FIG. 8 is an SEM image of a ZSM-23 molecular sieve prepared according to comparative example 2.
Detailed Description
The invention will be described in further detail with reference to the following examples for the purpose of better understanding of the present invention, but without limiting the invention thereto.
Example 1:
206g of distilled water, 8.2g of sodium metaaluminate, 2.9g of sodium hydroxide, 2.34g of self-made micron-sized ZSM-23 mother liquor and 164.1g of isopropylamine with the mass fraction of 70% are added into a 1000ml hydrothermal reaction kettle, evenly stirred, 390g of silica sol with the mass fraction of 30% is slowly added under the stirring state, then sealed and placed in a reactor with the mass fraction of 200 r/min. Stirring for 3h at 25 ℃, dynamically and hydrothermally crystallizing for 24h at 90 ℃ at low temperature, dynamically and hydrothermally crystallizing for 72h at 170 ℃ at high temperature, washing and drying a hydrothermally crystallized product, and roasting for 6h at 550 ℃ to synthesize the pure-phase nanorod ZSM-23 molecular sieve with high crystallinity. The molecular sieve obtained was measured to have a mass of 109.5g. The purity of the obtained molecular sieve is 100 percent, the crystallinity is as high as 98 percent, and the phenomenon of wall sticking is avoided. The XRD pattern, SEM pattern and kettle non-sticking state of the sample are shown in figures 1, 2 and 3.
Example 2:
344g of distilled water, 4.5g of pseudo-boehmite, 6.5g of sodium hydroxide, 1.9g of self-made micron-sized ZSM-23 mother solution and 118.5g of isopropylamine with the mass fraction of 70% are added into a 1000ml hydrothermal reaction kettle, and are stirred uniformly, 390g of silica sol with the mass fraction of 30% is slowly added in a stirring state, the hydrothermal reaction kettle is sealed, and is stirred for 4 hours at 25 ℃, then is dynamically and hydrothermally crystallized for 10 hours at a low temperature of 110 ℃, then is dynamically and hydrothermally crystallized for 60 hours at a high temperature of 180 ℃, and the hydrothermally crystallized product is washed and dried and then is baked for 8 hours at 500 ℃, so that the nanorod ZSM-23 molecular sieve with the crystallinity of up to 95% is obtained. The mass of the molecular sieve obtained was measured to be 101.1g.
Example 3:
180g of distilled water, 26.9g of aluminum sulfate octadecanoate, 8.6g of sodium hydroxide, 2.8g of self-made micron-sized ZSM-23 mother solution and 120g of isopropylamine with the mass fraction of 70% are added into a 1000ml hydrothermal reaction kettle, and are stirred uniformly, 468g of silica sol with the mass fraction of 30% is slowly added under the stirring state, the hydrothermal reaction kettle is sealed, and is stirred for 5 hours at 25 ℃, dynamically and hydrothermally crystallized for 3 hours at low temperature of 120 ℃, dynamically and hydrothermally crystallized for 36 hours at high temperature of 200 ℃, and the hydrothermally crystallized product is washed and dried and then baked for 12 hours at 400 ℃, so that the nanorod ZSM-23 molecular sieve with the crystallinity of up to 90% is synthesized. The mass of the molecular sieve obtained was measured to be 100g.
Comparative example 1:
exactly the same conditions and operating procedures as in example 1 were used, except that: the crystallinity of the obtained nano rod-shaped ZSM-23 molecular sieve is lower than 40 percent, the nano rod-shaped ZSM-23 molecular sieve has mixed crystals, the purity is lower than 30 percent and the wall sticking phenomenon is serious when the water addition amount and the rotating speed are 128g and 180 rpm. The XRD pattern, SEM pattern and kettle sticking state of the sample are shown in FIG. 4, FIG. 5 and FIG. 6.
Comparative example 2:
exactly the same conditions and operating procedures as in example 1 were used, except that: the adding amount of isopropylamine, namely 190g of isopropylamine with the mass fraction of 70 percent is added, and the crystallinity of the obtained nano rod-shaped ZSM-23 molecular sieve is lower than 75 percent, has mixed crystals and has the purity lower than 60 percent. The XRD pattern and SEM pattern of the sample are shown in FIG. 7 and FIG. 8.
While the invention has been described with reference to specific embodiments, those skilled in the art will recognize that the invention is not limited to the embodiments, but can be practiced with modification and alteration without departing from the spirit and scope of the appended claims.
Claims (6)
1. The synthesis method of the nanorod ZSM-23 molecular sieve is characterized by comprising the following steps of: sequentially placing sodium hydroxide, deionized water, an aluminum source, seed crystal mother liquor, a template agent and a silicon source into a hydrothermal reaction kettle, uniformly stirring, aging for 0.5-2 hours at room temperature, sealing the hydrothermal reaction kettle, placing into a reactor, stirring for 3-5 hours at 25 ℃, and crystallizing at a high speed at two stages of temperatures; washing, drying and roasting the hydrothermal crystallization product to obtain the nano rod-shaped ZSM-23 molecular sieve with high crystallinity;
the molar ratio of the silicon source to the aluminum source to the sodium hydroxide to the template agent to the water is 55-59:1:2-2.6:35-60:750-1100; wherein, the silicon source, the aluminum source and the sodium hydroxide are prepared according to oxide SiO 2 、 Al 2 O 3 、 Na 2 An O meter;
the seed crystal mother liquor is micron-sized ZSM-23 molecular sieve mother liquor, and the addition amount is 0.4% -2% of the mass of silicon dioxide in the raw material silicon source;
the crystallization at the two sections is carried out at a low temperature of 90-120 ℃ for 3-24 hours; the crystallization temperature is 170-200 ℃ at high temperature, and the crystallization time is 36-84 h;
the rotating speed of the high-speed stirring is 200-300 rpm;
the template agent is isopropylamine.
2. The method for synthesizing the nanorod-shaped ZSM-23 molecular sieve according to claim 1, wherein the silicon source is silica sol.
3. The method for synthesizing the nanorod-shaped ZSM-23 molecular sieve according to claim 1, wherein the aluminum source is at least one of sodium aluminate, pseudo-boehmite and aluminum sulfate octadeca hydrate.
4. The method for synthesizing the nanorod-shaped ZSM-23 molecular sieve according to claim 1, wherein the sodium hydroxide is replaced by potassium hydroxide.
5. The method for synthesizing the nanorod ZSM-23 molecular sieve according to claim 1, wherein the preparation method of the seed crystal mother solution comprises the steps of carrying out hydrothermal crystallization for 12-64 h at the temperature of 80-110 ℃ and the rotation speed of 20-30 rpm under the conditions that the mole ratio of silica sol, aluminum sulfate, sodium hydroxide, N-dimethylformamide to water is 95-105:1:35-36:67-68:4300-4321, and washing and drying a hydrothermal crystallization product.
6. The method for synthesizing the nanorod-shaped ZSM-23 molecular sieve according to claim 1, wherein the roasting temperature is 400-550 ℃ and the roasting time is 6-12 h.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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